Anal. Chem.

1998, 70, 119R-177R

Infrared Spectroscopy
Marianne L. McKelvy,*,† Thomas R. Britt,† Bradley L. Davis,† J. Kevin Gillie,*,‡ Felicia B. Graves,† and
L. Alice Lentz†

Analytical Sciences Laboratory, The Dow Chemical Company, U.S.A., Midland, Michigan 48667, and
Applied Extrusion Technologies, 15 Reads Way, Newcastle, Delaware 19720

Review Contents bands, the infrared spectrum, may be used to characterize the
Overview of Analytical Infrared Spectroscopy 119R material. Infrared spectral information may be used to identify
Books and Reviews 119R the presence and amount of a particular compound in a mixture.
Databases, Software, and Algorithms 120R Different classes of chemical compounds contain structural
Infrared Accessories and Sampling Techniques 122R units that absorb infrared radiation at essential similar frequencies
Quantitative Analysis 122R and intensities within that class of compound. These bands are
Spectra-Structure Correlation 124R called “group frequencies”. The infrared spectroscopist uses
Hypenated Techniques 125R knowledge of these group frequencies to predict the structures
Time-Resolved Infrared Spectroscopy 126R
of unknown molecules when standard infrared spectra are not
Reflectance Techniques 127R
available. Sample collection and presentation accessories exist
Single-Crystal and Bulk Analysis Applications 127R
Thin-Film Applications 127R which allow the analyst to collect spectra as solids, liquids, and
Interfacial Applications 128R vapors and in solution, at various temperatures, and while
Adsorption and Surface Reaction Applications 128R undergoing mechanical deformation. Experiments conducted
Attenuated Total Reflectance 129R under such conditions assist the spectroscopist in the determi-
Diffuse Reflectance 130R nation of the structures of molecules in different phases as well
Emission 130R as structure-property relationships of materials.
Process and in Situ Analysis 131R Modern instrumentation allows the collection of infrared
Environmental Analysis 139R
spectra of materials at low-picogram levels. The ability of infrared
Carbon and Carbon Complexes 141R
spectroscopy to examine and identify materials under such a wide
Chemical Reactions/Organic Chemistry 142R
variety of conditions has earned this technique the premier
Hydrogen-Bonding Studies 142R
Catalysis Studies 143R position as the “work horse” of analytical science.
Solvent/Matrix Effects 143R
Organic Reactions/Characterization 144R BOOKS AND REVIEWS
Food and Agriculture 144R A compilation of IR and Raman spectra of inorganic compounds
Biochemistry 146R was published (A1). A book regarding infrared spectroscopy of
Literature Cited 157R biomolecules provided a comprehensive review of this area (A2).
This work contains references to studies of protein structures,
This review covers the published literature for the period nucleic acids, ultrafast spectroscopy, lipids, enzymes, and cell
November 1995 to October 1997 on aspects of infrared spectros- surface polysaccharides. A textbook prepared as an instructional
copy that are relevant to chemical analysis. Our review is directed aid in the study of vibrational spectroscopy was presented (A3).
to papers written in English or in certain aspects of IR spectros- A book detailing applications of infrared spectroscopy in electro-
copy that are of particular interest to one or more of the coauthors. chemistry was published (A4). Computerized applications of
Where some overlap may occur in a particular area, a few selected infrared spectroscopy, such as data manipulation, databases,
references to Raman or FT-Raman spectroscopy are included. multivariate techniques, and spectrometer networking, were
detailed (A5).
OVERVIEW OF ANALYTICAL INFRARED Internet sites that deal with infrared spectroscopy and instruc-
SPECTROSCOPY
tional issues were listed (A6). Group frequency assignments for
Infrared radiation is commonly defined as electromagnetic
the major bands in 20 common polymers were compiled (A7).
radiation with frequencies between 14 300 and 20 cm-1 (0.7 and
Methods for obtaining characteristic group frequencies were
500 µm). When a normal molecular motion such as a vibration,
reviewed (A8). Resources and references for interpretation of
rotation, rotation/vibration, or lattice mode or a combination,
difference, or overtone of these normal vibrations results in a spectra were discussed (A9, A10).
change in the molecule’s dipole moment, a molecule absorbs Several general reviews of vibrational spectroscopy were
infrared radiation in this region of the electromagnetic spectrum. presented (A11-A13). The application of far-IR spectroscopy was
The corresponding frequencies and intensities of these infrared reviewed (A14). The infrared spectroscopy of radicals was
reviewed (A15). The role of step-scanning interferometers was
†
The Dow Chemical Co. reviewed by several authors for the study of polymeric systems
‡
Applied Extrusion Technologies. (A16, A17) and for transition metal complexes (A18). Progress
S0003-2700(98)00006-7 CCC: $15.00 © 1998 American Chemical Society Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 119R
Published on Web 04/24/1998
in the use of mid-IR optical fibers was presented (A19). Develop-
ments in infrared microspectroscopy were discussed (A20).
Emission spectroscopy was reviewed (A21). Reflection-absorp-
tion spectroscopy and its applications were discussed (A22).
Other infrared techniques for the analysis of surfaces were also
explored (A23). The applications of microcolumn LC/FT-IR were
discussed (A24).
A comprehensive review of infrared and Raman spectroscopies
of polymeric systems was published (A25). This publication
covers the entire field of analytical chemistry of polymer systems;
no other attempt will be made within the format of the current
review to expand on this treatment of polymer systems. Several
reviews with summaries of the application of mid-IR spectroscopy
to particular industries or product areas were presented for the
following: dyes (A26), wood products (A27, A28), textiles (A29),
petrochemicals (A30), pharmaceuticals (A31-A33), medicine
(A34), materialography (A35), and ionomers (A36).
A tutorial on the use of quantitative analysis via spectroscopic
data, with emphasis on sensitivity and selectivity measurements,
was published (A37). Chemometric procedures for quantitative
analysis via infrared spectroscopy were reviewed (A38-A40).
Quantitative analysis of glass structure and properties was sum-
marized (A41).
General applications of near-IR spectroscopy were reviewed
(A42-A45). Applications of this technique to analysis of agri-
cultural products (A46) and the food industry were presented
(A47-A50). Biological and medical applications were also
reviewed (A51). A comparison of near-IR and mid-IR procedures
for process analysis along with a discussion of the fundamentals
of these techniques was offered (A52). The use of multivariate
techniques as an aid to spectral interpretation was extensively
reviewed (A53). Interpretation of near-IR spectra was discussed
(A54). Calibration models and standardization of near-IR instru-
ments were reviewed (A55).
A review of the use of thermo-IR spectroscopy to study the
interaction between organic pollutants and clay minerals was
presented (A56). Open-path IR to monitor volcanic plumes was
discussed (A57).
Ab initio calculations of unstable organic molecules and
reactive intermediates were discussed (A58). The use of spec-
troscopic methods in the study of carbohydrate chemistry was
reviewed (A59). The role of infrared spectroscopy in the
characterization of surface colloids at solid-liquid interfaces was
presented (A60). The literature pertaining to the use of IR
spectroscopy to study ion solvation and ion association was
reviewed (A61).
Protein structure analysis was discussed (A62-A64). Isotope-
edited infrared spectroscopy for the study of biomolecules was
discussed (A65, A66). An extensive review of the IR spectra of
lipids was presented (A67). The use of IR to study liposomes
and biomembranes was presented (A68). Biomedical applications,
such as diagnosis of disease states and tissue analysis, were
reviewed (A69). Infrared measurement techniques for the
analysis of biofluids were compared (A70). Analysis of steroids
with spectroscopic methods was reviewed (A71). Reviews of the
application of IR to the study of photosynthetic reaction centers
were presented (A72). Studies of the spectroscopic determination
of bacterial cell structure were discussed (A73).
120R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
A review of spectroscopic techniques for characterization of
catalysts was presented, with discussion as to technological
improvements in this area (A74). Catalyst intermediate studies
were reviewed (A75). Reviews of infrared spectra of inorganic
nitrides were presented (A76, A77). Characterization of zeolites
by spectroscopic techniques was summarized (A78-A80). The
application of spectroscopic techniques in the study of metal
complexes was discussed (A81-A85). Metal oxide catalysts were
the basis of several reviews (A86, A87). The spectroscopy of
materials adsorbed on metal surfaces was reviewed (A88, A89).
Infrared spectroscopic techniques used to characterize metal-
electrolyte interfaces were presented (A90). Characterization of
Grignard reagents was summarized (A91).
The role of infrared and Raman spectroscopy in the study of
semiconductor alloys was reviewed (A92). Identification of defects
in semiconductor materials as monitored by IR microspectroscopy
was discussed (A93). Gap states in superconductors were studied
by infrared spectroscopy (A94).
DATABASES, SOFTWARE, AND ALGORITHMS
A review of databases associated with UV-visible, NMR, IR,
Raman, and mass spectral databases has been reported (B1). Also
included was a brief discussion of Moessbauer, NQR, XPS, and
CD databases. A strategy for knowledge acquisition in the
collection of IR spectra involving automated generation of cor-
relation tables has been reported. These tables are converted
into rules that can be used to infer the existence of molecular
substructures from the IR spectrum of an analyzed compound
(B2). Two computer programs have been designed for aiding
the library handing and microbial identification from IR spectra.
The programs run on IBM-PC compatibles (B3). Other reviews
on IR characterization included obtaining group frequency char-
acterization (B4) preprocessing methods and data transformations
(B5) and automatic spectrum interpretation techniques (B6). The
main features of GEISA-PC, an IBM-PC software package designed
for the use and management of large scaled databases of the
atmosphere physics and spectroscopy interests, were presented
(B7).
The performance of an IR library search system has been
examined using four different similarity measures for spectral
search (B8). A combinatorial library of catalyst candidates, each
consisting of a different metal element supported on alumina, has
been screened for hydrogen oxidation catalytic activity. This
method offers some promise for screening and optimizing catalyst
formulations more efficiently than current methods (B9). A novel
method for searching spectral libraries with spectra of mixtures,
using a mix-match search algorithm, was tested extensively with
good results (B10).
Several articles have been published in relationship to the
development of IR spectral databases or to enhancement of the
effectiveness of these databases to the spectroscopist. A knowl-
edge base has been proposed that adopts a set of rules that
express the laws of spectra interpretation and the experience of
special field experts in order to imitate the reasoning process of
the human brain in relation to the group frequency correlation of
organophosphorus compounds (B11). A strategy for the auto-
matic generation of correlation tables for IR spectral interpretation
has been proposed (B12). A combination of the IDIOTS algorithm
with the algorithm by Blaffert has been used to improve comput-
erized structure elucidation (B13). Hierarchical organization of
a knowledge base with IR spectral bands has been used to improve
expert system spectral interpretation (B14). Computerized IR
band assignment programs have been developed. One program
employs information from 700 functional groups to develop its
knowledge database (B15). A basis for simulating IR- and Raman-
active spectra of large-molecule systems has been developed using
the internal coordinate correlation based on molecular dynamics
algorithms and an autocorrelation function (B16). The develop-
ment of a computerized IR spectral library from scanned and
digitized IR spectra has been discussed (B17). A review covering
two strategies used in discriminate high-dimensional spectral data
analysis has been written. One method involves a preprocessing
method followed by a low-dimensional classifier. The other
method involves a high-dimensional classifier capable of handling
large numbers of variables (B18).
Nonparametric piecewise linear discriminant analysis (PLDA)
has been employed to develop an automated detection scheme
for FT-IR remote sensing interferogram data (B19). A method
has been developed for the simple and effective approximation of
the optical constants of neat liquids (B20). The issues of cross-
validation and missing data have been investigated relative to the
partial least-squares (PLS) algorithm. Both a full EM algorithm
and a reduced EM algorithm are discussed (B21). A comparison
of PLS and artificial neural networks in the prediction of concen-
trations of compounds involved in the fermentation process of
ethanol has been reported (B22). The use of calculations of
absorption bands and absorption intensities in conjunction with
present day theoretical methods have been used in the quantitative
IR analysis of compounds (B23). An algorithm for passive FT-IR
has been developed for implementation in air-monitoring systems,
with specific emphasis on military gases as measured from a
helicopter or tank (B24). An adaptation on an algorithm for plume
signature data analysis has been examined for open-path FT-IR
data reduction (B25). A new information content-based look-up
table technique for the fast computation of near-monochromatic
atmospheric transmittance in the IR that is well suited for satellite
and airplane observations has been developed (B26). A self-
modeling mixture analysis has been demonstrated using the
Simplisma and Tsimplisma approaches (B27). Computer simula-
tion of the IR spectra of substituted bicyclic and tricyclic amidines,
hexahydroimidazo[1,2-a]pyrazine-3,6-diones, and hexahydroimi-
dazo[1,2-a]imidazo[1,2-d]pyrazine-3,8-diones has been verified
using GC/FT-IR/MS (B28). Using a second derivative with PLS
techniques, NIR diffuse reflectance spectroscopy (NIRS) was used
to determine the active compounds in a pharmaceutical prepara-
tion (B29). A software-based digital signal processing method
has been used to demodulate the photoacoustic responses of step-
scan FT-IR photoacoustic measurements without any additional
hardware (B30). The interpretation of multivariate calibration and
rule induction classification models can be significantly improved
by adopting a new representation of data profiles containing
identifiable peaks using nonlinear curve fitting (B31). A meth-
odology has been developed for the in situ IR monitoring and
analysis of solid-phase organic reactions (B32). A simple PC-
based scientific spreadsheet has been used to construct a math
software package which provides a compliant solution to a design
problem for thermal imager performance (B33). A method for
the measurement of concentrations of an analyte present in a
biological fluid has been developed using NIR and an outlier
detection method (B34). An algorithm for the NIR-based portable
tissue oximeter has been developed and tested (B35). An
improved simulation of vibrational spectra for larger molecules
that removes artifacts has been developed by a direct transfer of
Cartesian molecular force fields and electrical property tensors
instead of internal coordinates (B36).
Passive FT-IR remote sensing techniques have been used in
the automated detection of trichloroethylene vapor in the presence
of a variety of IR background signatures. Using piecewise linear
discrimination developed in this study, successful detection of
trichloroethylene was achieved in 96% of the cases studied (B37).
An automated method for calculating the IO spectrum of open-
path FT-IR spectra has been developed and implemented to
correct for totally absorbing atmospheric species and instrument
drifts (B38). A rationing algorithm has been developed for the
quantitative analysis of the passive FT-IR spectrum of chemical
plumes. The algorithm removes the background, eliminates the
spectrometer internal signature, and enables quantitative examina-
tion of the spectral transmission (B39). A special algorithm for
the analysis of a cross structure of the temperature and concentra-
tion of emitting components for nonuniformly heated gas flows
using radiometric measurements in the IR band of a spectrum
has been proposed (B40). Testing of the MOPITT algorithm test
radiometer (MATR) has been done to provide support for the
prelaunch testing of the data retrieval algorithms for the MOPITT
satellite instrument (B41). Improvements have been made in the
Nimbus 7 limb IR monitor algorithms to improve the predictions
of ozone levels in the lower altitudes (B42). Stratospheric atlases
of high-resolution IR absorption spectra have been prepared from
balloon-borne spectrometer systems by the University of Denver.
These atlases contain spectra at 0.02- and 0.002-cm-1 resolutions
(B43). Observations of solid-state absorption features due to H2O
ice, CO ice, and silicate dust have been reported in the study of
the Herbig-Haro nebula in the R Coronae Australis dark cloud
(B44). A computer program for the interpretation of IR spectra
of organic compounds has been developed (B45). Solvent-induced
frequency shifts have been modeled using a continuum defined
by its static and high-frequency dielectric constants and application
to formaldehyde has been demonstrated (B46). A computer
program has been developed for automatic assignment of an IR
spectrum to create a knowledge database containing the informa-
tion of 700 functional groups (B47). The integrated spectrum of
interstellar metal-rich globular clusters has been synthesized using
the HR diagram and a stellar library (B48).
A method for accurate film thickness measurement has been
developed that separates the effects of interference and absorption
effectively (B49). FT-IR has been used as a continuous emission
monitor for on-line measurements of most volatile organics and
some inorganic compounds. This instrumentation can be used
for the monitoring of stack emissions and thermal treatment
processes (B50). A review of structural and spectroscopic
properties of transition metal compounds covering a variety of
modeling topics has been written (B51).
The problem with discontinuities in piecewise direct standard-
ization (PDS) has been identified and a procedure for its elimina-
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 121R
tion has been proposed (B52). A genetic algorithm has been
applied to optimization of PLDA with specific application to remote
sensing data (B53). A joint neural network has been developed
by combining gas-phase IR spectra with mass spectral data to
predict 26 different molecular substructures from multispectral
information. The combined database gives better prediction of
functional groups than either the IR or MS databases alone (B54).
A comparison of direct-deposition FT-IR and supercritical fluid FT-
IR spectra of quinones and barbiturates showed significant enough
variations of these spectra with KBr disk IR spectral libraries to
produce occasional incorrect identifications (B55). An IR spectral
library was prepared for the characterization of 55 nerve agent
homologues using GC/FT-IR spectroscopy (B56). Resolution
enhancement of the IR linear dichroic (IR-LD) spectra of partially
oriented molecules in a liquid crystal has been studied using
reference Fourier self-deconvolution (RFSD) (B57). Application
of an analog-digital converter to measurements made with a
charge-coupled device (CCD) has enabled a resolution enhance-
ment in the spectral features without limiting the measuring range
of the CCD (B58). NIR and NIT for use in the agriculture and
food industries have been developed by which the instruments
can be calibrated at the factory and can be used the day the
instrument is received (B59). Genetic algorithms have been
implemented in automated wavelength selection procedures to
build multivariate calibration models based on partial least-squares
methods for NIR (B60). A modification of the standardization
method of Shenk and Westerhaus for calibration model transfers
between NIR instruments has shown an improvement by use of
locally weighted regression (B61). Standardization of near-IR
spectrometric instruments using the piecewise direct standardiza-
tion method has been improved by modification of the algorithms
(B62). NIR pattern recognition has been improved using the
wavelet packet transform (B63). A recommendation has been
made that offers some improvement on the discrepancies ob-
served on NIR analysis of living tissues (B64). A pattern
recognition algorithm has been combined with near-IR reflectance
spectroscopy to function as a nondestructive analytical technique
for identifying dyes present in textiles (B65). Application of a
forward selection in the subsets selected by a genetic algorithm
for linear regression of near-IR spectroscopic data has been shown
to overcome some the selection of irrelevant variables (B66). A
detailed study of 13 conflicting patterns of change in cytochrome
c oxidase redox status from near-IR spectroscopy have identified
possible sources of error that could cause the discrepancies (B67).
A multivariate calibration procedure based on the use of a genetic
algorithm to guide the coupling of band-pass digital filtering and
PLS regression has been applied to near-IR spectroscopy for the
analysis of glucose in biological matrixes, resulting in better
correlation of results (B68). The vibrational spectra of (FeSi2 has
been calculated by molecular dynamics simulations with a tight
binding potential and verified by IR measurements on small
monocrystals (B69). NIR and NIT instruments for use in the
agriculture and food industry have been shown to be useble on
the same day as delivery by using a precalibration procedure.
Recommendations for enhancing the accuracy of the instrument
were also presented (B70). The spatial resolution of IR systems
used in IR thermography has been enhanced by use of a digital
image restoration technique based on the accurate determination
122R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
of the optical transfer function (B71). A recommendation of the
use of a weighted optimization for numerical correction of
spectrometric data has been proposed for resolution improvement
techniques (B72). A process to use multivariate signal responses
to analyze a sample has been proposed (B73). Principle compo-
nent analysis (PCA) has been applied to discriminate rapidly
between extractable compounds that are indigenous to papers and
nonindigenous compounds using SFE/SFC/FT-IR techniques
(B74). Infrasoft International (ISI) has developed NIR spectros-
copy programs that have been used in the determination of water,
oil, and protein content in food and agricultural products (B75).
A software-based method has been developed to remove spikes
in NIR spectra measured with Ge detectors (B76). NIR has been
used in refractive index modeling with PLS for hydrotreated gas
oils (B77).
A review has been published on the use of chemometrics in
NIR calibrations with emphasis on criteria and procedures for the
transfer of methods between instruments (B78).
INFRARED ACCESSORIES AND SAMPLING
TECHNIQUES
Articles were published on the use of Teflon tape (C1) and
disposable cards (C2, C3) as sample supports for IR spectroscopy.
A universal sampling tool for analysis of liquids and solids by IR
was described (C4). The use of rotational casting for preparation
of thin polymer films for IR analysis was discussed (C5). New
cells reviewed in the literature include a micro-FT-IR cell (C6), a
high-pressure IR cell for studying the interactions of polymers
and supercritical fluids (C7), modified NIR powder reflectance
cells (C8), a fiber-optic transmission cell for on-line SFE/FT-IR
(C9), and a channel flow cell for attenuated total reflectance
(ATR)/FT-IR measurements of species at an electrode (C10). A
scanning near-field IR microscope (C11) and a design enhance-
ment to increase the spatial resolution of FT-IR microscopes (C12)
were reported.
A review described four sample devices for NIR (C13). The
devices included a fiber-optic system, a robotic system, the use
of HPLC vials for scanning liquids in a sealed container, and a
moving blend cell. The use of an adapted FT-IR microscope to
follow a photoinitiated polymerization reaction was discussed
(C14). A ceramic sample heater for variable-temperature diffuse
reflectance FT-IR analysis of solids was described (C15). The
mechanochemical reactions that take place during preparation of
alkali halide disks were discussed in a review (C16). A new FT-
IR imaging technique has been developed by combining a focal
plane array detector with a step-scan Fourier transform interfer-
ometer (C17). The use of a movable two-dimensional Hadamard
mask and an FT-IR spectrometer for chemical mapping was
described (C18). Portable IR analyzers used for repetitive analysis
were reviewed (C19).
QUANTITATIVE ANALYSIS
A review has been written related to FT-IR emission spectros-
copy of solids. Also included in this review were a correction
equation for the single-beam emission spectra, proper data
manipulation procedures, and the use of a linear emission intensity
scale for quantitative work. Also included was a discussion on
multilayer samples (D1). A review of the application of quantita-
tive FT-IR spectroscopy to aqueous solutions has been written
(D2). This review was targeted at the evaluation of the ATR
technology. A variety of instrumentation and parameters were
used in the analysis. Results of these variations on the end results
are discussed. The examination of glasses with IR spectroscopy
has been reviewed with emphasis on obtaining information on
static dielectric constants and the calculation of semiempirical
calculations of vitreous solids’ IR spectra (D3). A review has also
been written on the use of multivariate quantitative infrared
analysis (D4). This review is focused at providing a tool to assess
quantitative methods and evaluate their conformity to ASTM
practices. A review of several methods for quantitative analysis
of gas-phase samples using FT-IR has focused on particular
advantages and disadvantages (D5). A review of the trends in
chemometrics as applied to NIR spectroscopy has been reported
with discussion of building databases of calibration samples,
regression models, and calibration transfer (D6).
A method has been developed for the utilization of synthetic
calibration spectra in calibration of instrumentation to provide
quantitative analysis of gas-phase IR spectra (D7). This method
uses the multiple atmospheric layer transmission (MALT) pro-
gram to create synthetic spectra that closely approximate real
measured spectra. This technique has proven useful in lung open-
path and solar FT-IR spectroscopy. A nonlinear multivariate
infrared analysis method has been used to research octane
number (RON) and other physical properties (D8). FT-IR with
curve fitting has been used in conjunction with NMR for the
quantitation of various components in rolling oils without their
separation (D9). FT-IR was used for quantitation of mineral oil
deposition on plant leaves (D10). FT-IR has been used in
conjunction with solid-state NMR (13C-SP/MAS) to determine
structural parameters of low-rank Czech coals (D11). An FT-IR
method has been developed to rapidly screen soil samples for
hazardous waste site (D12). The method was originally developed
to identify and quantify microgram concentrations of explosives
in soil samples, but offers promise to detection of volatiles,
semivolatiles, and pesticides. A method has been developed for
the quantitative analysis of multicomponent mixtures with un-
known individual spectra (D13). This method involves a two-
step optimization procedure which allows for high precision
results. A scanning IR polariscope with high spatial resolution
has been developed for the inspection of residual strains in III-V
compound wafers (D14). FT-IR has been used to determine
quantitative equilibrium constants between CO2 and Lewis bases
(D15). Step-scan FT-IR photoacoustic spectroscopy has been used
to quantify the content of brivudine and dithranol in a petrolatum/
drug ointment (D16). The FT-IR extinction/scattering technique
has been used to evaluate fuel vapor concentration in various spray
conditions (D17). FT-IR has been used to quantitatively analyze
levels of NH3 and HCN in hot combustion gases taken from the
combustion chamber of boilers fueled by coal (D18). An FT-IR
method has been developed for measuring norditerpenoid alka-
loids in larkspurs. The method was calibrated using high-pressure
liquid chromatography and gravimetric methods (D19). A com-
bination of remote infrared differential absorption lidar experi-
ments with a computational approach has been used to measure
four organic gases (D20). A fully automated procedure has been
developed for FT-IR determination of caffeine in soft drinks.
Detection limits with relative standard deviations were reported
(D21).
A calibration model based on DRIFT spectroscopy has been
developed for the rapid estimation of the chemical composition
of radiata pine wood samples. The model has been shown to
predict extractives, lignin, and carbohydrates (D22). Attenuated
total reflectance FT-IR spectroscopy has been used to monitor
the epoxidation of indene to indene oxide using multivariate
statistical methods (D23).
A methodology has been developed for selection of the best
calibration sample subset for principle component regression
analysis (D24). This method has been applied to both UV-visible
spectroscopy and near-IR spectroscopy effectively with a consider-
able reduction in cost. A calibration strategy has been proposed
for dealing with difficult calibrations using NIR spectroscopy
(D25). A preprocess step, dubbed piecewise mutiplicative scatter
correction (PMSC), has been successfully applied to NIR calibra-
tion spectra for the analysis of homogenized beef samples (D26).
This technique has shown up to 52% improvement on prediction
error. A noninvasive NIR quantitative measurement instrument
has been developed with removable finger inserts of various sizes
to enable variable sample size insertion for analysis (D27). A
method has been developed for the quantitative NIR spectroscopic
analysis of biological liquids without the use of any detection
reagents (D28). NIR spectroscopy with multivariate calibration
has been used in the quantitative determination of glucose,
fructose, sucrose, citric acid, and malic acid in dried orange juice
samples (D29). An FT-NIR instrument equipped with a fiber-optic
probe has been used to measure levels of resorcinol in water
between 9 and 35% independent of temperature (D30). A PLS
method has been developed for NIR in the analysis of orange
juices (D31). Using NIR with a partial least-squares model, a
method has been developed for the simultaneous determination
of ethanol, glycerol, fructose, glucose, and residual sugars in
botrytized grape sweet white wines (D32). A NIR method has
been developed for the quantitative determination of resorcinol
in aqueous solutions for industrial applications (D33). A NIR
technique has been developed using artificial neural networks to
study tobacco nicotine (D34). The application of FT NIR for
quantitative and qualitative analysis has been discussed (D35).
Quantitative determination of hemoglobin in turbid medium has
been demonstrated using NIR spectroscopy (D36). Statistical and
artificial network pattern recognition techniques have been applied
to NIR spectra of soy sauce samples and related to differences in
food flavorings (D37). A rapid FT-NIR spectroscopic method has
been developed for quantitative determination of peroxides in
edible oils. The method is based on a PLS calibration model and
offers an alternative to the iodometric method, avoiding the solvent
and reagent disposal problems (D38). A method and apparatus
for the noninvasive measurement of intravascular ketone body
concentration has been reported (D39). A patent application has
been filed for a method to determine tissue hemoglobin levels
using NIR spectroscopy (D40). A method of variable selection
for quantitative NIR determination of glucose concentrations has
been shown to reduce the number of calibration samples with no
loss in reliability (D41). The combination of NIR and mid-IR
spectra has been shown to provide improvements in calibration
results in the assay of lignin, cell wall digestibility, and dry matter
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 123R
digestibility on a variety of samples (D42). A PLS calibration
method has been successfully applied to NIR spectroscopy for
the measurement of malt quality constituents in whole grain
(D43). The use of toluene as a test for the calibration of an FT-
NIR spectrometer in the analysis of the hydroxyl content of
ethoxylated fatty acid produced a stable calibration over 120 days
(D44). A procedure to standardize across a network of instru-
ments has been proposed (D45). PCA has been applied to the
study of the dissociation process of oleyl alcohol using FT-NIR
spectroscopy (D46).
A comparison of the quantitative properties of IR vibrational
circular dichroism (VCD) and Raman optical activity (ROA) has
been done in the analysis of trans-pinene, cis-pinane, R-pinene,
and β-pinene (D47). Correlation was observed for the two
techniques for the strongly chiral and strongly achiral vibrational
modes. The use of quantitative VCD in the analysis of proteins
has been discussed with specific reference to effects of spectral
resolution, sample concentration, cell selection, and spectral
normalization (D48).
FT-IR with PLS techniques has been used in the simultaneous
on-line determination of gases in smoke from burning textiles
(D49). The compounds determined using this technology include
the following: water, CO2, CO, NO, NO2, SO2, C3H4O, HCl, HBr,
HCN, and HF. The shelf life of nitrocellulose containing single-
base propellants has been determined using FT-IR and PLS
calibration techniques (D50). A PLS method has been developed
using transmission FT-IR spectroscopy for the analysis of aldehyde
formation and anisidine value of thermally stressed oils (D51). A
PLS method has been developed for the quantitative FT-IR analysis
of fatty acid esters (D52). A multiple model approach has been
used to evaluate polyolefin formulations using discriminant
analysis with process, chemistry, and spectroscopic information
(D53, D54).
Using principle component regression (PCR) and PCA, a
classification method has been developed for the analysis of sugar
cane juices (D55). This method allows for the qualitative
classification of spectra without knowledge of their chemical
composition. The effect of PCA on mid-IR spectroscopy data has
been examined to determine the effects of instrumental instability
on results (D56).
FT-IR spectroscopy has been used to monitor gases generated
during chemical inhibition of fuel pool fires burning in the air
(D57). This technique was used in the analysis of acid gases
formed when Halon 1301 was used to extinguish fires. FT-IR
spectroscopy has been utilized in the study of nitric acid ices
formed from vapors containing water (D58). Passive FT-IR
remote sensing has been used in the analysis of effluent plumes,
such as controlled gas releases, power plant emission stacks, and
chemical manufacturing facilities (D59).
Reflectance FT-IR spectroscopy has been used to examine the
electrochemical mechanism for ethylene glycol oxidation by
polycrystalline platinum (D60). IR spectroscopy has been used
in the study of fullerene (D61). Information on intermolecular
interactions are also discussed.
Oxidation of mesocarbon microbeads has been followed by
thermogravimetric and FT-IR spectroscopic techniques (D62). The
quantitative determination of fluconazole has been demonstrated
using KBr pellets of the material and the transmission technique
124R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
(D63). FT-IR spectroscopy has been used for the quantitative
determination of dodecylbenzenesulfonate and tripolyphosphate
in solid compound samples of detergents (D64).
A gas flow equilibrium vapor cell has been shown to allow for
the quantitative analysis of vapor-phase species using Beer’s law
(D65). Using an equilibrated vapor cell with a closed-loop
circulation, vapor-air mixtures of volatile organic compounds in
water were examined. Mixtures of methanol, ethanol, 2-propanol,
acetone, and 2-butanone were found to follow Beer’s law at less
than 50 Torr (D66). An FT-IR classical computational method
has been applied to the direct quantitation of multicomponent gas
mixtures of organic compounds. The method has been used to
characterize mixtures of up to 10 compounds (D67).
FT-IR microspectroscopy has been used for the quantitative
study of solid-phase resin-bound chemical reactions of species
containing deuterium (D68). An artificial coalification series has
been analyzed by FT-IR microscopy using a diamond anvil
compression cell. The method has been applied to Mahakam coal
(type III organic matter) (D69).
FT-IR in conjunction with gravimetric methods has been used
in the quantitative analysis of CO chemisorbed on Pt surfaces
(D70). FT-IR spectroscopy has also been used in the study of
antiepileptic medications (D71). A combination of IR and MS
techniques have been used to determine the extinction coefficients
of adsorbed CO on Rh/SiO2 catalyst (D72). Water adsorption
on H-ZSM-5 zeolite has been evaluated using FT-IR spectroscopy
(D73). IR spectroscopy analysis has been used in conjunction
with nuclear reaction analysis in characterizing molar absorptivity
of hydroxyl bands in high-hydroxyl-content silica glasses (D74).
A nondestructive pulsed IR quantitative evaluation of defects in
metal surfaces has been developed for the inspection of aluminum,
steel, and turbine blades (D75).
SPECTRA-STRUCTURE CORRELATION
The SO2 stretching vibration in metal saccharinates for Na,
Mg, Mn, Fe, Co, Ni, Zn, Cd, and Pb have been studied using IR
spectroscopy (E1). An IR spectral study was made of kaolinite
samples before and after dehydroxylation and rehydration. The
surface areas of the samples were observed to effect the OH
stretching frequencies (E2). IR spectroscopy has been used to
interpret structural changes in silica glasses. Shifts in the Si-O
stretching band was used to monitor changes in average Si-O-
Si bond angles (E3). IR and Raman spectroscopy have been used
in the study of 1,3,5-tri-tert-butylpentalenes (E4). NMR and IR
spectroscopies have been used to characterize the effects of
physical surroundings and chemical structure information of
carbonyl stretching frequencies in various solvents (E5). Density
functional theory has been applied to the investigations of
harmonic force fields, vibrational frequencies, and IR intensities
of transition metal complexes (E6). The IR spectra of TiO2,
sodium titanates, and natisite have been examined, and differences
in the IR spectra have been correlated with structural features
(E7). The IR bands of cis- and trans-CHdCH and vinyl CHdCH2
groups of model compounds and polybutadienes have been
compared (E8). Group frequency assignments have been com-
piled for major IR bands observed in 20 common polymers (E9).
In a review article, some methods of obtaining characteristic group
frequencies, including empirical correlations, were discussed
(E10). Two-dimensional FT-IR correlation analysis was applied
to both the mid-IR and NIR regions to investigate changes in the
secondary structure of β-lactoglobulin in D2O solvent systems. A
mechanism for the change from the β sheet to the R helix was
proposed (E11). A review has been written on the two-
dimensional FT-IR and NIR correlation spectroscopies in the
studies of temperature-dependent spectral variations of self-
associated molecules (E12). The theory of fuzzy sets has been
applied to specific IR spectrum-structure correlations (E13).
Grazing-angle FT-IR spectroscopy has been used to study the
monolayer structure of self-assembly molecules with novel amido
linkages (E14). The secondary structure of photosystem II
reaction centers isolated from pea has been deduced from
quantitative analysis of the component bands of the IR amide I
spectral region determined by FT-IR (E15). A method for
determining the orientation of individual bonds within complex
macromolecules from polarized IR measurements on oriented
single crystals has been described (E16). The peroxide bond of
inorganic and organic peroxides have been studied by IR and
Raman spectroscopies. The results of the study are a narrower
range of frequencies for the vibration (845-875 cm-1) (E17). The
experimental vibrational frequencies of s-trans-1,3-butadiene were
used to determine the scale factors for its quantum mechanical
force field. This information was then used to determine the
location of the s-gauche rotamer band in the IR spectrum of the
gas phase (E18). The spectral structure arising from the pucker-
ing vibration of perfluorocyclobutane has been modeled with a
quadratic-quartic potential (E19). Two-electron correlation theo-
ries, second-order Moller-Plesset perturbation, and d functional
methods have been adopted to obtain fully optimized structures
of styrene, trans-stilbene, and cis-stilbene. The relationship of
intermolecular and intramolecular forces was discussed (E20).
The IR spectra of some hydroxy aromatic Schiff bases have been
recorded. The bands due to CdN and OH groups were assigned
and discussed in terms of molecular structure (E21). The
structures of the size-selected hydrogen-bonded phenol-(H2O)n
clusters were investigated by analyzing the OH stretching
vibrational spectral in S0, S1, and the ionic states. The charac-
teristics of the different states were discussed (E22). The spectral
characteristics of absorption bands of free and bound H-bonded
molecules of substituted anilines in solution were determined by
FT-IR spectroscopy (E23). Solvent effects on N-(3-chloro-2-benzo-
[b]thienocarbonyl)-N′-ethylthiourea were studied by examining the
changes in the IR bands belonging to the NH and CO bonds
(E24). Spectral deconvolution, using a specially developed
program, was used to characterize Co adsorbed onto alumina-
supported bimetallic catalysts containing either Fe or Ni (E25).
A review on matrix IR spectroscopy of intermediates with low-
coordinated carbon, silicon, and germanium atoms has been
written (E26). An FT-IR study of the bonding of methoxy on Ni-
(100) has been used to evaluate the effects of coadsorbed sulfur,
carbon monoxide, and hydrogen. Differences observed were
attributed to changes in the metal-oxygen bond (E27). The FT-
IR spectra of six para-substituted aniline deriviatives and nine 1-p-
aminophenylazoles and benzazoles have been recorded (E28). The
fundamental IR absorption band for CO in solution in four
chlorinated solvents has been reported. The changes in solute-
solvent interaction were discussed (E29). The IR spectra of Fe
and Ru 5-cyclopentadienyl carbonylmetallocarboxylates were
obtained in THF at -78 °C. The effect of the counterions on CO2
complexation was discussed (E30).
HYPHENATED TECHNIQUES
GC/FT-IR was used in the study of trimethylsilyl derivatives
of 10 hydroxy- and methoxyhydroxyflavonoid compounds. The
correlation between retention and gas-phase IR data was shown
to be useful in structural identification of compounds with very
similar chromatographic behavior. The carbonyl frequencies were
shown to give information on the presence of substituting agents
(F1). GC/MS and direct-deposition GC/FT-IR were applied at
the same level of sensitivity to the study of minute concentrations
of volatiles in green leaves (F2). The IR spectra of six monomeric
gaseous aromatic N-methyleneamines were reported from GC/
FT-IR experiments (F3). Gas chromatography/matrix isolation/
FT-IR (GC/MI/FT-IR) were used to confirm the identities of
trimethylsilyl derivatives of trichothecene mycotoxins found in
grains (F4). A comparison of pyrolysis GC and FT-IR spectros-
copy indicated the latter was able to discriminate fiber makeup
better (F5). FT-IR and gas chromatography were used to study
model samples containing various petroleum products and field
samples of the Vltava River. This study showed IR and GC to be
suitable to determine concentrations of 10-102 mg/L of lower
and middle petroleum fractions in water (F6). GC/FT-IR has been
used in the qualitative and quantitative determination of 1,2-
propanediol in Acyclovir cream (F7). Diffuse reflectance FT-IR
spectroscopy has been used to qualitatively and quantitatively
determine drugs (heroin, cocaine, codeine) separated by thin-
layer chromatography (F8). GC/FT-IR has been used as a rapid
method to distinguish cis and trans R,R-disubstituted piperidines
and pyrrolidines (F9). GC/FT-IR has been used to identify 42
monosaccharides as their trimethylsilyl ethers (F10). GC/MS
and GC/FT-IR have been used to determine ferrocenes (F11).
GC/FT-IR has been successfully used in the identification of
disaccharides after conversion to their methylsilyl ethers (F12).
GC/FT-IR and CCD Raman spectroscopy has been used to
differentiate cyclopentane- and cyclohexane-containing com-
pounds. The GC/FT-IR was viewed as a method to determine
individual naphthenes while the CCD Raman was viewed as a
means to measure bulk mixture properties (F13). GC/FT-IR has
been used to identify various fatty acids (F14). The total olefins
in gasoline can be determined on-line by process GC or FT-IR
spectroscopy. The FT-IR method uses PLS correlation calibration
and takes approximately 0.2 min per determination (F15).
Continuous FT-IR monitoring in conjunction with off-line pyrolysis
GC/MS was used to evaluate the oxidation of fossil organic matter
in Miocene and Silurian sediments. The oxidation of the organic
matter in the two sediments was compared (F16). The identifica-
tion of volatile organic compounds generated during polymer
processing has been performed by the use of TG-GC/IR-MS
spectroscopy (F17). A review on the application of multidimen-
sional GC/MS and GC/FT-IR to the analysis of components in
complex matrixes has been written (F18). The analysis of
dimethylphenanthrenes by direct-deposition GC/FT-IR has been
reported with quantitative procedures described (F19). GC/FT-
IR has been shown useful in the determination of the stereochem-
istry of carbon-carbon double bonds conjugated with a vinyl
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 125R
group (F20). Off-line pyrolysis GC/MS/FT-IR was used to
investigate oxidation of fossil organic matter in Miocene and
Silurian sediments (F21). The photochemical degradation of
dichoroprop and 2-naphthoxyacetic acid in water has been studied
by GC/MS and GC/FT-IR. The photodegradation pathways were
described (F22). An aqueous smoke flavoring employed in the
food industry has been studied using GC/MS/FT-IR spectroscopy.
The components were identified and discussed (F23). Headspace
GC/FT-IR has been used to study the in situ thermal decomposi-
tion products of O-ethyldithiocarbonate on mineral surfaces (F24).
DRIFTS has been coupled with GC to correlate changes in the
IR spectrum of a zeolite with the composition of the gas phase
(F25).
On-line trace enrichment combined with column LC/FT-IR
microspectroscopy has been used in the identification of herbi-
cides in river water. The identification limits for the herbicides
studied were reported (F26). Reversed-phase liquid chromatog-
raphy has been used with FT-IR by means of a solvent elimination
interface. Features studied included postcolumn band broadening,
phase separation efficiency, evaporation efficiency, and extraction
yield. This technique was applied to phenylureas and quinones.
FT-IR detection was demonstrated at the submicrogram per
milliliter level (F27). Reversed-phase liquid chromatography with
solvent elimination and FT-IR microscopy have been applied to
the characterization of additives in PVC and polypropylene at the
low-nanogram range (F28). HPTLC/FT-IR has been used on-
line to identify LSD, MBDB, and atropine in an in situ measure-
ment (F29). A review on microcolumn liquid chromatography
FT-IR has been written with attention to various approaches (F30).
Size exclusion chromatography (SEC) has been used with FT-IR
spectroscopy in studies of compositional distribution in copoly-
mers, impurity profiling, and branching in polyolefins (F31). Film
morphology of polymer systems (polyethylene-polystyrene blends)
have been studied by SEC-FT-IR (F32). A particle-beam LC/FT-
IR interface has been employed in the investigation of the effect
of chromatographic conditions, such as mobile-phase composition,
elution process, and stationary phase, on protein secondary
structure. Qualitative and semiquantitative measurements were
possible (F33). The applicability of IR spectrometric detection
in liquid chromatography, based on solvent elimination prior to
IR scanning, has been enlarged to gradient separations by
adaptation of a capillary column switching system and addition
of a postcolumn makeup liquid (F34). A mobile-phase elimination
interface originally designed for liquid chromatography IR spec-
troscopy has been shown to perform exceedingly well for packed-
column SFC/FT-IR. The technique was used in the separation
of Irganox 1076 (F35). Principle component analysis was applied
to discriminate rapidly between extractable compounds that are
indigenous to papers and nonindigenous compounds on the basis
of their IR spectra. This method was applied with on-line SFE/
SFC/FT-IR spectroscopy to yield an automated analysis of
compounds that can be extracted from very complex matrixes
(F36). The orthogonal projection approach has been applied to
the analysis of a reaction product by HPLC and LC/FT-IR in which
overlapping peaks were observed. The resolution of the overlap-
ping peaks into individual chromatograms and IR spectra were
discussed (F37).
126R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
Thermogravimetric analysis (TGA) FT-IR spectroscopy has
been used in the characterization of the reaction mechanism of
Pb(Zr, Ti)O3 (F38). Thermogravimetric FT-IR methods were
applied to characterization of used turbine engine lubricants
during a reclamation effort. A themogravimetric/secondary
oxidation/FT-IR method was developed to determine trace levels
of chlorinated contamination. The detection limit was reported
as 300 ppm (w/w) (F39). TGA/FT-IR has been used to study
the thermal degradation of PMMA (F40). A review has been
written on the applications of thermogravimetric analysis com-
bined with FT-IR spectroscopy. This review covers characteriza-
tion of coal, source rock, heavy hydrocarbons, biomass, waste
materials, and plastics (F41). Thermogravimetry/IR/mass spec-
trometric analysis (TG/IR/MS), a relatively new technology, has
been applied to the analysis of paper mill deposits as a rapid means
of identifying contamination sources (F42). Thermogravimetry/
FT-IR spectroscopy have been used in the analysis of recycled
cellulose pulps (F43). TC/FT-IR spectroscopy has been used in
the study of the incineration and pyrolysis of polyethylene, PVC,
and PET (F44). TG/MS/FT-IR has been applied to the study of
post-cross-linking and decomposition of a phenolic resin (F45).
A TG/FT-IR system was used in the study of modified phenolic
hardeners and curing of an epoxy resin. The technique was used
in the study of the evolved gases during the decomposition of
2,6-dimethylol-o-cresol and the product modification with hexahy-
drophthalic acid anhydride (F46).
TIME-RESOLVED INFRARED SPECTROSCOPY
A time-resolved IR double-resonance technique involving the
use of two CO2 lasers was employed in a study of the transfer of
vibrational energy between ozone and oxygen or nitrogen at 200-
300 K (G1). Oxidation of the lubricant in the ring pack of a
running diesel engine was detected by time-resolved FT-IR (G2).
Time resolution of 200 fs was achieved during time-resolved IR
and UV-visible spectroscopy by means of an ultrafast laser
apparatus (G3). Time-resolved FT-IR was used in a comparison
between cytochrome P-450cam carbon monoxide complex bound
with (1R)-camphor and same complex bound with (1S)-camphor
(G4). A review was given on time-resolved diode laser IR
reflection-absorption spectroscopy (G5). The reaction initiated
by pulse radiolysis of SF6/NO gas mixtures was investigated by
time-resolved IR and UV spectroscopy (G6).
Femtosecond time-resolved IR spectroscopy was used to detect
the reactive intermediates in an alkane C-H bond activation by
organometallic compounds at room temperature (G7). A review
of the application of time-resolved IR spectroscopy for the study
of organometallic photochemicals in solution was presented (G8).
The use of time-resolved IR spectroscopy to probe excited states
of transition metals was discussed (G9). Time-resolved infrared
spectroscopy was used to study the photolysis of 2-(methoxycar-
bonyl)phenyl azide and Cr(CO)4(2,2′-bipyridine) (G10, G11). The
photochemistry of certain metal carbonyl species dissolved in
supercritical noble gases or carbon dioxide was the focus of a
study using time-resolved IR and UV spectroscopy (G12). Time-
resolved IR spectroscopy was applied to the study of the
photochemical rearrangement of a rhenium dimetallacyclobutene
(G13). The propargyl radical produced by the UV photolysis of
allene was detected by time-resolved IR diode laser spectroscopy
(G14). The products produced by the photochemical ring opening
of 1,3-cyclohexadiene were investigated by time-resolved step-scan
FT-IR spectroscopy (G15). The experimental results for one- and
two-dimensional time-resolved FT-IR spectroscopy of liquid crys-
tals were presented (G16). Time-resolved FT-IR was used to
monitor behavior of ferroelectric liquid crystals in an electric field
(G17). A nematic solution of 2-naphthaldehyde in an electric field
was studied by time-resolved step-scan FT-IR (G18). A multi-
channel FT-IR spectrometer for single-event time-resolved spec-
troscopy was described (G19). Attenuated total reflection surface-
enhanced IR absorption spectroscopy combined with time-resolved
IR spectroscopy were used in monitoring electrochemical reac-
tions (G20). Step-scan time-resolved FT-IR emission spectroscopy
was used to study the photodissociation of ethylene at 193.3 nm
(G21).
A nanosecond time-resolved IR spectrometer with a photovol-
taic MCT detector was described (G22). A review was published
that encompasses both experimental and theoretical studies of
the vibrational relaxation of small molecules in solution (G23).
The bacteriorhodopsin photocycle was measured by time-resolved
ATR/FT-IR spectroscopy (G24). Nanosecond time-resolved FT-
IR spectroscopy was also used to study the early stages of the
bacteriorhodopsin photocycle (G25). Time-resolved FT-IR was
applied to the investigation of the last steps of the photocycles of
Glu-204 and Leu-93 mutants of bacteriorhodopsin (G26). Pico-
second tunable IR pulses were used in a time-resolved spectro-
scopic experiment to study the vibrational energy transfer in
nitromethane explosives (G27). Time-resolved impulse photo-
acoustic measurements of gases and solids were obtained with a
step-scan FT-IR spectrometer (G28). Picosecond time-resolved
near-IR was used to study the excited states of C70 (G29).
The release of ATP from “caged ATP” and partial reactions of
the Ca2+-pumping cycle of Ca2+-ATPase were followed by time-
resolved FT-IR spectroscopy (G30-G32). A review discussed the
use of time-resolved infrared spectroscopy to follow events in
protein folding (G33). The IR chemiluminescence of the products
for the NO + NCO reaction was monitored with time-resolved
FT-IR (G34). The intermediates in the migratory insertion of CO
into the metal-alkyl bond of manganese carbonyls were detected
by time-resolved FT-IR spectroscopy (G35).
REFLECTANCE TECHNIQUES
Symmetry, selection rules, and nomenclature in surface spec-
troscopies was reviewed (H1). The application of FT-IR, diffuse
reflectance, and attenuated total reflectance techniques toward the
analysis of soil materials was discussed (H2). A review described
the investigation of molecular chemisorption at single-crystal metal
surfaces by reflection absorption IR spectroscopy (H3). Recent
advances in the use of IR and Raman spectroscopies for the
characterization of polymer/polymer and polymer/substrate in-
terfaces was reviewed (H4). The theory and practice of external
IR reflection absorption spectroscopy as applied to films at the
air/water interface were described (H5). Time-resolved diode
laser IR reflection-absorption spectroscopy and its application was
discussed (H6). A book described the theory and practice of
attenuated total reflectance spectroscopy of polymers (H7), while
a review discussed the analysis of adhesives, sealants, and coatings
by the same technique (H8). The use of diffuse reflectance FT-
IR spectroscopy in heterogeneous catalysis studies was reviewed
(H9). The use of synchrotron radiation for reflection absorption
studies of surfaces was described (H10). New data on water
incorporation in glass as determined by IR reflectance spectros-
copy were reviewed (H11). The Raman and IR reflection spectra
of AlN (H12), BN (H13), GaN (H14) were reviewed. The analysis
of photocopy toners by diffuse reflectance, attenuated total
reflectance, microscopic reflection-absorption, and microscopic
IR techniques was evaluated (H15).
Single-Crystal and Bulk Analysis Applications. The
crystal field transitions for Nd3+ were studied by Raman and far-
IR reflectance spectroscopies (H16). Polarization-dependent far-
IR reflectivity measurements were made on single crystals of
anatase TiO2 (H17). The relaxation effect of IR reflectance spectra
of nanocrystalline composite oxides was investigated (H18).
Raman and IR reflectivity spectroscopies were used to study the
TeO2 crystal (H19) and the GaN crystal (H20). Hexagonal barium
titanate was studied by Raman and IR reflectivity spectroscopies
(H21). Polarized IR reflection spectra of TlClO4, TlBF4, and NH4-
BF4 single crystals were analyzed (H22). Bismuth disproportion-
ation in BaBiO3 was studied by infrared and visible reflectance
spectroscopies (H23). Yttrium and lanthanide copper oxides were
studied by X-ray diffraction and IR reflectance spectroscopy (H24).
The far-IR reflectance spectra of bismuth cuprates were analyzed
(H25). Phase transition dynamics in layered crystals were
investigated by IR reflectance and Raman spectroscopies (H26).
Cobaltite spinels were characterized by IR reflectance spectros-
copy (H27). The formation and characterization of Si/SiO2
multilayer structures by oxygen ion implantation into silicon was
studied by FT-IR reflectance spectroscopy (H28).
Cofacially stacked phthalocyanines doped with iodine were
studied by IR reflectance spectroscopy and X-ray diffraction (H29).
The application of reflectance micro-FT-IR spectroscopy to analyze
coal macerals was described (H30). Protonated and deuterated
ices compressed under high pressure showed IR reflectance
evidence of a phase transition (H31). The application of infrared
reflectance spectroscopy to mineral exploration was described
(H32). The coordination states of molybdenum and the nature
of copper ion sites in superionic glasses was investigated (H33).
Far-IR reflectance investigations of lead borate and lead alumi-
noborate glasses were described (H34). FT-IR microreflectance
measurements of the CO32- ion content in glasses were discussed
(H35). Polymer characterization by specular reflectance using
an FT-IR microscope was evaluated (H36). Microreflectance FT-
IR techniques for the forensic examination of documents was
discussed (H37). The application of real-time reflectance IR
spectroscopy to the study of photopolymerization reaction rates
of stereolithography resins was developed (H38). Aspects in
interpreting results of reflectance and attenuated total reflectance
spectra of semiconductor systems were discussed (H39). A
method was developed for the in situ investigation of corrosion
of copper in a gaseous environment (H40). The potential of IR
reflection-absorption spectroscopy for the study of high-temper-
ature oxidation of metals and alloys was demonstrated (H41).
Thin-Film Applications. Reflectance FT-IR spectroscopy
was used as a tool for surface inspection and contamination
detection (H42, H43). A method was developed that eliminated
the problem of interference fringes in reflection spectra of
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 127R
photoresist films (H44). The current approach in using IR
reflectance spectroscopy for thin-film measurement in the semi-
conductor industry was outlined (H45). Semiconducting iron
silicide films were characterized (H46). Polarized IR reflection
spectroscopy was used to identify boron nitride film phases (H47).
FT-IR spectra of borophosphosilicate films obtained by metal-
backed configurations were compared to those obtained by
conventional transmission (H48). IR reflectance and transmit-
tance spectra of chalcogenide glass layers were analyzed (H49).
Cupric oxide in thin-film form was studied by IR reflectance
spectroscopy (H50). Thin carbon films constructed from oriented
carbon nanotubes were studied (H51). Molecular association in
thin films of mesogenic cyanophenyl derivatives was investigated
by reflection IR spectroscopy (H52). The infrared spectra of oxide
films were modeled for microstructural analysis (H53). Silicon
oxynitride thin films were characterized (H54). Thin films of
lubricating oils on metal surfaces were examined by polarization
modulation reflection-absorbance spectroscopy (H55). Iron
oxide films deposited on a magnesium oxide substrate were
examined (H56). IR reflection-absorption spectra of aluminum
hydrides on a silicon oxide surface were done using a buried metal
layer substrate (H57). A spectroscopic study was done on the
self-assembling processes of organophosphates on evaporated
silver films (H58). The optimization of IR reflection spectroscopy
for the quantitative determination of borophosphosilicate glass
parameters was described (H59). FT-IR reflection-absorption
spectroscopy was used for in situ observation of photoinduced
vapor deposition polymerization of N-vinylcarbazole (H60, H61).
The redox-induced orientation change of a self-assembled mono-
layer of 11-ferrocenyl-1-undecanethiol was studied (H62). The role
of hydrogen bond and metal complex formation in amino acid
monolayers was investigated using IR reflection-absorbance
spectroscopy (H63). The effects of substrates on the IR spectra
of Langmuir-Blodgett films was discussed (H64). Structure
disordering during surface pressure relaxation of Langmuir films
of stearic acid was studied (H65). The structure and phase
transitions in a Langmuir monolayer of tetracosanoic acid was
measured (H66). Stearic acid and cadmium stearate films were
characterized by external reflection IR at various angles of
incidence (H67). Monolayer and multilayers of ferroelectric liquid
crystals were characterized by polarization-modulated IR reflec-
tion-absorption spectroscopy (H68). The vibrational spectros-
copy of thin films of water adsorbed on metal surfaces under
ultrahigh vacuum were discussed (H69).
Interfacial Applications. Samples at air/water and air/metal
interfaces were measured by differential polarized reflectance
spectroscopy (H70). The molecular order of chiral monolayers
at the air/water interface was determined by infrared reflection-
absorption spectroscopy (H71). Monolayers of behenic acid
methyl ester at the air/water interface and air/deuterated water
interface were used for the quantitative determination of chain
tilt angles (H72). Interfacial molecular interactions between
ferroelectric liquid crystal and poly(vinyl alcohol) films were
investigated by IR reflection-absorption spectroscopy (H73).
Electromodulated FT-IR reflectance spectroscopy was used to
investigate the interaction of tetramethylthiourea with a polycrys-
talline gold electrode (H74). Partial chain deuteration was used
as a probe of conformational order of different regions in
128R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
hexadecanoic acid monolayers at the air/water interface (H75).
The interfacial behavior of water molecules at a gold electrode
surface was analyzed (H76).
Adsorption and Surface Reaction Applications. Infrared
reflection-absorption spectroscopy has been used extensively to
characterize adsorbed molecules on a variety of substrates and
to monitor surface reactions. Butene isomer reaction products
evolved during the course of a surface reaction were identified
(H77). The photolytic decarbonylation of iron pentacarbonyl
adsorbed on a silica film was studied (H78). Adsorption and
reactions of formic acid on nickel surfaces was investigated (H79).
The reactions of water and ethanol with a silicon surface were
studied (H80). Copper corrosion products formed by atmospheric
corrosion were characterized (H81). Nitroglycerin photodecom-
position on titania surfaces was measured (H82). The catalytic
decomposition of 2-propanol was studied over molybdenum-iron
oxide catalysts (H83). The chemisorption of hydrogen at a silicon
surface was studied (H84). The mode of deactivation and coke
formation in H-SSM-5 zeolite during ethylbenzene dispropor-
tionation was investigated (H85). The infrared spectra of neutral
and ionic hydrogen-bonded complexes formed by interaction of
a series of bases with H-Y, H-ZSM-5, and H-mordenite were
compared with analogous adducts formed on H-Nafion (H86).
The dehydrocyclization of submonolayer coverages of 1-hexene
to benzene on a copper single-crystal surface was reported (H87).
The nitridation of GaAs surfaces was observed (H88). The
interaction of amyl xanthate with chalcopyrite, tetrahedrite, and
tennantite was studied (H89). Nitrous oxide generated by the
reduction of nitrite on a platinum electrode was monitored (H90).
In situ infrared measurements of the reductive and oxidative
removal of a nonanethiol monolayer from a gold single crystal
were made (H91). The adsorption and oxidation of carbon
monoxide on palladium was studied (H92). Kinetic studies of the
reactivity of ethylene on platinum surfaces were done (H93). An
in situ study was done of the electrooxidation of methanol on Pt-
Ru electrodes (H94). Mixed self-assembled monolayers were
used as a model surface to study the adsorption of dimethyl-
methylphosphonate and water vapor (H95). Reflection-absorp-
tion IR spectroscopy was used to study the H/D scrambling
reactions during the conversion of ethylene to ethylidyne in
coadsorbed layers on platinum (H96). The melting of ordered
monolayers of n-hexane, n-octane, and n-decane adsorbed on
platinum was studied (H97). The chemical adsorption of 1-hexene
on ruthenium was studied (H98). The bonding and orientation
of L-alanine on copper was determined (H99). Adsorption of
ethene on clean and ethylidyne-covered platinum surfaces was
investigated (H100).
The reflection-absorption IR spectra of chlorine adsorbed on
a silver surface were characterized (H101). Several adsorbates
on a copper surface were investigated at cryogenic temperatures
(H102). The chemisorptive behavior of CO on several monome-
tallic and bimetallic Pd, Cu, and Au catalysts was investigated
(H103). The various phases occurring in dichlorodifluoromethane
physisorbed on graphite were studied (H104). Thin films of nitric
acid hydrates and ammonium nitrate adsorbed on gold foil were
characterized (H105). Isotopic characterization was done of NO
adsorption, dissociation, and coadsorption with CO on platinum
(H106), as well as reduction of NO (H107). The spectrum of
iron pentacarbonyl adsorbed on gold surfaces was characterized
(H108). The spectra of 1-prooxide and a set of deuterated
1-propoxides on a copper surface were obtained and characterized
(H109). The adsorption of NO on a polycrystalline platinum foil
was studied (H110). Two types of linear CO were observed
adsorbed on a copper electrode, while only one type was observed
on a silver electrode (H111). The adsorption and reactivity of
NO on copper was studied (H112). In situ and ex situ infrared
studies of the nature and structure of thiol monolayers adsorbed
on cuprous sulfide were done (H113). Surface chemistry occur-
ring during electroreduction of CO on electrodes modified with
conducting polymer and inorganic conductor films was measured
(H114). The spectrum of 2,5-dihydroxybenzyl mercaptan ad-
sorbed on gold electrodes was obtained using attenuated total
reflectance and reflection-absorption techniques (H115). Far IR
spectra of copper and platinum electrode surfaces were studied
(H116). The adsorption and reduction of nitrate ions on gold and
platinum electrodes was studied (H117). The coordination,
bonding, and configurational transitions for benzene and pyridine
adsorbed on platinum and copper were studied by reflection-
absorption IR spectroscopy (H118). Silicon surfaces treated with
an HF solution were used to study the behavior of adsorbed F
atoms (H119). Reflectance absorbance spectra of methyl and
ethyl formates chemisorbed on nickel were found to be consistent
with surface coverage-dependent rotational isomerization (H120).
The orientation of adsorbed deuterated and isotopic ethoxides
on a copper surface was measured (H121). The adsorption of
cyclohexane on clean and O-modified nickel surfaces was studied
(H122). A study was done of D2O ice deposited on self-assembled
alkanethiolate monolayers to measure cluster formation and
substrate/adsorbate interaction (H123). A thin film of poly(o-
phenylenediamine) coated on a platinum electrode was character-
ized (H124). The molecular structures of self-assembled bimo-
lecular films on gold and silicon surfaces were studied (H125).
The orientation effects in physisorbed multilayers on copper were
investigated (H126). An in situ study of 4-cyanopyridine adsorp-
tion on a gold electrode was done (H127). Propyne chemistry
on nickel and copper surfaces was characterized, using analogies
with ethyne adsorption (H128). A study was carried out on the
coadsorption of D2O with preadsorbed K on cobalt (H129).
Monolayers of octadecylsiloxane were formed on silicon and glass
surfaces and studied by polarization- and angle-dependent external
reflection IR spectroscopy (H130). An in situ study measured
the coadsorption of perchlorate and bisulfate ions with adsorbed
Tl on platinum (H131). In situ IR reflection spectroscopy was
used in the qualitative and quantitative evaluation of heteroge-
neous adsorbed monolayers on a semiconductor electrode (H132).
The adsorption of methanol on nickel oxide grown on nickel was
studied (H133). The adsorption of ethylene on nickel was studied
(H134).
Attenuated Total Reflectance. A review was given on efforts
to find spectroscopic evidence for or against the formation of
bilayer islands of adsorbed surfactants (H135). A technique for
depth profiling using multiple-angle ATR FT-IR was described
(H136). A potential problem due to dispersion effects on infrared
spectra in attenuated total reflectance was described (H137).
Variable-angle ATR spectroscopy was used for depth profiling of
stratified layers (H138). Spectra of copy toners were obtained
using microscopical internal reflection spectroscopy (H139). The
use of diamond in an ATR design for analysis of highly corrosive
liquids was reported (H140). The evaluation of collector adsorp-
tion phenomena by infrared internal reflectance spectroscopy of
transferred Langmuir-Blodgett films (H141). A new chemical
sensor based on ATR FT-IR spectroscopy was fabricated by
coating an ATR crystal with a hydrophobic mesoporous silica film
which can extract hydrophobic analytes (H142).
ATR was used to monitor the decontamination reactions of
chemical warfare agents (H143). The developmental changes in
the content of carbohydrates and nitrogen-containing compounds
in amaranth plants was measured (H144). The effects of pH and
metal ions on the conformation of bovine serum albumin in
aqueous solution was studied (H145). Diffusion coefficients of
sodium p-aminosalicylate in sheep nasal mucosa and dialysis
membranes were determined (H146). The skin barrier function
was evaluated by measuring the rate of transepidermal water loss
by an in vivo ATR method (H147). The kinetics of adenosine
5′-triphosphate hydrolysis was measured (H148). The infrared
spectra of aqueous solutions of acetohydroxamic acid in soil and
groundwater, and of suspensions of goethite with adsorbed
acetohydroxamic acid, were measured (H149).
Thin amorphous silicon layers on crystalline silicon substrates
were characterized by infrared multiple internal reflection spec-
troscopy (H150). Surface processes occurring during chemical
vapor deposition of silica through tetraethoxysilane onto GaAs
were monitored by ATR (H151). Amorphous silicon monohydride
films were characterized before and after reaction with atomic
deuterium (H152). The hydrogen-bonding features of reacting
film surfaces during hydrogenated amorphous silicon deposition
were investigated (H153). Dissociative adsorption of methyl
iodide on silicon was followed by multiple internal reflection
spectroscopy (H154). In situ real-time measurements of chemical
etching processes were made on silicon surfaces in ammonium
fluoride solution (H155). The interfacial water near the hydro-
philic surface of a silicon single-crystal internal reflection element,
and the hydrophobic surface of a polymer-coated germanium
single-crystal reflection element was characterized (H156, H157).
An FT-IR ATR method was described for quantitative in situ
analysis of the adsorption and rinsing removal of surfactants from
silicon surfaces (H158).
In situ ATR investigations of water, HSiCl3, and Co2(CO)8 on
zinc selenide surfaces were done (H159). The nature of acid sites
present in cation-exchanged montmorillonite was studied by ATR
(H160). Bonding mechanisms of salicylic acid adsorbed onto illite
clay were examined (H161). Hydration processes at the bentonite
surface were studied (H162). The adsorption of polyamine, poly-
(acrylic acid), and poly(ethylene glycol) on montmorillonite was
investigated (H163). The interaction mechanism of sodium
dodecyl sulfonate with mineral fluorite was studied by ATR
(H164). The chelation of titanium oxide, zirconium oxide, and
aluminum oxide surfaces by catechol, 8-quinolinol, and acetylac-
etone was studied by a new in situ ATR spectroscopic method
(H165). Real-time monitoring of electrochemical reactions by
attenuated total reflectance/surface-enhanced IR spectroscopy was
described (H166). An order-disorder process in Langmuir-
Blodgett films of dioctadecyldimethylammonium chloride was
studied (H167). Trace levels of organic impurities in hydrofluoric
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 129R
acid solutions were measured using a clean silicon ATR crystal
to extract the organic impurities (H168). DMSO self-association
in acetonitrile solutions was investigated (H169). The hydrolysis
of trimethyl phosphate in aqueous solutions was studied (H170).
Polarized infrared ATR spectroscopy was used for the three-
dimensional structural analysis of long-chain compounds (H171).
The adsorption of acetic acid on n-CdTe photoelectrodes in
aqueous and nonaqueous solutions was studied (H172). Real-
time in situ ATR monitoring of mesoporous silicate syntheses was
performed (H173). The extent of adsorption and the spatial chain
orientation of adsorbed alkyl phosphate surfactants on alumina
were studied (H174). The poly(p-phenylene vinylene)/chromium
interface was characterized by ATR (H175). The electrochemical
doping and protonation processes of polyaniline were described
using in situ FT-IR-ATR (H176). In situ FT-IR-ATR spectros-
copy was used to characterize the reduced form of polyaniline
(H177, H178).
Diffuse Reflectance. An investigation was done to determine
whether increasing the scanned sample area would improve
results obtained by diffuse reflectance FT-IR spectroscopy (H179).
Diffuse reflectance was combined with gas chromatography as a
coupled technique for the characterization of catalysts (H180).
Diffuse reflectance was used to evaluate cleanliness of rough
surfaces (H181). Solid-phase reactions of solid resin beads were
investigated using diffuse reflectance spectroscopy (H182). The
surface composition of AlN samples exposed to atmospheric air
was analyzed as a function of their preparation method (H183).
The structure of hydroxylated alumina surfaces were characterized
(H184). The use of diffuse reflectance for the nondestructive
inspection of organic films on sandblasted metals was discussed
(H185). The application of diffuse reflectance in the preservation
of historical monuments by monitoring salt migration was de-
scribed (H186). Determination of the anti-sap-stain chemical
didecyldimethylammonium chloride on wood surfaces by diffuse
reflectance was shown to be effective (H187). In situ analysis
was performed on catalytic surfaces of membrane electrode
assemblies in working fuel cells (H188, H189). A study was done
on the reversibility of CdGeON sensors toward oxygen (H190).
The modifications afforded by chemical treatments to the main
functional groups of a bituminous coal were characterized (H191).
The catalytic removal of soot from diesel exhaust gases was
studied (H192). Diffuse reflectance spectra of explosives were
studied (H193). A comparison of several FT-IR sampling tech-
niques, including diffuse reflectance, was investigated for the
characterization of cement systems (H194).
The structural nature of polyacrylates adsorbed on alumina
from aqueous solution was investigated (H195). Adsorption
interactions of bipyridines with the surfaces of different alumina-
pillar interlayered clays were studied (H196). The photochemistry
of nitrates with alkali halides was studied (H197). The thermal
derivatization of porous silicon was measured using diffuse
reflectance spectroscopy (H198). The formation of ethyl tert-butyl
ether on H-modenite was measured (H199). A series of dealu-
minated hydrogen mordenites were investigated with and without
probe molecules CO and H2 (H200). The analysis of volatile
organic chemicals adsorbed onto bentonitic clays was discussed
(H201).
130R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
The application of diffuse reflectance FT-IR spectroscopy
toward heterogeneous catalyst studies was reviewed (H202). The
state of palladium on the surface of titanium dioxide-based carriers
was investigated (H203). The interaction of cobalt cations with
coordinated molecular oxygen species on Co-ZSM-5 emission
control catalysts was studied (H204). The adsorption of paraffins
on simple oxides was studied (H205). Acid-base properties of
the surface of zirconia and zirconia modified with yttria were
studied (H206). A kinetics and diffuse reflectance study of low-
temperature carbon monoxide oxidation over Au-TiO2 catalysts
was done (H207). In situ temperature-programmed diffuse
reflectance studies of V2O5/TiO2 catalysts were described (H208).
The active surface species and the reaction mechanism were
studied in the vapor-phase hydroformylation of ethene over Co/
SiO2 promoted with various noble metals (H209). The reaction
mechanism of catalytic reduction of nitrogen oxides by propene
in the presence of oxygen has been studied (H210). TiO2-
supported W- and Mo-selective catalytic reduction catalysts were
studied before and after poisoning with As3+ oxide (H211).
Colloidal hematite adhered onto silver and mercury electrodes
was studied (H212). Evidence of alloy formation was observed
in a study of CO adsorption on a bimetallic Pt-Pd catalyst
supported on NaY zeolite (H213). The direct thermal interaction
of elemental fluorine with hydrogenated and oxidized diamond
surfaces was investigated (H214). Diffuse reflectance spectros-
copy was used to characterize the adsorbed species when zirconia
is exposed to aqueous oleate and oleic acid over a range of pH
(H215). Adsorption complexes of triacylglycerol and oleic acid
on silica gel and synthetic magnesium silicate were observed
(H216). The thermal and adsorbed-water effects of a (3-amino-
propyl)triethoxysilane layer modified onto the surface of silica gel
were examined (H217). Boron nitride films deposited on steels
from borazine were investigated (H218). The properties of
different chromium oxide phases in the catalytic reduction of NO
by NH3 was studied (H219).
EMISSION
The use of FT-IR emission spectroscopy as a tool for the study
of chemical reactions was reviewed (I1). Another review dis-
cussed the use of FT-IR emission spectroscopy in observing
electronic, rotational-vibrational, and pure rotational transitions
(I2). The potential of near-IR emission spectroscopy for real-time
monitoring of gas-phase molecules was described (I3).
The means to detect, visualize, and survey different kinds of
gases within industrial and energy processes, technological
infrastructure, landfill bodies, and indoor and outdoor environ-
ments were discussed (I4). Exhaust gases from aircraft engine
plumes were analyzed through remote sensing using FT-IR
emission spectroscopy (I5-I7). A new technique was described
that makes possible the laboratory IR emission study of gases of
atmospheric interest, specifically CFC-12 (I8). A design for an
open-path atmospheric monitor that uses both emission and
absorption spectroscopies was discussed (I9). Remote sensing
FT-IR emission spectroscopy was applied to the study of Freon-
12 thermal fragmentation in an alcohol/air flame (I10). FT-IR
emission spectroscopy was used to measure nitric acid and ozone
in the winter polar atmosphere (I11).
 The cure chemistry and kinetics of aerospace epoxy resins
and prepregs were measured in real-time by FT-IR emission
spectroscopy (I12). The in situ analyses of reaction intermediates
and adsorbed species during chemical vapor deposition of silicon-
based films by infrared emission spectroscopy were described
(I13). The sulfidation of molybdenum oxide has been studied
by XPS and IR emission spectroscopy (I14). The dehydroxylation
of a series of the kaolinite clay minerals has been investigated by
FT-IR in situ emission spectroscopy (I15, I16).
The FT-IR emission spectra of several different molecular
species have been studied. These include the OH and OD stretch
of HOI and DOI (I17), the vibration-rotation bands of ND (I18),
the vibration-rotation bands of the CD radical (I19), and the
spectra of ScH and ScD (I20). Similarly, the emission spectra of
CoH (I21), BN (I22), Ge-As-S and Ge-Ga-S glasses doped
with Dy3+ (I23), and LaH and LaD (I24) were studied. The
emission spectrum of FeF was observed in the near-infrared region
(I25), while the radiative decay of hot two-dimensional plasmons
in AlO‚3GaO‚7As/GaAs heterostructures was studied by far-
infrared emission spectroscopy (I26). The far-infrared laser
emission spectra of ammonia isotopomers were reported (I27).
The blackbody infrared radiative dissociation of bradykinin and
its analogues was measured (I28).
The vibrational relaxation of isomerizing alkyl halide complexes
of perylene were measured by stimulated emission spectroscopy
(I29). Plasmas of fluorinated hydrocarbons under conditions
similar to those used in semiconductor surface processing were
analyzed using time-resolved FT-IR emission (I30). The time-
resolved FT-IR absorption and emission spectra of species
produced in hollow cathode molecular discharges were character-
ized (I31). A new method was described that obtains time- and
energy-resolved emission spectra using a step-scan FT spectrom-
eter combined with correlational analysis techniques, providing
superior dynamics and signal-to-noise ratios (I32). The quantita-
tive aspects of FT-IR emission spectroscopy and the simulation
of emission-absorption spectra were reviewed (I33).
PROCESS AND IN SITU ANALYSIS
FT-IR spectroscopy has been used in conjunction with in situ
ellipsometry to characterize the deposition of amorphous hydro-
genated silicon from a remote argon/hydrogen plasma. The FT-
IR results indicated a hydrogen content of 9-25 atom % (J1). IR
transmission spectra with submonolayer resolution of the initial
growth of amorphous hydrogenated Si deposited by F2 laser
chemical vapor deposition (CVD) have been reported. The
technique allows for the evolution of the H content and bonding
configuration on a Si substrate to be monitored during nucleation
and growth (J2). The H content and stoichiometry of silicon
suboxides in a plasma parallel PECVD system have been deter-
mined by FT-IR spectroscopy (J3). In situ IR spectroscopy has
been used to confirm the formation of gold-tetramethylthiourea
(TMTU) complexes from the etching of Au(111) electrode
surfaces in the presence of TMTU (J4). In situ FT-IR spectroscopy
has been used in the study on the nature of the metal complex-
immobilized polyaniline/Prussian blue-modified electrode in the
electroreduction of CO2 in an aqueous solution (J5). Neutral H2O
and H3O+ adsorbed on a Pt(111) electrode from acid solutions
have been identified by in situ IR spectroscopy (J6). The
interfacial oxides formed under steady-state anodic polarization
of p-silicon in fluoride electrolytes has been studied using
difference in situ IR spectroscopy (J7). The promoted electrooxi-
dation of aqueous sulfur dioxide at platinum electrodes has been
studied in acidic medium with the aid of cyclic voltammetry and
in situ FT-IR spectroscopy (J8). The five oxidation states of
osmium carbonyl clusters have been characterized in the elec-
trochemical redox processes using in situ FT-IR (J9). The
activation and reduction of CO2 on a functional dual-film electrode
has been studied by in situ FT-IR spectroscopy (J10). In situ far-
IR spectra of the surface films on Cu and Pt in aqueous solutions
have been obtained using a synchrotron source (J11, J12). A
comparison of static linear polarization selection and a new real-
time technique has been done for the in situ FT-IR spectroelec-
trochemical studies of copper electrodes. The species analyzed
in this comparison were the thiocyanate ion, imidazole, and
glucose (J13). In situ FT-IR spectroscopy has been employed in
the study of the electrode/electrolyte solutions at pH values of
1.2-3.4. The adsorbate associated with the anomalous peaks in
the cyclic voltammetry of Pt(111) in sulfate- and bisulfate-
containing solution was examined (J14). In situ FT-IR has been
used to examine the effects of incorporating redox-active pendant
[Ni(tetraazamacrocycle)]2+ in poly(3-methylthiophenol) on Pt
electrodes (J15). The underpotential deposition (UPD) of copper
and thallium on a Pt(111) electrode in a sulfuric acid solution was
studied by time-resolved in situ IR spectroscopy and electrochemi-
cal scanning tunneling microscopy. Surface changes were re-
ported (J16). In situ electrochemical FT-IR spectroscopy has been
extended to the study of a real carbon-supported platinum-
ruthenium catalyst. Results of the electrooxidation of methanol
at bulk Pt, Pt particles, and carbon black-supported Pt-Ru
electrodes were discussed (J17). The oxidation of propene in
aqueous HClO4 solution was studied on polycrystalline Au
electrodes using differential electrochemical mass spectroscopy
(DEMS) and in situ FT-IR spectroscopy. Reaction pathways and
products were discussed (J18). In situ FT-IR spectroscopy has
been used in the study of the oxidation of 2-propanol on Pt(111),
Pt(110), and Pt(100) electrodes. The reaction intermediates were
characterized for functional groups (J19). Linear polarization
absorption ratios were determined from data for carbon monoxide
and bisulfate anion adsorbed on Pt single-crystal electrodes (J20).
The adsorption of sulfate species at polycrystalline gold electrodes
were studied with in situ FT-IR spectroscopy in a HF/KF buffer
solution of pH 2.8. This method allowed for the clear distinction
between adsorbate and solution features (J21). The redox
processes of poly(thiophene-3-methanol)-modified Pt electrodes
were studied by cyclic voltammetry, in situ optical beam deflection,
and FT-IR techniques. FT-IR results were used to study the
insertion and release of ions into and from the polymer films (J22).
The electrochemical oxidation of thiourea on a Pt electrode was
studied at different potentials using voltammetry and in situ FT-
IR spectroscopy. The chemical changes during the reaction were
discussed (J23). The coadsorption of nitriles and CO on Cu-
ZSM-5 were studied using in situ FT-IR spectroscopy (J24). The
vibrational properties of CN-pseudohalide ions adsorbed on a
Pt(110) single-crystal electrode in aqueous neutral solution were
studied using in situ visible-IR sum frequency generation. The
adsorption behavior of both ions depends drastically on the
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 131R
electrode potential and on the immersion potential (J25). The
adsorption of nitrate ions on Au and Pt electrodes in acid solutions
was studied in acidic solution using in situ FT-IRS. Coordination
on the Au electrodes and reaction products was discussed (J26).
Under- and overpotential deposition of hydrogen on polycrystalline
platinum, Pt(100), Pt(110), and Pt(111) surfaces in sulfuric acidic
medium was monitored by IR-visible sum-frequency generation
(J27). The urea adlayers formed at the surface of Pt(100)
electrodes immersed in urea-containing solutions were character-
ized in situ by cyclic voltammetry and FT-IR spectroscopy. The
bonding orientation of the urea at the surface of the electrode
was discussed (J28). The ethanol electrooxidation on a coelec-
trodeposited Pt-Ru catalyst was studied by in situ FT-IR spec-
troscopy. Only CO2 was detected under the experimental con-
ditions that produced acetaldehyde, acetic acid, and CO2 for a Pt
catalyst (J29). In situ FT-IR spectroscopy was used to characterize
doped films of poly(5-amino-1-naphthol) electrodes. These elec-
trodes were effective in the reduction of chlorate anions (J30).
The electrosorption of CO and CO2 from aqueous solutions of
various pH values on polycrystalline Ni and Pd electrodes has
been studied using in situ IR spectroscopy techniques. Various
adsorbed species were identified (J31). With the help of in situ
multistep FT-IR spectroscopy, two types of adsorbed geminal CO
have been observed for the first time at an electrochemically
modified Rh electrode (J32). The adsorption of CO and interme-
diate species in the electrochemical reduction of CO2 to hydro-
carbons on a Cu electrode was examined using in situ IR
spectroscopy (J33).
The interaction of hydrogen with ZrO2 at high temperatures
has been studied by in situ FT-IR spectroscopy. A proposed
mechanism for the uptake of hydrogen by the surface of the
zirconia was proposed (J34). The role of surface hydrides and
fluorides in the Si-CVD process was studied by in situ FT-IR
spectroscopy (J35). The electrochemical reduction of CO2 by
electrogenerated 4,4′-dimethyl-2,2′-bipyridine-Ni and 1,10-phenan-
throline-Ni complexes was studied by in situ FT-IR spectroscopy.
The reactions of the carbonyl species with these complexes were
discussed (J36). In situ FT-IR has been employed to study the
formation of NH3 during reduction of NOx with propane on H/Cu-
ZSM-5 in the presence of excess oxygen (J37). A photogravi-
metric analyzer with FT-IR has been developed for the monitoring
of removal of nitroglycerin from a reaction process. The FT-IR
was used to analyze the nitroglycerin photodecomposition prod-
ucts on the surface of immobilized titania (J38). In situ FT-IR
spectroscopy has been used for the investigation of the interaction
of chlorinated ethylenes (vinyl chloride, 1,1-dichloroethylene,
trichloroethylene, and perchloroethylene with the surface of
chromium-exchanged zeolite Y (Cr-y) catalyst. The analysis was
performed at different temperatures between 25 and 300 °C (J39).
In situ FT-IR spectroscopy has been used to study the effect of
temperature on the acid-bridged OH groups of mordenite zeolite
with Si/Al ratios between 5.56 and 23.60 (J40). The initial activity
of chromia/alumina catalyst in butane dehydrogenation was
studied in a flow reactor using on-line FT-IR gas analysis. The
time resolution for this analysis was on the order of seconds (J41).
The mixed-valence isopolyanion Mo6O193- was investigated by
means of cyclic voltammography, in situ FT-IR, and UV-visible/
near-IR spectroelectrochemical methods. The characteristics of
132R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
the anionic species were discussed (J42). The decomposition
reaction of methyltrichlorosilane was investigated by an in situ
IR spectroscopic method. The decomposition products were
characterized (J43). In situ IR spectroscopy has been used to
study the interaction of polypeptides and proteins with monomo-
lecular films of phospholipids (J44). FT-IR spectroscopy has been
used in the study of new molecular precursors of titanium oxide
for the sol-gel process (J45). In situ FT-IR has been applied to
the study of the conversion of methane to methanol in a gas
mixture with Fe-Al-P-O catalysts (J46). The absorptions of
SO2 and CO2 to fresh and aged forms of CaO and Ca(OH)2 have
been investigated using in situ IR spectroscopy. This study
focused on the chemistry of SO2 with the deterioration of
calcareous stone monuments (J47). In situ time-resolved FT-IR
spectroscopy was used to study particulate formation in radio
frequency discharges in mixtures of silane, Ar, and N. An
explanation of the results was discussed (J48). FT-IR was used
to probe the nanostructures of novel polymer/organically modified
silicon oxide hybrids obtained from sol-gel reactions of mixtures
of tetraethoxysilane and diethoxydimethylsilane in perfluorosul-
fonic acid films (J49). FT-IR spectroscopy was used to study the
gas-phase thermal decomposition of [Y(TMHD)3], [CU(TMHD)2],
and [Ba(TDFND)2‚tetraclyme] under vacuum and at high tem-
peratures (J50). In situ IR spectroscopy has been used in the
determination of high-pressure phase diagrams of methane/heavy
hydrocarbon mixtures (J51). In situ FT-IR spectroscopy has been
employed in the monitoring of the SiC deposition in an industrial
CVI/CVD reactor. The gaseous species observed were discussed
(J52). In situ FT-IR spectroscopy was used to study syndiotactic
poly(methyl methacrylate) films exposed to high pressure and
supercritical CO2. The effect of mobility changes on spectral
features was discussed (J53). The electrochemical reduction of
CO2 by electrogenerated LNi(0), where L was 4,4′-dimethyl-2,2′-
bipyridine or 1,10-phenanthroline, was studied using in situ FT-
IR spectroscopy (J54). Activation and reduction of CO2 on the
bis(1,8-dihydroxynaphthalene-3,6-disulfonato)iron(II) complex-
fixed polyaniline/Prussian blue-modified electrode was studied by
in situ FT-IR spectroscopy. The site of attachment of the CO2
was discussed (J55). FT-IR has been integrated with a sampling
system and control software as a continuous emission monitor
for the analysis of volatile organic materials and some inorganic
compounds (J56). In situ FT-IR has been used to characterize
the oxidative degradation of working polymeric light-emitting
devices with active layers of poly[2-methoxy-5-(2′ethoxyhexoxyl)-
1,4-phenylenevinylene] (J57). The electrooxidation of methanol
on single-crystal surfaces was characterized by the formation of
strongly adsorbed intermediates. Adsorbed species from this
reaction were detected by in situ FT-IR spectroscopy (J58). The
reactions of acetaldehyde on the surface of CeO2, Pd/CeO2, Co/
CeO2, and Pt/Co/CeO2 were examined by FT-IR spectroscopy.
Identification of the reaction products was discussed (J59). IR
spectroscopy has been used in the analysis of the uniform drying
process of the paper process. This analysis gives information
about temperature distributions along the paper track, supplying
better process control (J60). Toluene alkylation with methanol
over zeolites has been studied using FT-IR (J61). FT-IR spec-
troscopy of CO adsorbed at liquid nitrogen temperatures on zeolite
K-L has aided in the understanding of the interaction of the CO
with the zeolite surface (J62). IR measurement of single layers
and coextruded plastic films has been reported. The application
of this to measure film thickness has been discussed (J63).
ATR FT-IR was used in the analysis of the in situ adsorption
of alkyl- and (perfluoroalkyl)trichlorosilane molecules on Si
substrates. The information from this analysis was used to
determine the Gibbs surface excess of adsorbed surfactants (J64).
Real-time ATR FT-IR monitoring of M41S-type mesoporous silicate
syntheses were performed which allowed the observation of
simultaneous changes in both the organic and inorganic phases
of the mixtures (J65). The chemistry of Si(100) and -(111)
surfaces during immersion in dilute HF solutions was studied by
multiple internal reflection IR spectroscopy (J66). In situ real-
time ATR IR measurements of chemical-etching processes on
Si(111) and Si(100) surfaces in NH4F solutions have been carried
out for the first time (J67). The chemical nature of the Si(100)
and Si(111) surfaces during immersion in dilute HF solution was
investigated using ATR FT-IR spectroscopy (J68, J69). The
dissolution of silicon oxides in hydrofluoric acid at the surface of
a chemically oxidized silicon surface has been characterized by
ATR IR with a spectrochemical cell (J70). A new ATR FT-IR setup
has been used for the in situ spectroscopic study on the ZnSe
crystal surfaces in the range of 600-4000 cm-1. This technique
was used to study very thin water films on the crystal surface
and the formation of polysiloxane films with Si-H bonds at the
surface (J71). The vibrational properties of 2,5-dihydroxybenzyl
mercaptan irreversibly adsorbed on gold electrodes were exam-
ined in 0.1 M HClO4 by ATR FT-IR and by FT-IR RAS techniques.
The surface features were discussed (J72). In situ FT-IR/internal
reflection spectroscopy has been used to study interfacial water
near the hydrophilic surface of a Si single-crystal internal reflection
element. A depth profile of the H2O structure was examined and
reported (J73). In situ ATR FT-IR spectroscopy was used the
examine the extent of adsorption and spatial chain orientation of
adsorbed alkyl phosphate surfactant molecules on alumina. The
effects on surface properties were discussed (J74). In situ
cylindrical internal reflection FT-IR (CIR-FT-IR) was used to
examine the behavior of subcritical and supercritical hydrocarbons
processing over a Y-type zeolite at high temperatures and
pressures (J75). The effect of coke formed by the conversion of
ethylbenzene as well as ethylene on the sorption capacity and
diffusivity of benzene and ethylbenzene in H-ZSM-5 was inves-
tigated by an in situ FT-IR technique. The coke species formed
during this test were characterized (J76). Using in situ FT-IR ATR
spectroscopy, the electrochemical polymerization process of 2,2′-
thienylpyrrole monomer in electrolytes containing LiClO4,
Bu4NClO4, Bu4NBF4, and Bu4NPF6 was studied (J77). The
investigation of the base-acid transition process of emeraldine
(polyaniline) has been carried out by in-situ FT-IR spectroscopic
methods (J78). ATR FT-IR spectroscopy, in conjunction with FT-
Raman, was used to elucidate the mechanism of the reaction of
benzonitrile and hydrogen peroxide in alkali medium (J79). In
situ high-resolution FT-IR spectroscopy was used to study the
photopolymerization of C60 film. A C60 dimer structure was
postulated from the results of this analysis (J80). In situ high-
resolution FT-IR spectroscopy was used to study the orientation
phase transition of a H2O-free C60 film by examining the
temperature dependence of line shift, half-width, and integrated
absorbance of the four fundamental IR-active modes in the high-
resolution IR spectrum (J81). In situ FT-IR spectroscopy was used
to monitor the production of air toxics during the pyrolysis and
combustion of benzene and o-dichlorobenzene. The effects of
temperature and Cl concentration on the formation of polynuclear
aromatic hydrocarbons were discussed (J82). In situ FT-IR was
used to study the polynuclear peroxo complexes formed in a
H2O2- cerium(IV) decatungstate ion-reacting system. The effect
of H2O2 concentration on complexes and reactions was discussed
(J83). The polymerization of 2,2′-thienylpyrrole and the redox
behavior of the resulting polymer film electrodes were studied
by FT-IR ATR experiments. The polymerization process was
studied in aqueous solutions of different pH containing NaClO4,
LiClO4, and NaBF4 (J84). The electrochemical redox processes
of poly(thienylpyrrole) in acetonitrile solutions containing Bu4-
NClO4 or Bu4NPF6 were investigated using FT-IR-ATR spectros-
copy (J85). The effect of moisture on a model silane coupling
agent-modified adhesive bond was studied using FT-IR ATR
spectroscopy. The silane studied was vinylbenzyl(trimethoxysilyl)-
propylethanediamine hydrochloride (J86). In situ FT-IR ATR
spectroscopy has been used to gain a picture of the base-acid
transition of leucoemeraldine, the reduced form of polyaniline in
electrolytes containing KPF6/HPF6, NaClO4/HClO4, and NaReO4/
HReO4 (J87, J88). The electrochemical doping and protonation
process of polyaniline processes have been described using in-
situ FT-IR-ATR spectroscopy (J89). In situ FT-IR MIR spectros-
copy has been used in the study of the electrosynthesis and redox
process of poly(1,5-diaminonaphthalene) (J90). Analytical expres-
sions have been derived within the Leveque approximation, for
the steady-state concentration profile of a reactant or stable
product generated via first-order kinetics at an electrode in a
channel-type electrochemical cell under fully developed laminar
flow. This study has implications on the application of quantitative
ATR FT-IR in a channel-type spectrochemical cell (J91). The
adsorption of acetic acid on the n-CdTe photoelectrode in aqueous
and nonaqueous solutions has been studied using ATR FT-IR
spectroscopy (J92). Theoretical aspects of the application of in-
situ attenuated total reflectance infrared spectroscopy to the study
of a channel-type spectrochemical cell have been developed (J93).
The in situ FT-IR internal reflectance spectroscopy (FT-IR IRS)
analysis of interfacial water near hydrophilic and hydrophobic
surfaces has led to a better understanding of the water structure
near these regions (J94). In situ ATR FT-IR spectroscopy has
been used to investigate the polymerization of aniline on the p-Si
electrode. From this work, a mechanism of the polyaniline
synthesis has been proposed (J95). An ATR IR sensor has been
developed and constructed to monitor the progression of chemical
reactions during processing (J96). A model-assisted feedback
control algorithm was developed to manipulate the mold temper-
ature and control the curing during liquid composite molding of
siloxane (J97). In situ IR spectroscopy has been used to study
and model the hydrogenation steps in ethylene hydroformylation
on 4 wt % Rh/SiO2 (J98).
The adsorption of phosphate species on the well-ordered
Au(111) single-crystal surfaces has been studied with in situ FT-
IR spectroscopy. The spectral features of the adsorbed H2PO4-,
HPO42-, and PO43- have been identified (J99). The surface
roughness and porosity during the photoelectrochemical etching
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 133R
process has been studied by in situ FT-IR spectroscopy using
multiple internal reflection techniques (J100, J101). TiO2 single
crystals were studied in aqueous electrolyte with in situ FT-IR.
Both photoinduced evolution of oxygen from the water and the
oxidation of model organic compounds can be followed with this
technique (J102). The role of surface hydrides and fluorides in
the Si CVD process has been studied by in situ FT-IR spectros-
copy. The conditions for replacement of hydrides by fluorides
and subsequent etching were reported (J103). The anodic
dissolution of p-Si in fluoride media has been studied using in
situ IR spectroscopy for various compositions of the electrolyte.
The IR spectra of the oxide layer revealed information on the
disorder of the oxide in the current plateau (J104). In situ FT-IR
spectroscopy was used to study the adsorption of NO and the
reaction of NO with O2 on H-, NaH-, CuH-, and Cu-ZSM-5
zeolites. Decomposition of NO was observed for all catalysts, but
the rates were observed to differ significantly for the different
materials (J105). The adsorption of acetone and its coadsorption
with CO were studied on a solid-state ion-exchanged Cu-ZSM-5
catalyst using in situ FT-IR spectroscopy. Changes in the C-O
stretching vibrational frequencies of the adsorbed species were
characterized (J106). The adsorption of MeCN and its coadsorp-
tion with CO on a solid-state ion-exchanged Cu-ZSM-5 catalyst
were studied by FT-IR spectroscopy (J107). In situ IR absorbance
spectra of NaVO3 was obtained at pressures up to 300 kbar. Two
distinct phase transformations were observed (J108). In situ FT-
IR microscopy has been utilized in the study of the nature,
strength, and reactivity of the sorption sites of single crystals of
the microporous gallophophate cloverite. Two kinds of structural
hydroxyl groups were identified (J109). Dehydrated Cd-ex-
changed zeolite HY reacted with H2S to give (CdS)4 in zeolite hosts
has been studied by IR spectroscopy. The coordination around
the Cd atoms was discussed (J110). The characterization of the
coordination geometry or Cu ions included within zeolites was
carried out with in situ XAFS, photoluminescence, and IR mea-
surements (J111). The adsorption of phosphate species on
Pt(111) and Pt(100) has been monitored by FT-IR spectroscopy
(J112). The adsorbed residue originating from the contact of SO2
with smooth platinum electrodes was characterized by in situ FT-
IR and cyclic voltammtery in 1 M HF solutions. A potential
dependent spectral feature ranging between 980 and 1020 cm-1
was reported (J113). FT-IR spectroscopy has been employed to
investigate the effect of both the deposition parameters and
subsequent thermal processing on phosphosilicate glass (J114).
In situ IR has been used to study ethylene hydroformylation
catalyzed by silica-supported [Rh12(CO)3O]2- cluster anions. The
counterions in the study were Li+, Na+, K+, and Zn2+ (J115). In
situ IR studies of the oxydehydrogenation reaction of propane over
VPO/TiO2 catalyst indicated the Lewis acid sites are linked to
COx formation and Brønsted sites to propene formation (J116,
J117). The reactivity of adsorbed CO toward H on Rh/SiO2
catalyst has been examined by IR spectroscopy. The effect of
linear CO and bridged CO on the reaction was discussed (J118).
In situ FT-IR was used to study the oxygen adspecies on SrF2/
La2O3 catalyst during the oxidative coupling of methane (J119).
The electrooxidation of CO adsorbed on polycrystalline Pt, Ru,
Pt0.5Ru0.5, and Pt0.7Ru0 was studied by in situ IR spectroscopy
(J120). Internal reflection spectroscopy has been used to obtain
134R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
the in situ IR spectra of ruthenium(II) bipyridyl dicarboxylic acid
adsorbed to Degussa P25 and sol-gel TiO2 films. The site
adsorption structure was discussed (J121). The adsorption of CO
on the Au(332) surface was studied by LEED, surface potential
measurements, temperature-programmed desorption, and IR
spectroscopy. The IR band at 2120 cm-1 was observed to move
to lower wavenumbers with increasing coverage (J122). The
adsorption and reaction of CO on La2O3 has been examined with
UV reflectance and FT-IR spectroscopy. The structural features
of this interaction were discussed (J123). The stretching fre-
quency of adsorbed CO (IR) and the 195Pt NMR of Pt catalysts on
zeolite-NaY have been correlated. The chemisorption results of
this study indicate that a steric effect as well as an electronic effect
was operating (J124). FT-IR spectroscopy has been used to study
the protonic sites of HXSM-5 zeolite effects on adsorption of
methane at low temperatures. These sites are the active sites
for methane conversion at high temperatures (J125). The phy-
sisorption of CO at low temperatures on a catalyst of H-mordenite
embedded into an amorphous silica alumina matrix was investi-
gated by FT-IR. The technique provides a means of characterizing
the porosity of the catalyst (J126). The low-temperature methane
adsorption and coadsorption of methane and CO on HZSM-5 and
Mo/HZSM-5 were investigated by FT-IR spectroscopy. The
assignment of observed bands was discussed (J127). The
coordination geometry of Cu ions within zeolites was studied using
photoluminescence and IR spectroscopy (J128). Gravimetric
measurements with FT-IR analysis were used in the quantitative
analysis of CO chemisorption on Pt/H zeolites (J129). The
reactivity of Pt metal clusters supported on KL zeolite toward CO
was studied by FT-IR spectroscopy at various pressures (J130).
The interaction of CO and N2 with ferrisilicate MFI-type zeolites
has been studied by FT-IR spectroscopy. The surface chemistry
of the interaction was discussed (J131). The chemistry of the
interaction of dimethyl ether with H-ZSM-5 zeolites has been
studied using in situ IR spectroscopy (J132). The effects of
structural defects and alloying of Pt/ZnO on adsorbed CO
chemistry have been studied using FT-IR spectroscopy (J133).
The surface reactions of CCl4 with zeolites have been examined
by FT-IR spectroscopy. The Fermi resonance observed was
explained by reaction intermediates (J134). The IR spectra of CO
adsorbed at 77 K on ZnO ex-carbonate, on CoO and on CoO-
ZnO solid solutions have been characterized (J135). The adsorp-
tion and oxidation of CO over gold supported on ZnO and TiO2
were studied by FT-IR and mass spectroscopy. Two kinds of sites
on the particles were identified (J136). The structure of adsorbed
CO on nanostructured Pt-Ru electrode surfaces has been
examined by FT-IR spectroscopy (J137). IR spectroscopy has
been used in the study of metal support interactions in the
adsorption of CO on supported platinum in Pt/LTL and Pt/SiO2
catalysts (J138). CO adsorption on high-loading Ni/MgO samples
treated at 800 and 900 °C was studied by IR spectroscopy. Linear
and bridged monocarbonyls were characterized (J139). IR
spectroscopy was used in the study of the CO stretching mode
with respect to Brønsted and Lewis acidity of dealuminated acid
ZSM 5, ultrastable Y, fluorinated USY, and Y zeolites. Changes
in the OH IR bands on the surface of the zeolites were discussed
(J140). The measurement of the shift in the stretching frequency
of Brønsted hydroxyl groups on adsorption of a weak base has
been proposed as a quantitative measurement of the strength of
acid sites in zeolites. This information might prove useful in the
development of catalysts (J141). The IR spectrum of CO adsorbed
on Ni(100) has been shown to display an additional high-frequency
band at approximately 2200 cm-1. This absorbance has been
attributed to the internal stretching mode of CO molecules weakly
bonded to the Ni surface atoms (J142). The picosecond mid-IR
pump-probe experiments were used to study vibrational relax-
ation of CO bound to synthetic metalloporphyrins with different
metal atoms (Fe, Ru, Os), different axial nitrogenous ligands, and
differently substituted porphyrins (J143). Ag clusters were
prepared by either gas aggregation or matrix aggregation. The
clusters were embedded in CO and CO/Ar matrixes, and the CO
stretch frequency of the monolayer coverage was discussed
(J144). The structure and hydrogen bonding of solid N1-alkyl-
arylthioureas was studied by 13C CP/MASS and IR spectroscopy.
It was concluded that, with the exception of cyclic dimers of N1
propenethioureas, hydrogen bonding occurs at N1 and N2 of the
structure (J145). The electrooxidation of CO adsorbed on
polycrystalline Pt, Ru, and Pt-Ru alloys has been studied by in
situ IR spectroscopy. The effects of increased Ru content on the
IR spectrum of the CO stretch vibration were discussed (J146).
The Cu2+ ion sites in copper-exchanged ZSM-5 for activation and
methanol synthesis have been studied by XPS and FT-IR spec-
troscopy (J147). The adsorption of CO and the coadsorption of
CO and H2 on Ni/Al2O3 catalyst were studied by FT-IR. The
interaction of the CO molecules with the surface was described
(J148). The adsorption of CO2 and CO2/H2 on SiO2-supported
Cs-doped Cu catalyst has been examined by FT-IR spectroscopy.
Two forms of adsorbed carboxylate were identified also (J149).
The adsorption of CO, NO, and C2H4 and reaction of CO+H2 on
well-dispersed FeOx/TIO2 and FeOx/Al2O3 catalysts were studied
with pulse adsorption and temperature-programmed desorption
of NO and FT-IR. The adsorption properties and reaction products
of the study were discussed (J150). Some Ru and Co carbonyl
clusters in zeolite pores were prepared by a ship-in-bottle
technique and characterized by FT-IR and EXAFS (J151). Some
Cu and Cu-Ni-on-silica catalysts were characterized by IR
spectroscopy of adsorbed CO. The interactions of surface species
were discussed (J152). The adsorption of CO and CO2 on two
series of palladium-based catalysts was compared by IR spectros-
copy (J153). The adsorption of Co on CuO/SiO2 and Cu-ZSM-5
catalysts was studied by IR spectroscopy (J154). The vibration
frequencies of adsorbed CO molecules on Pd/MgO(100) have
been examined by fast FT-IR spectroscopy (J155). Both linear
and bridged forms of adsorbed CO on Pt/ZrO2 catalyst have been
observed using FT-IR spectroscopy (J156). IR spectroscopy has
been used to study the decomposition of CO2 on a copper-
containing methanol catalyst (J157). The transient nature of
adsorbates for the reaction of NO with CO over a 4 wt % Rh/SiO2
catalyst has been studied by in situ IR spectroscopy combined
with pulse transient techniques (J158). The reactivity of adsorbed
CO toward H has been studied using a temperature-programmed
reaction technique coupled with IR spectroscopy. This combina-
tion provided information on the structure and reactivity of
adsorbates, activation energy, and kinetic data for the CO
hydrogenation reaction (J159). The adsorption of CO on the
MgO(100) surface prepared in situ was studied using polarization
FT-IR spectroscopy. The IR spectra from p- and s-polarization
were discussed (J160). Physically adsorbed acetonitrile, THF,
diethyl ether, and methanol-d in supercritical SO2 on silica gel
were studied by FT-IR at pressures up to 15 MPa (J161). The
acid properties of pure and sulfated zirconias were studied by FT-
IR spectroscopy of adsorbed CO and NH3 probe molecules. Two
types of Brønsted acidic centers and two types of Lewis acid
centers were identified (J162). The oxidation state of Rh/Al2O3
catalyst was investigated by XPS and IR spectroscopy of adsorbed
CO (J163). The dynamics of adsorbed species on Rh/SiO2 catalyst
during CO hydrogenation to form methane was studied by in situ
IR spectroscopy combined with steady-state isotopic transient and
pulsing CO methods (J164). In situ MIR IR studies of semicon-
ducting electrode surfaces have provided information of surface
chemistry of HF-rinsed silicon (J165).
The adsorption and decomposition of N2O over ZrO2 has been
studied in situ by in situ diffuse reflectance IR Fourier transform
DRIFT, TPD, TPR, and XPS. The surface chemistry was dis-
cussed (J166). An in situ DRIFTS technique was used in the study
of the active surface species and the reaction mechanism of the
vapor-phase hydroformylation of ethene over Co/SiO2 promoted
with various noble metals (J167). DRIFT spectra of two humic
sodium salts have been recorded to study structural changes
caused by heating (J168). In situ DRIFT spectroscopy has been
introduced as a method for studying the catalytic surfaces of
membrane electrode assemblies in working fuel cells (J169). The
catalytic surfaces of membrane electrode assemblies in direct
methanol/oxygen fuel cells were investigated in situ by FT-IR
diffuse reflection spectroscopy. Possible mechanisms for metha-
nol, formaldehyde, and formic acid oxidation at the anode surfaces
were discussed (J170). In situ DRIFT spectroscopy was used to
study both the adsorbed and desorbed species produced on high-
surface-area anodes (Pt-Ru, Pt black) and cathodes (Pt black)
of direct methanol/oxygen fuel cells (J171). In situ DRIFT
spectroscopy has been used in the study of chromia on titania
catalysts containing different chromium oxide phases used for the
low-temperature selective catalytic reduction of nitric oxide by
ammonia (J172). In situ DRIFT spectroscopy has been utilized
in the high-temperature study of OD stretching vibrations on the
surface of various Li ceramics. The frequency of the stretching
vibration of the OD group has a strong correlation with the LI/O
ratio of the ceramics (J173). Hydroxyl groups on the surface of
Li2O were studied by DRIFTS at high temperatures under
controlled D2O and D2 partial pressures (J174). Temperature-
programmed DRIFT spectroscopy has been proposed to follow
in situ temperature-programmed reduction and the temperature-
programmed programmed desorption experiments of catalyst
systems. TPDRIFTS studies of desorption and reduction of a
conventional V2O5/TiO2 catalyst have been carried out (J175). The
reaction mechanism of catalytic reduction of nitrogen oxides by
propene in the presence of O2 has been studied by in situ DRIFT
spectroscopy (J176). In situ FT-IR ATR spectroscopy with mass
spectroscopy were used in the kinetic investigation of the reaction
mechanism of CO2 methanation over a catalyst (J177). The
oxygenation functions issued from the oxidative thermal treatment
of mesocarbon microbeads at 320 °C were investigated by
DRIFTS. Some information about the reaction kinetics and
mechanism were discussed (J178).
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 135R
 In situ reflection IR spectroscopy with electrochemical modula-
tion was used to study the coadsorption of anions for the system
Tlads/Pt(111) in dilute H2SO4 and HClO4. Possible structures of
the Tl-ClO4 and Tl-HSO4 adlayers at Pt(111) were discussed
(J179). The potential-dependent structural change and irreversible
anodic decomposition of the self-assembled monolayers of 3-mer-
captopropanenitrile and of 8-mercaptooctanenitrile on gold elec-
trode were studied by SNIFTIRS (J180). SNIFTIRS has been used
in the study of the structure of the double layer for the system
Pt(hkl)/acetonitrile with tetraethylammonium perchlorate and
sodium perchlorate electrolytes (J181). The SNIFTIRS results
obtained on polyaniline films containing heteropoly anions in acidic
solutions have been reported. The report focused on the behavior
of the anions during the redox switching of the polymer (J182).
SNIFTIRS has been used to probe the concentration change of
the perchlorate anion in the electrochemical double layer at
Au(100) (J183). SNIFTIRS and two internal reflectance modes
have been used in the study of the surface chemistry of Li
electrodes and nonactive electrodes polarized to low potentials
in LiC(SO2CF3)3 solutions in 1,3-dioxolane and THF (J184). The
electrooxidation of hypophosphite ions on polycrystalline nickel
in alkaline solutions was studied using cyclic voltammetry,
chronoamperometry, and in situ IR spectroscopy (J185). SNIF-
TIRS studies on the electrooxidation of hypophosphite at poly-
crystalline and single-crystal Ni electrodes indicated a process
dependent upon the structure of the crystal plane exposed for
the electrolyte (J186). The subtractively normalized interfacial
FT-IR technique has been applied to the in situ IR spectroscopic
study of electrochemical doping of poly(N-vinylcarbazole). The
doping of ClO4- anion was shown to be limited by cross-linking
of the polymer (J187). Subtractive normalized FT-IR spectroscopy
studies were performed on the electroreduction of CO2 at a Cu
electrode, using isotopically labeled CO2 and HCO3- in H2O and
D2O (J188).
In situ external reflection FT-IR spectroscopy was performed
during cyclic voltametric polymerization of poly(p-phenylene) films
(J189). Nitridation of GaAs(001) surfaces grown by MBE was
observed by detection of reflectance change caused by the
formation of Ga-N and As-N bonds by reflection FT-IR spec-
troscopy (J190). In situ external reflection absorption FT-IR
spectroscopy was used to understand the dynamics of the organic/
inorganic interface during crystal growth. The dynamics of
template-directed calcite crystallization were studied (J191). In
situ reflectance FT-IR spectroscopy has been used to study the
adsorbed species, reactive intermediates, poisoning intermediates,
and reaction products of the electrocatalytic oxidation of methanol
on Pt-Ru electrodes (J192). In situ IR reflectance spectroscopy
combined with spectral simulation has been applied to the study
of the supramolecular structure of ethyl xanthate (C2H5OCS2-)
species on cuprous sulfide. The identity of adsorption products
was discussed (J193). External reflectance FT-IR spectroscopy
was used to study the electrochemical deposited poly(o-phen-
ylenediamine) on a Pt electrode. The film was doped with ClO4-
and the resulting features were characterized (J194). IR reflec-
tance spectroscopy for thin-film measurement has been applied
in the semiconductor industry. This technique has been used
for the multilayer thickness and doping concentration determina-
tions (J195).
136R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
The potential-dependent structure change and irreversible
anodic decomposition reaction of a 2-(11-mercaptoundecyl)hy-
droquinone monolayer on a gold electrode surface in 0.1 mol/L
HClO4 solution was studied by electrochemical in situ FT-IR
reflectance absorbance spectroscopy (J196). The effects of Ar,
H2/AR, and H2/O2/Ar downstream microwave plasmas on the
surface structure and properties of poly(vinyl chloride) films have
been studied using in situ IR reflection-absorption spectroscopy
(J197). Real-time IR reflectance spectroscopy has been employed
to identify the hydrogen incorporation and release process that
control the final hydrogen content of hydrogenated amorphous
silicon films (J198). In situ IR reflectance absorbance spectros-
copy has been used to detect reaction products resulting from
the etching of Si in Cl2 plasmas. The species in the gas phase
and at the surface were characterized (J199). The electrochemical
behavior of an azobenzene containing a self-assembled monolayer,
10-[4-(phenylazo)phenoxy]decane-1-thiol, was examined by in situ
FT-IR reflection absorption spectroscopy. The process and
architecture were discussed (J200). In situ reflectance IR spec-
troscopy was used in the real-time monitoring of the metallorganic
vapor-phase epitaxy growth of InGaAsP films (J201). In situ IR
ellipsometry was used to demonstrate the efficiency of several
plasmas in the removal of hydrocarbon contamination from
metallic surfaces prior to film deposition (J202). In situ IR
reflection spectroscopy has been combined with spectral simula-
tion in the study of monolayers of ethyl xanthate formed at a
controlled potential on cuprous sulfide (J203). An approach to
the use of IR reflectance spectroscopy for thin-film measurement
in the semiconductor industry has been described. The multilayer
thickness and doping concentration of IC wafers can be deter-
mined by a single-angle, unpolarized IR reflectance measurement
using an FT-IR spectrometer (J204). Reflectance IR spectra of
tungsten oxide films have been used to determine the refractive
index and extinction coefficients (J205). The behavior of diethyl
carbonate electrolyte on lithium with a surface film was examined
by in situ FT-IR spectroscopy. Solvent penetration of the film and
reaction with the lithium was observed (J206). In situ IR
absorption spectroscopy was measured for a hot-filament diamond
growth process. Absorptions of CH4 and C2H2 were detected
(J207). In situ IR absorption was used to monitor diamond films
prepared by hot-filament CVD. The presence of C2H2 in the
diamond film was proposed as the active radical in diamond
growth (J208). The enhancement of copper growth in the
chemical vapor deposition of Cu(II) by auxiliary reagents has been
monitored by FT-IR spectroscopy (J209). In situ IR reflection-
absorption spectroscopy has been used for conformational analysis
of different regions of partially deuterated fatty acid and phos-
pholipid Langmuir films (J210). A versatile, thin-layer cell to
perform in situ IR spectroelectrochemistry has been used to
monitor the electrochemical reaction of oxyhalide electrolytes
(J211). The interaction of hydrophobic and hydrophilic species
at the surface of minerals has been studied using in situ FT-IR
reflection spectroscopy and ATR FT-IR spectroscopy (J212). In
situ IR spectroscopy was used to monitor the adsorptive and
catalytic events occurring at the gas/solid interfaces during
2-propanol decomposition over pure and MnOx-modified aluminas
(J213). The atomic layer controlled deposition of silicon nitride
has been studied by FT-IR reflection absorption spectroscopy
(J214). The real-time in situ observation of deposition and re-
evaporation of N-vinylcarbazole polymer on a Ag-coated glass plate
was performed using FT-IR RA spectroscopy (J215). Real-time
in situ FT-IR RA spectroscopy has been used to evaluate the vapor
deposition polymerization of N-vinylcarbazole (J216). Reflectance
FT-IR spectroscopy was used to study the abnormal optic proper-
ties of adsorbed CO on a dispersed Pt layer on different substrates
(J217). Reflectance absorbance IR spectroscopy has been used
to study the adsorption and oxidation of CO on Pt(110) (J218).
Reflectance absorbance IR spectroscopy has been used to ob-
served the reversible phase transition between chemisorbed CO
on Cu(100) with physisorbed overlayers (J219). FT-IR RA spectra
obtained for a set of D- and isotopic carbon-labeled ethoxides
adsorbed on the Cu(111) surface have been used to determine
the orientation of the adsorbed ethoxide (J220). The thermal
desorption of CO and NO on MO2C has been studied using
reflectance absorbance IR spectroscopy (J221). The adsorption
and desorption of CO and hydrogen on K-modified Ir(111) has
been studied using reflectance absorbance IR spectroscopy (J222).
Polarization modulation IR reflectance absorption spectroscopy
has been applied for the first time to the study of the adsorption
of CO on Co(001) (J223). RAIRS has been used to identify and
characterize three distinct coverage-dependent phases for CO on
Co(1010). The orientation of the CO on the surfaces was
discussed (J224). The adsorption of cyclohexane on clean and
O-modified Ni(111) surfaces was studied by RAIRS. The orienta-
tion of the cyclohexane at the surface was discussed (J225).
Adsorption of CO on Ni(100) surfaces has been studied by
reflectance absorption IR spectroscopy (J226). In situ reflectance
FT-IR has been used for the evaluation of the photoinduced
reaction at an aqueous solution/semiconductor interface of a (S)-
lysine solution (J227). The coadsorption of H2O and SO3
molecules on Pt(111) has been studied by reflectance-absorption
IR spectroscopy. The structure at the surface of the electrode
was shown to be a double layer (J228). Reflectance-absorbance
IR spectroscopy in conjunction with scanning tunneling micros-
copy has been used to study the structure of irreversibly adsorbed
cyanide adlayers on a Pt(111) electrode (J229). The nitrous oxide
generated by the electrochemical reduction of nitrite on a
polycrystalline platinum electrode in aqueous HClO4 was moni-
tored by in situ FT-IR reflection adsorption spectroscopy. IR
observations were found to agree with on-line mass spectrometry
(J230). The interfacial behavior of water molecules at a polycrys-
talline gold electrode surface in aqueous sodium halide solutions
was studied by in situ FT-IR reflection absorption spectroscopy.
Frequency shift dependence on the electrolyte anion was observed
(J231).
The acidity of cloverite was studied by in situ FT-IR microscopy
of sorption of probe molecules with varying basicity. Changes in
the cloverite lattice were discussed (J232). Spatially resolved IR
microscopy was used in conjunction with the contact method to
conduct in situ diffusion experiments of photocured polymer-
dispersed liquid crystals (J233). In situ diffusion and miscibility
studies of polymer-dispersed liquid crystals dissolved in a polymer
matrix were carried out using FT-IR microscopy. This technique
was used to study the miscibility of a liquid crystal (E7) in poly-
(butyl methacrylate) (J234). Single-bead FT-IR microscopy was
used for the real-time monitoring of the catalytic oxidation of
alcohol to aldehydes and ketones on resin support (J235).
Methodology for the in situ IR monitoring and analysis of solid-
phase organic reactions has been developed. This technique has
been applied to the analysis of solvent diffusion into and subse-
quent washout from aminomethyl polystyrene beads (J236). The
interaction of allylbenzene with oxide catalyst surfaces having
different surface characteristics has been investigated by FT-IR
spectroscopy (J237).
A prototype FT-IR-based measurement system designed for
continuous emission monitoring has been tested in full-scale and
pilot plant-scale fossil fuel-fired combustors. The results of these
applications are discussed (J238, J239). IR absorption spectra of
molecular clusters formed in a supersonic free jet expansion were
measured at various conditions. Cluster size and distribution were
discussed (J240). Emission IR spectroscopy has been demon-
strated to be an effective technique for in situ analysis of reaction
intermediates and adsorbed species during chemical vapor deposi-
tion of Si-based films at high temperatures (J241). In situ IR
spectroscopy was used to study the intermediates of the reaction
of NOx reduction with propane in excess O2 on Cu-ZSM5- zeolites
(J242). FT-IR technology has been successfully applied to the
monitoring of emission gases from an oil refinery. This technique
monitors CO2, SO2, NOx, NH3, and HCl in the presence of H2O
(J243). Gas-phase FT-IR has been applied to the on-line analysis
of effluents containing trimethylamine and methanol quantitatively
using PLS (J244).
NIR spectroscopy has been used to develop a method for the
determination of lubrication properties of oils (J245). On-line NIR
monitoring to a polyol process resulted in a decrease in production
of out-of-specification material and increased the plant throughput
(J246). A proposal for the use of mid-IR spectroscopy to provide
linear calibration numbers to calibrate on-line NIR monitors with
nonlinear features has been suggested (J247). On-line NIR in
hostile environments has been shown to be advantageous in many
incidents. The calibration problems have been noted, but the
highly precise results from the NIR is a strong drawing point
(J248). A report has been written on the practicality of keeping
NIR working in an industrial environment. Calibration model
transfer and maintenance were two topics covered (J249). NIR
spectroscopy has been applied to the noninvasive on-line detection
of cortical spreading depression in the pentobarbital-anesthetized
rat (J250).
An automated system for the on-line monitoring of powder
blending processes has been developed and applied to give a real-
time determination of blend homogeneity (J251). NIR spectros-
copy has been evaluated as an on-line technique to monitor the
homogeneity of a pharmaceutical blend containing 10% sodium
benzoate, 39% microcrystalline cellulose, 50% lactose, and 1%
magnesium stearate. The experiments were carried out using
fiber optics, a commercially available NIR spectrometer, and a
blender (J252).
The suitability of diffuse reflectance NIR spectroscopy as an
on-line method to monitor process streams was tested in a pilot
plant-scale oil sand extraction plant. The feasibility of monitoring
feed stream conditions was demonstrated by principal component
analysis of the measured spectra (J253). Diffuse reflectance NIR
spectroscopy was applied in an at-line process analytical interface
to determine moisture content in bulk hard gelatin capsules. No
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 137R
sample pretreatment was required, and the analytical time was
1-2 min (J254).
The need for stable, high-quality process NIR and IR spectro-
scopic analysis has been discussed. Steps to condition the
samples prior to analysis have been presented (J255). A method
has been developed for the NIR monitoring of the cracking
property of a feed to a steam cracking process (J256, J257). NIR
using a ripple calibration technique has been described and
applied to the characterization of web thickness and coating
monitoring (J258). A new on-line process control spectrometer
for measurements from the UV to the IR has been developed and
tested in combustion gas analysis of a waste incineration plant
(J259). A high-pressure and temperature in situ transmission IR
reactor cell has been developed and applied to the study of
adsorbates in CO hydrogenation and NO-CO reaction on Rh/
SiO2 (J260). A transmission IR cell of simple construction has
been developed to study heterogeneous catalysis in situ. The cell
was demonstrated on the catalytic NOx removal (J261). A
generalized mathematical treatment has been developed that
enables the quantitative analysis of various in situ spectroscopic
experiments involving detection of solution-phase species gener-
ated at the surface of a rotating disk and ring disk, channel, and
tube-type electrodes under steady state (J262). An attempt at
application of modern IR spectroscopy as a noncontact-nonde-
structive technique for evaluation of chemical processes has led
to an improved sample handling system. Use of this has been
recommended for off-line as well as on-line applications (J263). A
fixed-volume sample of a reaction mixture of a chemical process
has been injected into a liquid carrier stream. The stream was
passed through an IR detector which was used to monitor a
species of the reaction mix (J264). Chemometrics has been
applied to the NIR monitoring of the manufacturing of ethyl
glucoside fatty ester (J265).
A closed loop on-line NIR spectrometer has been used in the
analysis of the gasoline blending process. This has enabled the
operation to gain tighter control of the octane number of their
process (J266). On-line prediction of 10 gasoline properties
including research and motor octane numbers, vapor pressure,
API gravity, and aromatic contents were carried out using NIR
spectroscopy and fiber optics (J267). NIR spectroscopy with fiber
optics has been used in on-line determination of hydrocarbon
gases at a petrochemical plant in mixtures of ethane, ethene,
propane, and propene (J268). Fiber-optic FT-IR spectroscopy has
been applied to the in situ monitoring of input partial pressures
of organometallic precursors in a vertical rotating-disk OMVPE
reactor (J269). A novel H2O-cooled mid-IR fiber-optic probe with
calcogenide fibers and a ZnSe internal reflection element has been
use in the in situ analysis of an acid-catalyzed esterification reaction
in toluene at 110 °C (J270). An IR fiber-optic sensor has been
developed for the in situ detection of chlorinated hydrocarbons
and other pollutant species in water (J271). NIR process applica-
tions focused on the use of fiber optics and probes to interface to
the process have been carried out in single-point and multiple-
point NIR process analysis. The technique has been reported to
produce a result in 45 s or less (J272). NIR spectroscopy using
fiber optics has been applied as a monitor of homogeneous and
heterogeneous reactions. This technique has been applied
directly to full-size chemical reactors (J273).
138R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
Imaging NIR radiometry has been employed successfully for
radiance measurements of the closed coupled atomization of nickel
base superalloys. The technique provides opportunities for real-
time process control feedback (J274). A spatially resolved IR
imaging technique has been developed to monitor the linear
adsorbed CO coverage on supported catalyst surface to better
understand the dynamics of spatitemporal patterns on heteroge-
neous catalyst (J275).
NIR spectroscopy has been used as a process monitor for the
anionic polymerization of styrene and isoprene in cyclohexane and
in THF (J276). In situ real-time NIR monitoring has been
demonstrated in the reaction of phenyl glycidyl ether with aniline
and bisphenol A diglycidyl ether with 1,8-diaminonaphthalene in
and epoxy resin-amine reactions (J277). The esterification
reaction between acid or anhydride and an alcohol has been
monitored by NIR spectroscopy for both small molecules (J278)
and polyesters (J279). NIR has been used to measure and control
properties of polyamide formation in the manufacturing of poly-
amide yarn (J280). The application of IR and UV photometers in
the continuous monitoring of product purity has been discussed
(J281). The thermal elimination of NaCl from sodium chloro-
acetate, a polymerization reaction that takes place between 150
and 200 °C in the solid state, has been monitored by in situ IR
spectroscopy. The polymerization process, intermediates, end
groups, and byproducts have been explained from these results
(J282). Direct control of fermentation by on-line NIR spectroscopy
has been described (J283). NIR spectroscopy has been shown
to provide tighter process control, greater process knowledge,
and improved product quality assurance in fermentation process
analysis (J284). NIR spectroscopy has been applied to the process
control of antithrombin III production using a partial least-squares
algorithm (J285). NIR spectroscopy has been applied to the
postconsumer package identification. A correct classification rate
of better than 97% for six major types of packages in household
garbage was reported (J286).
An aqueous supercritical fluid extraction (SFE) FT-IR spec-
troscopy technique was used to monitor dodecane in water
ranging from 200 to 12.5 ppm (J287). A simple on-line SFE FT-
IR transmission cell has been used to obtain both qualitative and
quantitative information about analytes in supercritical fluids
(J288).
A review has been written on the available spectroscopic
techniques for the in situ study of combustion chemistry occurring
in an internal combustion engine chamber (J289).
FT-IR spectroscopy has been used in the study of fluorine
dopant levels in plasma-enhanced chemical-deposited fluorinated
silica glasses. The effects of dopant levels on peak positions,
areas, film thickness, and physical properties were reported (J290).
FT-IR spectroscopy has been used to monitor exhaust gases
produced from the plasma-supported gas-phase cleaning of
PECVD facilities (J291).
A list of Internet sites has been presented which may be of
interest to anyone dealing with IR and near-IR spectrochemical
analysis (J292). A new mathematical correction method has been
developed for on-line film thickness determination for FT-IR
analysis incorporating both optical interference and absorption
methods (J293). FT-IR spectroscopy has been applied to the
analysis of pollution prevention systems in ceramic processing
(J294). FT-IR has been applied to the determination of chemical
concentrations of constituent classes of hydrocarbon feed to a
catalytic cracking process (J295). Discriminant analysis using
principle components of mid-IR spectral data has been shown to
be a powerful quality validation tool for manufacturing processes
(J296). Initial studies on open-path FT-IR for measurements at a
refinery, chemical plant, and natural gas processing facility have
proven promising. The effects of water vapor interference have
been reduced using software algorithms (J297). The open-path
FT-IR technology was applied for a four-week period around the
process area of an industrial chemical facility. Methods for dealing
with background collection, quality assurance techniques, predic-
tion modeling, and data storage, presentation, and retrieval were
discussed (J298). The translational energy of CO2 produced from
CO oxidation on Pd foil at 600 K was studied using high-resolution
IR chemiluminescence spectroscopy. The rotational structure of
certain vibrational transitions was fully resolved using a FT-IR
spectrometer operating at 0.006-cm-1 resolution (J299). This
technique has also been applied to the catalytic oxidation of CO
on Pt(110), Pt(111), and polycrystalline Pt surfaces. The vibra-
tional temperatures of the resulting products were discussed
(J300). A combined IR and MS technique has been used to
determine extinction coefficients of adsorbed CO on the 4% Rh/
SiO2 catalyst. The procedure provides a fast and accurate method
for the determination of extinction coefficients of adsorbed surface
species (J301). The structure of a triruthenium ketenylidene
cluster deposited on MgO, SiO2, and SiO2-Al2O3 has been
examined by FT-IR and Raman spectroscopy (J302). A cell and
optics design for in situ far-IR spectroscopy study of electrode
surfaces using synchrotron radiation has been discussed. Precau-
tions necessary for good results were also discussed (J303).
Explanations on application of interferometer- and grating-based
IR spectrometers on process analysis with calibration strategies
have been published (J304).
Octane number has been calibrated successfully with accuracy
and precision sufficient for ASTM conformance using an acous-
tooptic process spectrometer (J305). Oxidation of CO over a
palladium/zirconia catalyst obtained from an amorphous Pd25Zr75
precursor was investigated by time-resolved FT-IR spectroscopy
(J306). Two types of adsorbed geminal CO have been observed
for the first time at an electrochemically modified Rh electrode
using in situ multistep FT-IR spectroscopy (J307). The reaction
of dimethylaluminum hydride with photochemically deposited
hydrogenated amorphous silicon was studied in situ with polariza-
tion modulation IR spectroscopy (J308, J309).
ENVIRONMENTAL ANALYSIS
A review of the environmental applications of near-IR spec-
troscopy was presented (K1). The use of FT-IR for monitoring
processes at coal-fired power plants was reviewed (K2). FT-IR
was included along with other spectroscopic techniques in a
review of methods for studying combustion chemistry in an
internal combustion engine chamber (K3). The use of IR
techniques such as DRIFT and ATR for soil analysis was described
in a review (K4).
FT-IR, NMR, and chromatographic techniques were used in
the differentiation of chlorinated dibenzo-p-dioxin isomer pairs
(K5). Seven tetrachlorobutadiene isomers were identified using
ab initio calculations and GC/MS/FT-IR (K6). The absorption
of SO2 and CO2 on CaO and Ca(OH)2 was studied by in situ IR
(K7). Results from this study may aid in understanding how
polluted air can lead to the deterioration of stone monuments and
buildings. IR and X-ray diffraction methods for determination of
quartz in coal and airborne dust were compared (K8).
Motor oil contamination in sandy loam was determined using
near-IR reflectance spectroscopy (K9). Hazardous organic com-
pounds were detected in sandy soil using IR fiber-optic sensors
(K10). An IR method to screen soil samples from waste sites for
explosives, pesticides, and some volatile or semivolatile organics
was discussed (K11). Explosives in soils were detected via the
pyrolysis products using tunable infrared laser differential absorp-
tion spectroscopy (TILDAS) (K12). An FT-IR spectrometer and
fiber-optic probe were used for real-time analysis of soil for organic
contaminants (K13). FT-IR was among the techniques used to
investigate the inorganic compounds present in coal ash from
power plants (K14). The use of a polypropylene filter and IR for
the quantitative determination of respirable cristobalite in airborne
dust was reported (K15).
Chemometrics and a near-IR analyzer that uses acoustooptic
tunable filter (AOTF) spectrometry were employed to identify
organic contaminants in pretreated wastewater (K16). Volatile
organic compounds (VOCs) were detected in water using solid-
phase microextraction of the VOCs into Parafilm and IR analysis
of the Parafilm (K17). Chlorinated pesticides in water were
concentrated into a chloroparaffin-plasticized PVC coating on an
ATR element or optical fiber and analyzed by FT-IR (K18). A
Teflon-coated silver halide optical fiber was evaluated as a sensor
for the FT-IR analysis of chlorinated hydrocarbons in water (K19).
Herbicides in river water were identified by liquid chromatogra-
phy/FT-IR (K20). Low concentrations of hydrocarbons in water
were detected by coupling an aqueous supercritical fluid extraction
vessel to an FT-IR spectrometer (K21). An evanescent field
absorbance sensor operating in the near-IR region was used for
the detection of hydrocarbons in water (K22). A filter-based
infrared analyzer for measurement of oil contaminants in water
was described (K23). Reports were published on the evaluation
of IR sensors capable of detecting oil spills on water at night (K24,
K25). The nondispersive IR organic carbon analyzer and the CO2
coulometer were compared as methods for the determination of
dissolved inorganic carbon (DIC) in water (K26).
Examples were given to illustrate how process analysis
monitors can be used for pollution control (K27). The desorption
of greenhouse gases (CO2, N2O, H2O) from a thin film of poly-
(methyl methacrylate) was followed by FT-IR (K28). The impact
of the ban on the manufacture of Freon 113 was discussed in
relation to the IR analysis of water or soil for hydrocarbons (K29).
A paper was published that describes the design and use of a
micromachined, integrated optical bench for a carbon dioxide IR
sensor (K30). Quality assurance measurements for consistent
instrument operation and performance prediction of passive FT-
IR data collection systems for air analysis were developed (K31).
In another paper, the quality assurance aspects for FT-IR analysis
using a short cell and high concentrations of gases were
considered (K32).
Gas analysis is an important aspect of monitoring the environ-
ment. A number of devices for the analysis of gases by IR
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 139R
spectroscopy were described in various papers. These include a
tubular IR waveguide sensor with a functionalized self-assembled
monolayer (K33), fiber-optic sensors for on-line gas monitoring
(K34), a portable FT-IR, real-time, gas analyzer (GASMET) (K35),
an IR imaging volatile organic carbon field sensor (K36), an
intercavity diode laser near-IR spectrometer (K37), and a dual-
cell extractive FT-IR ambient air monitor (K38).
Sources of noise in FT-IR instruments used for trace gas
analysis were the subject of an investigation (K39). Heated
extractive FT-IR was used for the analysis of volatile emissions
from production facilities (K40). Fugitive emissions (carbon
tetrachloride, 1,3-butadiene, propane) from piping components
were analyzed with a portable IR analyzer (K41). Trace gas
analysis was carried out by means of a Midac FT-IR equipped
with a multipass cell and Grams/386 software (K42). FT-IR was
used for time-resolved air monitoring for methyl bromide con-
centrations after fumigation of buildings (K43). Ammonia and
HCl were detected in flue gases using a GASMET gas analyzer
(K44). The IR spectra of 18 hydrochlorofluorocarbons and
hydrofluorocarbons were measured and used to calculate radiative
forcing and global warming potentials (K45). A portable FT-IR
was used for the measurement of hexahydrophthalic anhydride
in air at a manufacturing site (K46). Volatile organic compounds
and some inorganic compounds were detected on-line using an
FT-IR spectrometer as a continuous emission monitor (K47). IR
spectroscopy and gas correlation techniques were used for the
visualization of gas flows (K48). FT-IR was used for the deter-
mination of consumer exposure to solvents during paint stripping
operations (K49). An algorithm was developed for quantitative
analysis of the FT-IR spectrum of a chemical plume (K50).
Several papers outlined the use of FT-IR spectroscopy for the
analysis of emissions from the burning of coal (K51-K54). FT-
IR has also been used as a continuous emission monitor for stack
gas at an oil refinery (K55) and incinerator (K56). In situ and
extractive FT-IR techniques for the analysis of compounds from
incineration of chlorinated hydrocarbons were discussed (K57).
Quantitative analysis of the toxic gases produced during chemical
quenching of JP-8 fuel fires was performed using FT-IR spectros-
copy (K58). FT-IR spectroscopy and a chemometric technique
(partial least squares) were investigated as a means to obtain the
concentrations of compounds in the smoke from burning textiles
(K59).
Sampling techniques and FT-IR methods for analysis of
nonmethane organic gases in automotive exhaust were presented
(K60). The gases from aircraft engine exhaust were analyzed by
an on-board FT-IR spectrometer (K61). An emission FT-IR
technique was used to detect water, carbon dioxide, and carbon
monoxide in aircraft engine exhaust (K62). Nitric oxide, nitrogen
dioxide, and water were measured in aircraft engine exhaust with
a tunable IR diode laser system (K63). FT-IR spectroscopy was
used in a study of vehicle exhaust emissions from oxygenated
fuel blends (K64). Four analyzers are normally used to test
vehicle emissions for CO, CO2, NOx, and total hydrocarbons for
the IM240 inspection test. The results from an FT-IR analyzer
were compared to those of the four analyzers (K65). FT-IR was
used in studying the catalytic conversion of NOx (K66).
The use of IR spectrometry for the analysis of certain gases
(such as ClO, NO, and HCl) in the upper atmosphere was
140R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
reviewed for the period from 1969 to 1992 (K67). Chlorine
monoxide was detected in the lower stratosphere via FT-IR
measurements (K68). Ground-based FT-IR was used in the
determination of the concentration of ozone in the atmosphere
(K69-K71). A passive remote IR sensing system for monitoring
atmospheric pollution was discussed (K72). The CO column
abundance in the atmosphere over Tokyo was measured by IR
(K73). Column densities of various trace gases were obtained
by high-resolution FT-IR solar absorption spectrometry (K74).
Considerations for using IR to determine the distributions of nitric
acid and nitric oxides in the Earth’s atmosphere were discussed
(K75). The use of a ground-based FT-IR spectrometer as a remote
monitoring device for pollutants such as CFCs was reported (K76).
The influence of aerosols and cloud absorption on the FT-IR
determination of atmospheric pollutants was studied (K77). Mid-
IR measurements of the atmosphere above the South Pole yielded
information about water vapor content, trace gases, temperature
profiles, and aerosols (K78). Trace gases in the atmosphere
(including HCl and ClONO2) were detected from a high-resolution
FT-IR spectrometer operating from a stabilized balloon gondola
(K79). A high-resolution FT-IR spectrometer carried on an aircraft
and used for remote sensing of atmospheric emission was
described (K80). The HBr profile in the stratosphere was
measured via far-IR emission spectroscopy (K81). A review
covered the remote sensing of Earth’s atmosphere from space
via IR (K82). Another review discussed far-IR remote monitoring
of the atmosphere (K83). An FT-IR that will be placed on a
satellite (CESAR) and used to monitor trace gases in the
atmosphere was described (K84). A review discussed the use of
mid-IR tunable diode lasers for monitoring trace gases in the
atmosphere and remote sensing of exhaust gases (K85). An
airborne tunable diode laser IR spectrometer (FLAIR) was used
in the measurement of trace gases in the troposphere (K86).
NIR tunable diode laser systems that use fiber optics were
described. The instruments can be used for stack monitoring
(K87). An IR emission spectrometer carried on an aircraft was
used to monitor a number of gases from wildfires in the western
United States (K88). Methods for achieving background sup-
pression to facilitate FT-IR monitoring of volatile organic com-
pounds were discussed (K89). Fourier transform near-IR spec-
troscopy was used for remote monitoring of volatile organic
compounds (K90). Remote sensing of smoke stack plumes was
achieved with high-resolution FT-IR spectroscopy (K91, K92). The
feasibility of remote measurement of HNO3 and SO2 in aircraft
exhaust gases was investigated through computer modeling of
the IR spectra of the exhaust plume (K93). Industrial fugitive
emissions of hydrocarbons were measured by the FT-IR tracer
method (FTM) (K94). A new remote optical fiber sensor for near-
IR detection of CO2 was reported (K95). Near-IR vapor sensors
were developed that depend on the detection of compounds
adsorbed on thin-layer chromatography plates (K96). An in situ
monitor for underground waste sites uses an FT-IR system and a
fiber-optic reflectance probe (K97). A fiber-optic IR reflectance
probe was also used in the remote detection of trichloroethylene
in soil (K98). Band-pass digital filtering and linear discriminant
analysis were applied to portions of the interferogram data from
a passive FT-IR system in order to detect trichloroethylene vapor
in the presence of other chemicals (K99). The reactions of
alumina powder with halomethanes were studied by in situ FT-
IR as part of an investigation of the impact of alumina from solid-
propellant rocket motors on the chemistry of the stratosphere
(K100).
The application of open-path FT-IR at three Shell Oil sites was
discussed (K101). An automated open-path FT-IR system was
used to monitor volatile organics from a wastewater treatment
plant (K102). The gases produced from controlled biomass fires
were detected by open-path FT-IR at 0.12-cm-1 resolution (K103).
The use of open-path near-IR tunable diode lasers for the detection
of fugitive emissions was reported (K104, K105). Air pollutants
in a petrochemical industrial park were measured with open-path
FT-IR remote sensing techniques (K106, K107). Indoor tracer
gas concentration profiles were obtained with an open-path FT-
IR spectrometer and computed tomography (K108). These two
techniques were also used to obtain two-dimensional maps of air
pollutants (K109). Open-path FT-IR analysis of emissions from
volcanoes and extractive FT-IR analysis of gases from polluted
groundwater were discussed in a study describing the use of FT-
IR for environmental monitoring (K110). Open-path FT-IR in
combination with synthetic calibration was found to be useful for
the analysis of smoke from biomass fires (K111). The effects of
spectral resolution on open-path FT-IR measurements were
investigated (K112-K114). The U.S. EPA has contracted the
development of standardized procedures (document TO-16) for
obtaining quantitative data from FT-IR remote sensors. The
contents of these procedures were described (K115). Details
were provided on methods for estimating emission rates from
nonhomogeneous fugitive sources using open-path FT-IR (K116).
The results of an open-path FT-IR field study of air pollutants by
the API and U.S. EPA were presented (K117). Both FT-IR and
UV systems were used at a Superfund site in an evaluation of
open-path fenceline monitoring and emission rate estimation
(K118). Open-path FT-IR and UV were also used to monitor
volatile organics during excavation at a petroleum refining site
(K119). Modeling techniques to estimate emissions from air
pollution sources by open-path FT-IR were reported (K120).
Quality assurance programs for open-path FT-IR air monitoring
at 20 U.S. industrial plants and waste sites were reviewed (K121).
A fence line FT-IR monitoring system around the perimeter of an
industrial facility was described (K122). An exposure chamber
was used in the evaluation of the accuracy of an open-path FT-IR
spectrometer (K123). The use of open-path FT-IR for measure-
ment of air pollutants in industry and agriculture was discussed
(K124). The design of an open-path atmospheric monitor contain-
ing an acoustooptic tunable filter for emission spectroscopy and
lasers for mid-IR and far-IR absorption spectroscopy was described
(K125). The methodology used in open-path FT-IR monitoring
of a process area was presented along with recommendations for
improvement (K126). The results of open-path FT-IR measure-
ments at a Kodak industrial complex and the Hanford site were
reported (K127, K128). A paper detailed the use of a program to
calculate open-path FT-IR reference spectra for temperatures at
which no spectra are available (K129). A report was presented
on the methods used in a training course in Taiwan on open-path
FT-IR technology (K130). Calibration of an open-path FT-IR
spectrometer via multipass cells was described (K131, K132).
CARBON AND CARBON COMPLEXES
Carbon cluster anions, trapped in an Ar matrix, were studied
spectroscopically. New bands found in the IR spectra were
assigned to asymmetric stretching modes of the C3, C5, C7, and
C9 anions (L1). The IR spectra of neutral linear carbon clusters
were studied in Ne, Ar, and Kr matrixes. Thermal annealing and
high-level ab initio and density functional theory calculations were
used to locate unknown bands of C8 and C9 clusters (L2). The
n7 stretching mode of the linear C9 carbon cluster has been
observed at 1601.0 cm-1. Comparison to isotopic shifts and
theoretical calculations confirm the assignment (L3). Two previ-
ously identified fundamentals, n4 of the linear C7 cluster, were
confirmed using 13C isotopic shifts and theoretical calculations
(L4).
New assignments for the silent-mode vibrational frequencies
in C60 are proposed that are consistent with the Raman and IR
spectra, isotopically induced frequency shifts, and theoretical
calculations (L5). The room-temperature IR and Raman spectra
for the pressure-induced rhombohedral, tetragonal, and orthor-
hombic C60 polymers and the C60 photopolymer have been
explored (L6-L8). Fluorinated C60 fullerenes were examined
spectroscopically (L9). A quantitative IR method has been
established for the determination of C60/C70 concentrations in
mixtures (L10).
The influence of the method of deposition on the atomic scale
structure of amorphous hydrogenated carbon has been analyzed
using IR spectroscopy and inelastic neutron spectroscopy (L11).
The bonding configurations of hydrogen in hydrogenated amor-
phous carbon (a-C:H) has been studied using IR spectroscopy
and thermal effusion experiments (L12). IR spectroscopy was
used to examine thin solid films of hydrogenated amorphous
carbon under conditions near decomposition (L13). Structural
changes induced by nitrogen doping amorphous hydrogenated
carbon films hacw been investigated using IR and photolumines-
cence spectroscopy (L14). An IR analysis of amorphous hydro-
genated carbon films has been performed to determine the sp3/
sp2 ratio (L15).
Infrared and Raman spectroscopies were used to characterize
the structural changes that occurred in hydrogenated diamond-
like carbon film upon implantation with heavy energetic ions
(L16). The interactions of hydrogen and methyl radicals with
diamond (C111) surfaces were examined using IR-visible sum-
frequency vibrational spectroscopy (L17).
The interactions between acetone and pure carbon surfaces
and carbon surfaces doped with cations (Ni2+, Cu2+, Cr3+) were
explored. The IR spectra indicate that acetone can be both
physisorbed and chemisorbed on the pure carbon surfaces.
Acetone can also be used to probe the surface for Lewis acidic
sites (L18).
The measurement of C13/C12 ratios in carbon samples
converted to CO2 gas can be accomplish using IR spectroscopy
(L19). Pressure broadening of the 2350-cm-1 band permitted
isotope ratio differences of 0.02 at. % above the natural abundance
of 1.11 at. % to be detected (L20).
The far-IR spectra of carbon disulfide under high pressure in
a diamond anvil cell did not reveal a solid-state phase transition.
The intramolecular bonding weakens at high pressure and the
intermolecular bonding increases at the pressures studied (L21).
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 141R
 The distribution of functional groups in coal macerals can be
examined using reflectance IR microspectroscopy. The technique
yielded information on the character of aliphatic chains of vitrinite
and liptinite macerals from high-volatile bituminous coal and can
be used to study the degree of oxidation and reactivity of vitrinite
and semifusinite (L22). Specular reflectance IR microspectros-
copy was also used to account for reflectance anomalies seen in
the Brent coal series of the North Sea. The variations in the
chemistries of the vitrinites and oxidation biased the reflectance
measurements (L23). Self-deconvolution and curve-fitting of the
IR spectra of coal varying in rank were used to gain additional
information on structural changes that occur during coalification
(L24). Chemical treatment modification of coal samples was
followed using diffuse reflectance IR spectroscopy (L25). The
weathering process in stockpiled coals, including zones where
signs of high oxidation and self-ignition, were studied using IR
spectroscopy (L26).
The coal properties of volatile matter, fixed carbon, ash, carbon,
hydrogen, and vitrinite reflectance could be successfully deter-
mined from models based on derivative diffuse reflectance IR
spectroscopy (L27). Compressed infrared data from osculating
polynomials gave slightly better correlations for these same
properties of coal (L28).
The middle oil fractions of high-temperature coal tar were
examined and chemical components identified using gas chro-
matography/infrared spectroscopy (L29).
Chemical changes that occurred during thermal decomposition
of rockrose to produce char and activated carbon have been
examined using IR spectroscopy (L30). IR spectroscopy has been
used in a comprehensive program to elucidate the structure and
reactivity of carbon black (L31). Multicomponent absorption
kinetics of gases in activated carbon was studied by a batch
absorber IR technique and compared to a model for predicting
multicomponent dynamics in a differential adsorption bed system
(L32).
CHEMICAL REACTIONS/ORGANIC CHEMISTRY
Hydrogen-Bonding Studies. Infrared studies of the hydra-
tion of di-, tri-, tetra-, and pentamethonium halides supported the
formation of planar hydrate clusters (M1, M2). The hydrogen-
bonded complexes between N-methylsuccinimide and phenols
were investigated (M3). The associative interactions of hydrop-
eroxides to form hydrogen-bonded dimers and complexes with
cycloalkanones were studied (M4). Hydrogen bonding in imida-
zolium salts was studied, and the implications for the structure
and solvent properties of the ionic liquids were discussed (M5).
The infrared spectra of associated molecules of N-methylacetamide
were calculated and compared with experimental data (M6). The
intra- and intermolecular H bonds between the H on the N and
the ferrocenyl for N-methylferrocene aniline compounds were
studied (M7). The FT-IR spectra of the H-bonded complexes
between HCl and substituted pyridines, benzimidazole, purine,
and 4-aminopyrimidine were investigated (M8). Crown ether
complexes with urea and thiourea showed significant differences
in their respective interactions (M9). The influence of hydrogen
bonding in 3-hydroxyazabicyclo[2.2.2]octane pentachlorophenolate
was described (M10). The geometry and complexing ability of
142R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
aminoquinolines in carbon tetrachloride solutions were examined
(M11).
Near-infrared was used to study the hydrogen bonding
between thioacetamide and N,N-disubstituted benzamide deriva-
tives in CCl4 (M12). The hydrogen-bonding influence on the
molecular vibrational spectra of liquid methanol was studied by
molecular dynamics simulation (M13). The IR bending vibrational
band of water in aqueous haloethanol mixtures was studied as a
measure of hydrogen-bonding strength (M14). FT-IR studies of
hydrogen bonding between unsaturated esters and several alco-
hols were correlated with the enthalpy of hydrogen bond forma-
tion (M15). The infrared absorption spectra of acetone and
methanol mixtures in a solid argon matrix showed H-bond
interactions (M16). The integrated intensities of bent hydrogen
bonds in o-dialkylaminomethyl phenols and deuterated analogues
were measured (M17). An infrared study was done of intramo-
lecularly hydrogen-bonded aromatic carbonyl-containing com-
pounds in various solvents (M18). The hydrogen bonds in
different crystal phases and melts were determined for a group
of alcohols derived from 2,2-dimethylpropane (M19). Substituent
effects on hydrogen bonding were measured for ortho-substituted
nitrobenzenes and 2,4-dinitrobenzenes in chloroform and aceto-
nitrile (M20). Complexes of five pyridines and nine pyridine
N-oxides with 2,6-dichloro-4-nitrophenol were studied by infrared
spectroscopy (M21). The far-infrared hydrogen bond vibration
was studied as a function of the pKa of the donor or acceptor
molecules for systems of complexes (M22).
The self-assembling properties of pyridone and the structure-
breaking effects of organic solvents were investigated (M23). The
self-association of several N-urethanyl-L-amino acids in carbon
tetrachloride was investigated by FT-IR (M24). A potassium salt
of acetylenedicarboxylic acid was used as a model to study a
strongly hydrogen-bonded system (M25). The hydrogen bond
structure in benzoic acid solutions was investigated (M26). The
influence of intramolecular hydrogen bonding on the structure
and photoisomerization of urocanic acid derivatives was studied
(M27). The hydrogen bond energies of crystalline carboxylic acid
salts were determined (M28). Differences in the types of
hydrogen bonding occurring in oxamic, malonamic, and succi-
namic acids in the solid state were investigated (M29, M30).
Hydrogen bond structures of partially methylated p-tert-butylcalix-
[6]arenes were investigated in both solution and the solid state
by FT-IR (M31). Infrared was used to characterize the crystal
and molecular structure of new diketone enols designed to have
known packing features (M32). The interaction by hydrogen
bond formation of 1,1,1-trichloro-2-methyl-2-propanol with some
ethers and acetone in CCl4 was investigated (M33).
An infrared study was done in the region of the fundamental
NH stretching vibration for six N-methylbenzamide-aromatic
donor systems (M34). The infrared spectra of butyl halides
dissolved in CCl4 and deuterated DMSO were investigated to
determine the degree of hydrogen bonding occurring (M35).
Intramolecular hydrogen bonding in 8-hydroxy-N,N-dimethyl-1-
naphthylamine was studied (M36). An FT-IR study of the proton
polarizability and Fermi resonance effects as a function of
temperature for hydrogen-bonded systems in Mannich bases of
2,2′-biphenol was done (M37). The temperature effects on
hydrogen-bonded complexes of NH donors with proton acceptors
were studied (M38). Peak shifts in the infrared spectrum of
benzoic acid crystals when compressed with methylated additives
were investigated (M39). The equilibrium kinetics and vibrational
energy transfer between the free acid Et3SiOH and its 1:1
hydrogen-bonded complex with acetonitrile were studied using
picosecond time-resolved IR double-resonance spectroscopy (M40).
Catalysis Studies. The infrared spectral methods of studying
catalysis mechanisms were reviewed (M41). Acetonitrile adsorp-
tion onto hydroxylated zirconium dioxide and the mechanism of
hydrolysis were studied by in situ FT-IR spectroscopy (M42). The
hydration of acetonitrile toward acetamide by a silica-supported
rhodium catalyst was investigated (M43). A study was made of
the interconversion of isomeric unsaturated C4 nitriles over
strongly basic Na/NaY (M44). The cracking of 1,3,5-triisopro-
pylbenzene over deeply dealuminated Y zeolite was monitored
by infrared spectroscopy (M45). The IR spectra of species formed
from the adsorption of butene isomers on 12-tungstophosphoric
acid showed primarily saturated C-C bonds (M46). The selective
synthesis of 2-methylnaphthalene over a variety of zeolites was
studied (M47). Infrared was used to characterize zinc-promoted
H-ZSM-5 catalysts used for conversion of propane to aromatics
(M48). A diffuse reflectance study was used to monitor the state
of an H-mordenite catalyst during ethyl tert-butyl ether synthesis
(M49). Methanol adsorption and dehydrogenation over stoichio-
metric and nonstoichiometric hydroxyapatite catalysts were
characterized (M50). IR spectroscopic investigations were per-
formed of the adsorption and surface reactions of CH3Cl over
acidic, basic, and neutral zeolite catalysts (M51). Kinetic studies
using in situ FT-IR characterized the mechanism of methanol
synthesis over a zirconia-supported catalyst (M52). The H/D
isotope-exchange reactions of adsorbed formate and methoxy
species with D2 on zirconia were investigated (M53). The low-
temperature adsorption of methyl chloride and methyl iodide on
silica-supported Pt catalysts was studied (M54). The conversion
of methyl radicals to methanol and formaldehyde over vanadium
oxide catalysts was confirmed by infrared spectroscopy (M55).
Infrared spectroscopy and temperature-programmed desorption
were used to investigate the chemistry of methyl iodide adsorbed
on silica-supported copper nanoparticles (M56). The interaction
of propene and butenes with a butene oxydehydrogenation catalyst
was studied (M57). The decomposition of perfluorodiethyl ether
on alumina was studied at 300 and 500 K (M58). An infrared
study of chromium carbonyl complexes on silica-alumina showed
ligand loss resulting in an active ethene polymerization catalyst
(M59). Infrared studies of methylation of pyridine over zeolites
were performed to understand the correlation between catalyst
acidity and activity/selectivity for the reaction (M60). The
reaction products from acetone decomposition on silver were
identified by infrared spectroscopy (M61). Infrared was used to
study the interaction of Ge(n-C4H9)4 with the surface of partially
dehydroxylated alumina and silica-alumina (M62). The adsorp-
tion of 4,4′-bipyridine on the surfaces of silica, alumina, and titania
was characterized by infrared spectroscopy (M63).
The mechanisms in the oxidation and dissociative chemisorp-
tion of ethanol on platinum electrodes were characterized by
infrared spectroscopy (M64). Infrared was used to study the
adsorption and oxidation of propene on multiphase Bi, Mo, and
Co catalysts (M65). The mechanisms of light alkane catalytic
oxidation and oxydehydrogenation for n-butane conversion over
magnesium chromate and a magnesium-vanadate catalyst were
characterized (M66). The interaction of propane and propene and
of C1-3 oxygenates on cobalt oxide surfaces was studied (M67).
In situ FT-IR spectroscopy was used to study oxygen-adsorbed
species over SrF2/Nd2O3 (M68). The selective oxidation of
nitrosobenzene to nitrobenzene by metal oxides was studied
(M69). The adsorption, decomposition, and oxidation of methyl
chloride on tin oxide catalysts were investigated (M70). Infrared
spectroscopy was used in characterizing the bonding geometry
of the carbonyl group during hydrogenation on Pd/SiO2 catalysts
(M71). The hydrogenation of propyne on a range of supported
palladium catalysts was investigated (M72). The hydrogenation
and dehydrogenation of isobutene on platinum were monitored
(M73).
Several infrared studies have characterized the adsorption,
reaction mechanism and products of NO and NOx reduction over
a variety of catalysts (M74-M83). The products and mechanism
of the gas-phase reaction of NO3 radicals with 2-butyne in purified
air were investigated (M84). The chemical transformations of
silica-supported iron rhodium complexes and the catalysis of
propylene hydroformylation were investigated (M85). The inter-
actions of supported RhO and Co- and Fe-promoted RhO with the
silica surface were studied by infrared spectroscopy (M86). The
adsorption of methanol and formaldehyde on rhodium-containing
catalysts was studied (M87). The skeletal isomerization of butene
by alumina-supported tungsten oxide catalysts was studied (M88).
Infrared studies characterized the isomerization of methyl formate
and ethyl formate chemisorbed on nickel (M89).
Solvent/Matrix Effects. The conformational behavior of
trimethyl phosphate was studied by infrared spectroscopy in the
liquid phase and as 1% solutions in a wide range of solvents (M90).
Rotational isomerism of desyl chloride in solvents of varied
dielectric constants was examined by infrared spectroscopy (M91).
Conformational isomerism and self-association of calixarene in
nonpolar solution were studied by FT-IR (M92). The molecular
states of alkali metal acetates in glacial acetic acid were investi-
gated (M93). Solvation of lauric acid was investigated in different
solvents by infrared and Raman (M94). Aqueous ATR FT-IR
spectra of 24 aliphatic monocarboxylates were correlated with the
pKa values of these acids (M95). An infrared study of R-haloacetic
acids in solution was done (M96). The infrared spectra of cyclic
and noncyclic ureas in solution were interpreted with respect to
structures and interactions with a variety of solvents (M97). Using
model spectra of toluene and cyclohexane and variable-tempera-
ture spectra of chlorocyclohexane, curve resolution of infrared
profiles from nonconformational mixtures and conformational
equilibria is discussed (M98). The tautomeric (enol-keto) and
dimeric equilibria of 2-hydroxypyridines and 1,3-cyclohexanedi-
ones in chloroform and/or CCl4 solutions were studied by FT-IR
(M99). The interactions in binary mixtures of acetone and
chloroform-d were studied by infrared and Raman spectroscopies
(M100). The dynamics of the carbonium ion solvated by molec-
ular hydrogen was studied (M101, M102). The solvent-induced
shift of the fundamental vibrational mode of the carbonyl group
in 2-butanone was measured in 27 solvents (M103). Self-
association of medium-chain alcohols in n-decane solutions was
studied by the infrared absorption of the fundamental OH
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 143R
stretching vibration (M104). An experimental and theoretical
study of the structure and aggregation of diphenylguanidine in
nonpolar and low-polarity solvents was performed (M105). In-
frared measurements of N-acetyl- and N-benzoylaminopyridines
in a set and in mixtures of solvents were discussed in terms of
bulk and solute-solvent interactions (M106). The solvation of
2-hydroxypentylphosphonates was studied (M107). Liquid mix-
tures of pyridine with carbon disulfide, benzene, and carbon
tetrachloride were studied in the far-infrared region as a function
of concentration and temperature (M108). The solvation of
amides and peptides was studied by infrared and NMR (M109).
Solute/solvent interactions of 1-substituted 2-pyrrolidinones and
related compounds in a variety of solvents were studied by infrared
spectroscopy (M110). Infrared spectroscopy of the OH stretching
vibrations of hydrogen-bonded tropolone complexes was discussed
(M111). Tautomerism of thioguanine was studied using matrix
isolation infrared spectroscopy (M112). The infrared spectra of
some hydrogen halide salts of methamphetamine were observed
to display significant variations dependent upon the alkali halide
matrix in which the salt was dispersed for analysis (M113).
Organic Reactions/Characterization. A review described
the use of ab initio infrared spectra in the identification of highly
reactive organic molecules and intermediates (M114). Changes
occurring in the infrared spectrum of ethylene-CO alternating
copolymer as a function of temperature were analyzed (M115).
The reaction products generated by pulsed flash pyrolysis of
2-ethynyl-1,1,1-trimethyldisilane were characterized by matrix
isolation IR spectroscopy (M116). Isomeric silylenes were gener-
ated by pulsed flash pyrolysis and identified by matrix isolation
IR spectroscopy (M117). The methane elimination during silation
of partially dehydroxylated alumina was studied (M118). The
kinetics and products of the gas-phase reactions of silanes and
siloxanes with hydroxyl radical and atomic chlorine were studied
by FT-IR and mass spectrometry (M119). The highly substituted
cyclohexane derivatives synthesized from the Michael-Michael
aldol condensation of chalcones with cyanoacetylurea and cy-
anoacetylpiperidine were characterized by IR and NMR (M120).
The interconversion of isomeric unsaturated C4 nitriles in the
presence of butyllithium was investigated by means of FT-IR and
UV-visible spectroscopy (M121). FT-IR spectroscopic studies
were performed on the mechanisms of the halogen atom-initiated
oxidation of haloacetaldehydes (M122). The products and mech-
anisms for the gas-phase reactions of the nitrate radical and
haloethenes were studied (M123). The hydrothermolysis kinetics
and pathways of guanidinium nitrate and urea in were described
as examples of the use of IR spectroscopy for determining the
rates and pathways of hydrolytic decomposition reactions of
organic and inorganic compounds in aqueous media in conditions
up to 400 °C and 350 atm (M124). Quantitative characterization
of protolytic reactions of o,o′-dihydroxyphenylazonaphthyls using
IR spectroscopy was described (M125). The reaction of ketenes
in pyridine matrixes to form ketene--yridine ylides was observed
by IR spectroscopy (M126). The decomposition products of
ethylenediammonium dinitrate through hydrothermal reactions
were studied (M127). The results of studies on the protonation
of a series of sulfinamides using IR and NMR were reported
(M128).
144R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
The ab initio MO method was used to study the decomposition
of carbamic acid and its thio and sila derivatives (M129). Diffuse
reflectance FT-IR was used to study two humic sodium salts and
structural changes caused by heating (M130). The thermal
decomposition of acetic anhydride was monitored by vacuum-UV
absorption and IR emission (M131). The evolved products from
the melting, vaporization, and thermal decomposition of alkyl- and
arylureas were analyzed by IR spectroscopy (M132). The
decomposition reaction of methyltrichlorosilane was investigated
by in situ IR spectroscopy (M133). The analytical capacity of FT-
IR for the analysis of works of art was discussed (M134). The
mineralization of cellulose and protein fibers was investigated
using FT-IR microscopy (M135). Motor oil degradation was
characterized by IR spectroscopy (M136).
The stabilization of water-soluble surfactants at the air/water
interface with gegenion complexation was studied by IR spec-
troscopy (M137). A Raman/IR spectroscopic study investigated
the stoichiometry and conformation of the azacrown moiety in
sodium complexes of azacrown ethers (M138). Near-infrared
absorption was used to characterize and measure the association
constants of the inclusion complexes between aromatic com-
pounds and cyclodextrins (M139). IR spectroscopy was used in
establishing the structure of complexes of phenols with com-
pounds containing SOx groups (M140). The formation of com-
plexes of picric acid with hexamethylbenzene, 2-iodoaniline, and
1-aminoanthracene was examined using FT-IR spectroscopy
(M141). The interaction of 2-chloro-3,5-dinitropyridine with aniline
and its derivatives and the structure of the formed complexes were
studied using IR and electronic absorption spectroscopy (M142).
Several 1:1 chloranilic acid-amine complexes were studied by
IR, UV, and NMR (M143). The complex formation between
o-cresol and propionitrile was investigated by FT-IR (M144).
Complexes formed by phenols with 1,3,4,6,7,8-hexahydro-1-methyl-
2H-pyrimido[1,2-a]pyrimidine were studied as a function of the
pKa of the phenols by FT-IR (M145). Infrared measurements of
the kinetics and decomposition pathways of aqueous urea and
guanidinium nitrate were described (M146).
Infrared spectroscopic studies of photoinduced reactions of
methyl radical in solid para-hydrogen were described (M147). The
ultraviolet photolysis of acetyl and propionyl radicals was studied
by infrared emission spectroscopy (M148). The composition of
aerosol generated in the photooxidation of 1,3,5-trimethylbenzene
was investigated in a smog chamber experiment using IR
spectroscopy (M149). IR characterization of the UV photoinduced
reactions of matrix-isolated 1-diazido-1-germacyclopent-3-ene was
described (M150). The photochemistry of phenyl azides bearing
2-hydroxy and 2-amino groups was studied by matrix isolation
spectroscopy (M151).
FOOD AND AGRICULTURE
Near-IR spectroscopy continues to be a focus of application in
the food and agricultural industries. The proceedings from two
conferences provide a good review of the varied applications (N1,
N2). A review of infrared spectroscopy and microspectroscopy
as related to food applications has been presented (N3). Applica-
tion of photoacoustic spectroscopy in the near-IR and mid-IR
regions to determination of the principal components of food has
also been reviewed (N4).
 Mid-IR and near-IR spectroscopy techniques have been applied
in the dairy industry. By using the second derivative of the IR
spectrum, simplified models could be developed to determine the
fat and protein contents of raw milk (N5). Determination of fat,
protein, casein, and noncasein in milk by near-IR (N6) is reported.
Fermented milk composition was also examined using near-IR
spectroscopy (N7). Mid-IR techniques have been adapted to
determine microorganisms (especially Clostridium) in dairy (N8).
The composition of cheese was examined using optothermal near-
IR and mid-IR attenuated total reflectance (N9) and near-IR
reflectance spectroscopy (N10).
The examination of sugars for composition and quantitation
using mid-IR and near-IR has been reported. A multivariate
analysis of the infrared spectra of biological samples allows for
the quantitation of a mixture of sucrose, fructose, and glucose
(N11). The theoretical recoverable sugar (TRS) can be predicted
from near-IR spectra and can be used to assess the quality of cane
and beet sugar sources (N12). Sucrose can be determined in
raw sugar cane juices using spectral data from mid-IR attenuated
total reflectance (N13). The thermal degradation of sugar cane
bagasse through to carbonization has been studied using mid-IR
spectroscopy (N14). Sugar refinery streams can be analyzed
using near-IR spectroscopy (N15, N16).
Edible oils and fats have been analyzed using IR spec-
troscopies. A review of the application of mid-IR to edible oil
analysis stresses key elements associated with developing suitable
fat and oil analysis (N17). IR spectroscopy is compared to
chromatographic techniques for the determination of trans fatty
acids in oils and fats (N18-N20). Supercritical fluid extraction
of oils in food samples coupled to a high-pressure flow cell has
been used to monitor the vinylic C-H band to determine the
amount of unsaturated fat (N21). Near-IR spectroscopy is
demonstrated for determination of palmitic, oleic, and linoleic acids
in edible oils (N22). Classification of edible oils and fats with
regard to their origin can be accomplished using mid-IR spec-
troscopy (N23). A mid-IR spectroscopic technique for determining
the solid fat index of oils and fats was developed (N24).
Fruit, fruit juices, and vegetables have received the attention
of mid-IR and near-IR spectroscopies. Determination of sugars
and acid in a variety of fruit juices has been accomplished (N25-
N28). Sesquiterpene hydrocarbons in citrus essential oils have
been identified using cryofocusing GC/IR (N29). Adulteration
of raspberry purees can be detected using mid-IR spectroscopy
and attenuated total reflectance sampling (N30). A nondestructive
method for determination of soluble solids in tomatoes based on
near-IR spectroscopy has been demonstrated (N31). The growth
period of Japanese pear fruit was monitored using the constituent
sugar concentrations (N32). Biochemical changes in peaches
associated with ripening during storage were followed using mid-
IR (N33).
Identification and detection of adulteration of coffees using both
mid-IR and near-IR spectroscopy have been reported. DRIFT and
ATR sampling techniques are suggested as alternatives to wet
chemical methods (N34, N35). Partial success was demonstrated
in using near-IR to discriminate between coffees prepared from
several different beans (N36).
The components of sausage products were simultaneously
determined using near-IR transmission with precision as good as
reference methods (N37). Near-IR spectroscopy can also be
applied to the analysis of oil and moisture (N38) and fat content
of salmon (N39).
The prediction of total dietary fiber in cereal and grain products
(N40) and the effect of residual moisture on total dietary fiber in
cereals (N41) have been examined using near-IR reflectance
spectroscopy.
Infrared microspectroscopy has been used to elucidate the
microstructural details of phase-separated polysaccharide-protein
mixtures (N42). Near-IR reflectance spectroscopy can provide a
nondestructive method to predict the solubility and digestibility
of protein heated under high pressure (N43). Determination of
heme and nonheme iron in raw muscle meats is possible using
near-IR spectroscopy (N44). Pressure-induced changes in food
components measured using a diamond anvil cell and mid-IR
spectroscopy were compared to temperature-induced gel forma-
tion (N45). The adsorption of triacylglycerol and oelic acid on
synthetic magnesium silicate was studied using diffuse reflectance
FT-IR spectroscopy and compared to magnesium silicates used
to treat degraded frying oil (N46). It is possible to perform starch
content determination on digestive samples using near-IR spec-
troscopy (N47).
The temperature effects and calibration methods have been
studied to demonstrate the feasibility of using mid-IR spectroscopy
for determination of major compounds of alcoholic fermentation
(N48).
The ability to differentiate meat speciation, the detection of
frozen or thawed meat, and semiquantitative analysis of meat
mixtures using mid-IR ATR have been demonstrated (N49). Near-
IR is also suggested as a technique for differentiating frozen and
unfrozen beef (N50). The phospholipid content of intramuscular
fat can be determined using the band between 1282 and 1020 cm
-1 (N51). Polarized IR microspectroscopy can be used to assess
the orientation of the mineral and matrix components of calcified
tissue (N52).
Near-IR spectroscopy has been used to screen the crude
glycinin fraction and the effects of growing temperature and
genotype on this fraction (N53). The effects of bound water on
the mid-IR spectrum of glycinin was also studied (N54). The
ruminal protein content in roasted soybeans can be estimated from
the near-IR spectrum (N55). Near-IR spectroscopy can be used
to quantitate moisture, protein, and starch in buckwheat flours
but failed to correlate with the amylose and tannin content (N56).
Several quality characteristics in rice by analysis of whole-grain
milled samples can be measured using near-IR reflectance
spectroscopy (N57).
Determination of forage composition was not improved by
using models based on a combination of both mid-IR and near-IR
spectra over models based on just a single spectral range (N58).
The value of Leucaena, a fast-growing tree used in the tropics for
forage, can be evaluated using near-IR spectroscopy with differ-
ences observed between species, varieties, and hybrids (N59).
The prediction of energy value of compound feeds for swine and
ruminants based on near-IR spectroscopy is slightly better than
other analytical methods (N60). Partial success in determining
the composition of biomass feedstock has been accomplished
using near-IR spectroscopy (N61).
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 145R
 Near-IR spectroscopy can be used as a rapid-scanning tech-
nique for the determination of chemical compositions of plantation
eucalypti woods (N62). Residues and extracts from eucalyptus
wood have been characterized by IR spectroscopy, UV spectros-
copy, and HPLC (N63).
It is possible to determine the resistance of sugarcane to
sugarcane borer infestation using predictive models based on the
near-IR spectrum of stalk surface wax (N64). External and
internal insect infestation in stored wheat grain could be detected
using near-IR reflectance spectroscopy (N65). Mid-IR spectros-
copy has shown that significant differences may exist within the
plasma membrane ATPase of corn roots (N66).
A sensor based on a polymer-coated attenuated total reflectance
element of a silver halide optical fiber and mid-IR spectroscopy
has achieved a 2 ppm limit of detection for atrazine and alachlor
in water (N67). The use of infrared techniques applied to organic
and inorganic soil materials has been reviewed (N68).
BIOCHEMISTRY
To determine the effects of age on bone quality, human bone
tissue taken from adult subjects deceased from violent death was
analyzed by means of FT-IR in the diffuse reflectance mode (O1).
FT-IR and FT-Raman spectra of human brain tissue are presented
in this article (O2). This paper describes a nondispersive IR
spectrometer for the measurement of the 13CO2/12CO2-ratio in
breath samples (O3). Untreated and bleached hair samples were
analyzed by FT-IR spectroscopy for cysteic acid and cysteine
S-thiosulfate using different data manipulations and various
sampling techniques (O4). Absorption spectra of human teeth
sections were measured by FT-IR to identify absorption peaks for
amides I, II, and III, carbonate, and phosphate (O5). To establish
age-related lipid composition-membrane structure relationships,
the hydrocarbon chain structure of lipid membranes from the
human lens cortex and nucleus was examined by infrared and
near-infrared spectroscopies (O6). The feasibility of obtaining
reproducible spectra of skin oils from individuals with a very
simple, noninvasive technique is reported (O7). Direct vapor
generation FT-IR spectrometry is a new procedure proposed for
a direct determination of ethanol in plasma and whole blood (O8).
The secondary structure of myelin basic protein in reconstituted
central nervous system myelin was studied FT-IR spectroscopy
(O9). A new method of IR spectroscopic imaging is described
and applied to the instantaneous, noninvasive mapping of the
molecular constituents of unprocessed brain tissue (O10). A
simple and rapid method for the analysis of poly(ethylene glycol)-
400 (PEG-400) in human urine is described using FT-IR spec-
trometry (O11). Mid- and near-IR spectra of viable and clipped
human finger nails are presented (O12). Toluene and a mixture
of the isomeric xylenes are common organic solvents that have
been implicated in false ethanol results produced by older models
of the Intoxilyzer 5000, a breath alcohol analyzer that uses IR
spectrophotometry to quantitate ethanol in breath samples (O13).
This review with 87 references is of experiments in which the
photoreactions of the visual pigments rhodopsin and octopus
rhodopsin were investigated by FT-IR spectroscopy (O14). This
paper reviews a study to analyze the IR spectra of a liquid-
simulating simulating food and an artificial saliva following
exposure to resin composites (O15).
146R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
This symposium report with three references discusses the
molecular structure of penicillin transition metal complexes (O16).
This paper describes the interference of volatile anesthetics with
infrared analysis of carbon dioxide and nitrous oxide tested in
the Draeger Cicero EM using sevoflurane (O17). From the two
wagging frequencies of the para amino group identified by IR and
laser Raman spectroscopy in the local anesthetic benzocaine, the
inversion barrier height and optimum inversion angle of this group
were calculated and reported (O18). The interaction of calf
thymus DNA with aspirin is investigated in aqueous solution, and
FT-IR and laser Raman difference are used to determine drug
binding sites, sequence preference, and DNA secondary structure,
as well as the structural variations of aspirin-DNA complexes in
aqueous solution (O19). This paper discusses in situ FT-IR and
calorimetric studies of the preparation of a pharmaceutical
intermediate (O20). Raman and FT-IR were used to analyze the
interaction of the antibiotic lasalocid with DPPC membranes
(O21). The mechanism of action of Timolor, used in the treatment
of ocular hypertension in glaucoma, was studied using FT-IR
spectroscopy (O22). The equilibria and structures of some
azobarbiturate and benzylidene barbituate compounds were
investigated based on different spectral and pH-metric methods
(O23). This work presents FT-IR spectra of tetracycline and
ampicillin, the major drugs used for the treatment of fatal bacillary
and coccal infections (O24). FT-IR, along with DCS, has been
used to study the interaction between a new antineoplastic drug
and diastearoylphosphatidylcholine bilayers (O25).
FT-IR spectroscopy has been applied to the investigation of
synovial fluids aspirated from arthritic joints (O26). Glycogen
levels in the tissue samples obtained from carcinomas and normal
sections of the human lungs were studied by measuring the IR
band intensities due to glycogen (O27). This review with 44
references has been written on the use of IR spectroscopy for
diagnosis and determination of prognosis of malignant neoplasia
such as breast and endometrial carcinomas (O28). This paper
describes the analysis of urinary calculi by infrared spectroscopy
(O29). Tumor progression to the metastatic state involves
structural modifications in DNA markedly different from those
associated with primary tumor formation. These modifications
alter vibrational and rotational motion and are discussed in this
article (O30). FT-IR microscpectroscopy, combined with principal
component analysis, was applied in the study of exfoliated cervical
cells to investigate the techniques feasibility as a biodiagnostic
tool for cervical cancer (O31). Newly developed FT-IR spectro-
scopic analysis techniques were applied to the diagnosis of
adulthood disease and to reveal the role of unsaturated fatty acids
in neuronal function (O32). Determination of whewellite, uric
acid, weddellite, dahllite, and struvite in their mixtures was studied
by X-ray diffraction and IR spectroscopy (O33). The IR spectra
of organic constituents of urine from cancerous bladders of some
patients were recorded and classified (O34). The secondary
structure and the thermal stability of human liver and heart fatty
acid-binding proteins were analyzed, in the absence and in the
presence of oleic acid, by FT-IR spectroscopy (O35). The authors
determined the structural changes in the bladder carcinoma cell
line J82-NVB induced by navelbine using FT-IR spectroscopy
(O36). The anticoagulant effect of tungstophosphoric acid salt
was studied by IR spectroscopy (O37). FT-IR spectra of 75
biopsies from 55 cases of breast carcinoma were studied in
comparison with histomorphometry and were found to be very
different from the spectra of normal tissues (O38). The transmis-
sion IR spectra of exfoliated endocervical mucin-producing co-
lumnar epithelial cells and the ATR IR spectra of the single-
columnar cell layer on the endocervical tissues has been measured
and compared with the corresponding IR spectra of the ectocer-
vical squamous cells and squamous epithelium (O39). The
authors report the conformation of intersubunit region from three
serotypes of influenza A virus and the MAP-1 peptide, with and
without the fusion peptide, as revealed by comparative CD and
FT-IR spectroscopy measurements (O40).
FT-IR and laser Raman difference spectroscopic techniques
were used to establish correlations between spectral modifications
and drug binding mode, sequence specificity, DNA melting, and
conformational changes, as well as structural variations of calf
thymus drug-DNA complexes in aqueous solution (O41). The
secondary structure of P2 protein, isolated from bovine peripheral
nervous system myelin, in reconstituted myelin was studied using
FT-IR spectroscopy (O42). Unoriented films of calf thymus Na
DNA were prepared and studied by Raman and IR spectroscopy
(O43). FT-IR spectroscopy, along with X-ray diffraction and
electron microscopy, was used to study apatite crystals isolated
from chicken and bovine calcified cartilage (O44). This article
describes the spectroscopic analysis of the FT-IR spectra of pig
citrate synthase using the factor analysis method (O45). Aqueous
dispersions of dipalmitoyl phosphatidylcholine, calf lung surfactant,
and an organic solvent extract of calf surfactant were examined
by FT-IR spectroscopy in the presence and absence of calcium
(O46). This paper discusses the possibility of detecting in a
semiquantitative manner alterations in the collagen content of
heart tissue following myocardial infarction (O47). Infrared was
used to study the effects of pH and KCl on the conformations of
creatine kinase from rabbit muscle (O48). The authors apply
high-fidelity FT-IR imaging to noninvasively generate image
contrast in sections of monkey brain tissue and to relate these
data to specific lipid and protein fractions (O49). The interaction
of diethylstilbestrol with calf thymus DNA was investigated with
FT-IR and Raman spectroscopy (O50). The interaction of calf
thymus DNA was studied with Al and Ga cations using FT-IR
spectroscopy (O51). FT-IR spectroscopy was used to investigate
the secondary structure of boar sperm proacrosin to determine
structural changes following protein autoactivation to β-acrosin
and to study the effect of suramin binding on protein secondary
structure (O52). FT-IR was used to study the conformational
differences of ovine and human corticotropin releasing hormone
(O53). FT-IR was used to obtain conformational data on the
monomeric form of insulin, which is believed to be the physi-
ologically active form of the hormone (O54). The secondary
structure of human fibrin from normal donors and from bovine
and suilline plasma was studied by FT-IR and a quantitative
analysis of its secondary structure was suggested (O55). FT-IR
spectroscopy combined with a resolution enhancement technique
has been used to characterize pressure-induced structural changes
in bovine pancreatic trypsin inhibitor (O56).
The goal of this work was to develop a portable and rapid laser-
based air sampler for detection of specific chemical contraband
and to compile a spectral database in both the near- and mid-IR
of sufficiently high quality to be useful for gas-phase spectroscopic
identification of chemical contraband (O57). A review with 13
references has been written on technique, drug distribution and
sampling homogeneity for drug hair analysis (O58). FT-IR was
used to survey and compare heroin seized throughout Israel in
1992 to detect salt forms and additives and compare the powders
for intelligence and investigation purposes (O59). A review has
been written on the use of IR spectrometry in the analysis of
narcotics (O60).
Preliminary investigations of solvent and temperature effects
upon the IR spectra of organophosphorus pesticides were carried
out and are discussed in this article (O61). This article discusses
the use of IR spectrometry to determine the configurations of
water molecules absorbed in isolated plant cuticles (O62). The
authors discuss FT-IR and Raman spectroscopic evidence for the
incorporation of cinnamaldehydes into the lignin of transgenic
tobacco plants with reduced expression of cinnamyl alcohol
dehydrogenase (O63). The IR absorption characteristics of a
highly alkaline soil and its derivatives were studied, and efforts
were made to detect polluting metals in the soil by studying the
characteristics of their IR curves (O64). This article discusses a
FT-IR investigation of the structural differences between two lipid
binding proteins extracted from plants (O65). Eleven actino-
mycete melanins from Brazilian soils were characterized by IR
analysis (O66).
This paper focuses on the increasing use of FT-IR spectroscopy
for the analysis of biomacromolecules (O67). The effect of
temperature on the secondary structure of β-lactoglobulin was
studied by FT-IR (O68). The polymorphic phase behavior of a
homologous series of saturated 1,2-diacylphosphatidylglycerols
was studied by FT-IR, DSC, and NMR (O69). The secondary
structure of apolipoprotein B-100 in low-density lipoprotein sub-
fractions was analyzed by FT-IR spectroscopy (O70). FT-IR
difference spectroscopy with self-deconvolution and second-
derivative methods as well as curve-fitting procedures are applied
to the interaction of Al and Ga cations with proteins of the
photosystem II-enriched membranes in order to determine the
cation binding mode, the protein conformational changes, and the
structural properties of metal-protein complexes (O71). The FT-
IR spectra of adenosine in the polycrystalline state were recorded
as part of a series of normal coordinate analyses of nucleic acid
components and their analogues (O72). A review has been
written with 20 references on bioorganometallic chemistry in
receptorology and analysis (O73). FT-IR and molecular modeling
have been used to characterize the interaction of Ca2+ with
hydroxy and non-hydroxy fatty acid species of cerebroside sulfate
(O74). FT-IR spectroscopy has been used to determine the cation
content of alginate thin films (O75). The FT-IR spectrum of the
oxygen-evolving center was analyzed by using spinach PSII
membranes perturbed in various ways such as calcium depletion,
chloride depletion, H-D exchange, and 15N-labeling (O76).
Comparison of the effects of amikacin and kanamycins A and B
on dimyristoylphosphatidylglycerol bilayers was investigated by
FT-IR spectroscopy (O77). The QA and the QB binding sites of
Rhodobacter sphaeroides R26 reaction centers have been investi-
gated by FT-IR spectroscopy (O78). A review with many refer-
ences has been written covering applications of the separation
and characterization of peptides and proteins by liquid chroma-
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 147R
tography, mass spectrometry, FT-IR spectroscopy, CD, and NMR
(O79). A review with 30 references has been written on the
potentially powerful technique for determining the interaction
configurations of water molecules in macromolecular systems
(O80). The aim of this study was to analyze the Raman and IR
spectra of eight common mammalian bile acids in order to identify
intermolecular interactions between hydroxyl and carbonyl groups
(O81). An infrared spectroscopic study was conducted on the
conformational fluctuation and ion permeation of lipid bilayers
doped with azobenzene derivative (O82). The reconstitution of
the retinal-containing protein bacteriorhodopsin from the apopro-
tein and retinal has been studied by FT-IR difference spectroscopy
(O83). This article focuses on the recent advances in IR
spectroscopy that have made it possible to study structural and
dynamic properties of biomembranes and model systems at the
molecular level by spectral analysis (O84). Conformational studies
of the cyclic L,D-lipopeptide surfactin were investigated by FT-IR
spectroscopy (O85). Structural changes of R-lactalbumin in
response to pH, ionic strength, sugars, and heat treatment were
investigated by DSC and FT-IR spectroscopy (O86). FT-IR
spectroscopy was used to characterize the stretching vibrations
of the ester carbonyl groups and the amide I vibration of the amide
group of N-acylphosphatidylethanolamine bilayers (O87). FT-IR
spectroscopy of dry, multilayer films has been used to study γ
radiation and UV-C light-induced lipid peroxidation in 1,2-
dilinoleoyl-sn-glycero-3-phosphocholine liposomes (O88). The
secondary structures of two forms of Saccharomyces cerevisiae
palsma membrane H+-ATPase were examined by FT-IR spectros-
copy (O89). The vibrational modes of photoactive yellow protein
and its photoproduct were studied by FT-IR spectroscopy (O90).
FT-IR spectroscopy was used to identify the molecular sites in
vesicles constituted of phosphatidylglycerol (PGV) and photosys-
tem II (PSII) that determine the formation of the PSII-PGV
complex and the sites affected by Mg(II) (O91). The kinetic
behavior of human serum albumin adsorbed on a reversed-phase
support was studied by FT-IR spectroscopy and chromatographic
methods (O92). The results of Raman and IR spectroscopic
investigations of the vibrational model of dimethyl phosphorothio-
ate anion are reported (O93). This review with 32 references
presents different techniques of FT-IR spectroscopy to investigate
microorganisms in biofilms (O94). This review has many refer-
ences and summarizes the main conformation-sensitive regions
of phospholipid IR spectra and details three recent applications
of new FT-IR methods that provide quantitative information about
phospholipid microphase separation and acyl chain conformation
(O95). Two computer programs were designed for helping in
library handling and microbial identification by means of their IR
spectra (O96). The hydration of ω-gliadins and partially deami-
dated and esterified ω-gliadins was studied by FT-IR spectroscopy
(O97). Results obtained by FT-IR spectroscopy on the influence
of Ca2+ binding on the secondary structure of calsequestrin are
reported (O98). FT-IR spectra were reviewed for glycine oligo-
mers and polyglycine (O99). The conformational variability of
the basic subdomain of c-Jun was assessed through the study of
the secondary structure of its N-terminal peptide and C-terminal
peptide fragments using FT-IR spectroscopy (O100). FT-IR
spectroscopy using principal component analysis and principal
component regression were used for the determination of K+ ions
148R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
in biological solutions by investigating interactions between the
cation and sucrose molecules (O101). The secondary structure
of native D-glyceraldehyde-3-phosphate dehydrogenase was com-
pared with its partially folded intermediate and aggregated states
obtained during guanidine hydrochloride denaturation using
transmission FT-IR and micro-FT-IR measurements (O102).
Environmental chemicals are known to induce a higher degree
of hydroxyl radical-mediated damage in DNA. FT-IR and principal
components analysis were used to test the hypothesis that this
exposure leads to new forms of DNA (O103). FT-IR spectroscopy
was applied to cytochrome P 450 to analyze the protein secondary
structure (O104). FT-IR spectra have been obtained from solid
egg white lysozyme (O105). An IR spectroscopic study has been
conducted on the structure and phase behavior of long-chain
diacylphosphatidylcholines in the gel state (O106). Pilot experi-
ments were performed to analyze the potential of FT-IR spectros-
copy for classification and identification of actinomycetes (O107).
The author has recently reported the use of a combination of
multidimensional statistical analysis and FT-IR spectroscopy for
the quantitative determination of sugars in a biological sample
(O108). A spectroscopic study was conducted on polymer/protein
interactions in composite films (O109). FT-IR studies have been
carried out to investigate the secondary structure and thermal
stability of hen egg white avidin and its complexes with biotin
and with a biotinylated lipid derivative (O110). A review with 32
references has been written on the use of FT-IR spectroscopy in
determining analytes in blood and characterization of disease
states (O111). Differences in conformational dynamics of bovine
pancreatic RNase A and RNase S were investigated using 1H-2H
exchange in conjunction with FT-IR spectroscopy (O112). The
secondary structure of the black-eyed pea trypsin/chymotrypsin
inhibitor was analyzed from the FT-IR spectrum of the protein in
D2O solution (O113). The conformation and stability of recom-
binant tetrameric human tryrosine hydroxylase isoenzyme 1 was
studied by IR spectroscopy (O114). Highly purified adenylate
kinase was characterized by FT-IR spectroscopy. Analysis of the
FT-IR spectra and estimation of secondary structure revealed a
global protein structure similar to that of other adenylate kinase
enzymes (O115). This paper reports the spectroscopic charac-
terization of two de novo peptides (O116). The effect of H/D
exchange on a FT-IR difference spectrum between the S1 and S2
states of the oxygen-evolving center in photosystem II has been
investigated (O117). A review with many references has been
written discussing the main conformation-sensitive regions of
phospholipid FT-IR methods that provide quantitative information
about phospholipid microphase separation and acyl chain confor-
mation (O118). A three-component model for the lipid barrier of
the stratum corneum consisting of ceramide III, cholesterol, and
perdeuterated palmitic acid has been characterized by FT-IR
spectroscopy (O119). FT-IR spectroscopy demonstrates that
lyophlization alters the secondary structure of recombinant human
growth hormone (O120). Thermal denaturation processes of
chicken egg white ovomacroglobulin and human serum R-2-
macroglobulin with and without chymotrypsin have been studied
(O121). An FT-IR spectroscopic study was conducted to deter-
mine protonation, conformation, and hydrogen bonding of nico-
tinamide adenine dinucleotide (O122). Grouping of Spherobacter
mitis strains grown on two different growth media was made by
FT-IR spectroscopy (O123). Effects of R-tocopherol and R-toco-
pheryl acetate on dipalmitoylphosphatidylcholine multilayers have
been investigated by FT-IR and Raman spectroscopies (O124).
Changes in conformation of oligosaccharides, and the constraints
imposed by hydrogen bonding with the solvent, were studied by
means of FT-IR and Raman (O125). A review with many
references has been written outlining four approaches, FT-IR,
Raman, CD and calorimetry, to probing protein and peptide
properties (O126). This paper describes a spectrophotometer
dedicated to the polarization modulation IR reflection-absorption
spectroscopic study of monolayers spread at the air/water
interface (O127). FT-IR measurement disclosed formation of a
thiol ester bond between a cysteine of arylmalonate decarboxylase
and an active site-directed inhibitor strongly suggesting that the
enzyme initially activates the substrates in a similar mechanism
(O128). The thermotropic phase behavior of aqueous dispersions
of dipalmitoylphosphatidylcholine and its analogues was examined
by DSC, and the organization of these molecules in those hydrated
bilayers was studied by FT-IR spectroscopy (O129). This review
with 83 references was written on the properties of lipid vesicles
studied by FT-IR spectroscopy (O130). Examination of L-tyrosine
spectra by various IR techniques allows some conclusions on the
molecular interactions in the examined systems (O131). A review
with 23 references has been written on the relative advantages
and disadvantages of various spectroscopic techniques for identify-
ing and measuring concentrations of multicomponent mixtures
(O132). The authors discuss infrared spectroscopic studies of
vancomycin and its interactions with N-acetyl-D-Ala-D-Ala and N,N′-
diacetyl-L-Lys-D-Ala-D-Ala (O133). This paper discusses spectro-
scopic characterization of the interferon-γ and analogue II in
hydroorganic solution or adsorbed on an hydrophobic chromato-
graphic support (O134). The secondary structures of staphylo-
coccal nuclease have been assigned and semiquantitatively
estimated from the deconvoluted FT-IR spectrum (O135). FT-IR
spectroscopy has been used to investigate the structure and
temperature stability of the acetylcholinesterase from Torpedo
californica (O136). The cyanide complex of iron(II) myoglobin
was studied by FT-IR spectroscopy and compared with complexes
of microperoxidase and hemoglobin (O137). FT-IR spectroscopy
has been used to investigate the structural properties of the
channel-forming integral membrane protein present in phospho-
lipid vesicles suspended in aqueous media (O138). The plant
growth hormone auxin and its natural analogue, as well as their
synthetic congeners, were studied by FT-IR spectroscopy (O139).
FT-IR spectroscopy was used to investigate the local structure
around the chromophore of rhodopsin and its change upon
photoisomerization (O140). Chemical changes in the medium,
induced by the fermentative species Lactobacillus plantarum and
Lactobacillus brevis and by the enzymic action of a proteolytic,
spoilage species, were analyzed using FT-IR spectroscopy (O141).
A complete set of vibrational spectra obtained from several
spectroscopic techniques has been used in order to assign the
vibrational modes of uracil on the basis of an ab initio scaled
quantum mechanical force field (O142). FT-IR has been used to
analyze protein conformational stability on surfaces (O143).
Structural differences between two genetic variants of bovine
β-lactoglobulins in aqueous solutions were characterized using
FT-IR and CD spectroscopies (O144). The FT-IR spectra of
several coiled coil proteins have been shown to possess unusual
features in the amide I′ region (O145). The authors of this paper
used FT-IR to measure secondary structures of isolated domains
of types III and IV intermediate filament proteins and of the
solution tetramers and the filaments formed by type III intermedi-
ate filament proteins (O146). A review with 142 references has
been written on the determination of protein secondary structure,
IR spectrometry measurement of H-D exchange in proteins, and
probing protein structure at the level of individual chemical groups
(O147). This article discusses the use of 13C-labeled molecules
in the conformational analysis of proteins by FT-IR spectroscopy
(O148). FT-IR spectroscopy has been used to compare S-cis and
S-trans conformations of planar dithiooxamides (O149). A review
with 20 references has been written on an IR spectroscopy-based
multicomponent assay of biofluids such as whole blood, urine,
and synovial fluid (O150). The redox reactions of the cytochrome
c oxidase from Paracoccus denitrificans were investigated in a thin-
layer cell designed for the combination of electrochemistry under
anaerobic conditions with UV-visible and IR spectroscopies
(O151). Hydrated sites in biogenic amorphous calcium phos-
phates have been studied by infrared spectroscopy (O152).
Similarities in the architecture of the active sites of Ni hydroge-
nases and Fe hydrogenases have been detected by means of
infrared spectroscopy (O153). The adsorption of a membrane
protein of flagellar FliF and its derivatives onto chemically
modified surfaces has been studied by FT-IR spectroscopy (O154).
FT-IR spectra of a dilute solution of N-acetyl-Pro-Leu-Gly-NH2 have
been measured and reported (O155). Changes in the secondary
structure of adsorbed IgG and F(ab′)2 was studied by FT-IR
spectroscopy (O156). An unusually high hydrogen-deuterium
exchange of the CHIP28 protein (aquaporin) from red blood cells
was observed by FT-IR spectroscopy (O157). Cyanide binding
to the heme-copper binuclear center of bo-type ubiquinol oxidase
from Escherichia coli was investigated with FT-IR and EPR
spectroscopies (O158). A combination of CD and IR spectroscopy
helps to build a molecular picture of the thermal denaturation and
conformational changes of β-lactoglobulin (O159). An FT-IR
spectroscopy study was conducted to determine conformational
order of phospholipids incorporated into human erythrocytes
(O160). A new method for the determination of R-amylase activity
in aqueous solutions and human serum by FT-IR spectroscopy is
proposed (O161). The authors of this paper synthesized and
studied by FT-IR spectroscopy monosalts of diamides as models
for the active site of aspartic proteinases (O162). In situ and ex
situ structural analysis of phospholipid-supported planar bilayers
was studied using infrared spectroscopy and atomic force micros-
copy (O163). A comparative study using IR spectroscopy was
conducted to determine the interaction of two lipid binding
proteins with membrane lipids (O164). FT-IR and FT-Raman
spectra of 5′-dAMP were determined and a normal coordinate
analysis of the mononucleotide was carried out (O165). The aim
of this study is to demonstrate the reliability of the use of FT-IR
spectroscopy to monitor conformational changes when a protein
is adsorbed under chromatographic conditions on silica material
(O166). Variants of recombinant staphylokinase were investigated
by FT-IR spectroscopy for a correlation between thermal stability
and structural features of staphylokinase and the selected mutants
(O167). FT-IR spectroscopy studies of lipoxygenase showed
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 149R
changes in the amide I′ band which correlate to structural changes
of the enzyme (O168). Free amphipathic peptides and peptides
bound to dimyristoylphosphatidylcholine were studied directly at
the air/water interface using polarization modulation IR reflection
absorption spectroscopy (O169). The possibility of using FT-IR
spectroscopy to detect subtle differences in the molecular dynam-
ics in biomembranes is discussed (O170). This paper reports the
spectroscopic characterization of two de novo peptides (O171).
Mid-IR pump-probe experiments were used to study vibrational
relaxation of CO bound to synthetic heme and porphyrin com-
plexes with different metal atoms and different promixal ligands
(O172). Mitochondrial F1 ATPase from beef heart was treated
with different buffers to modulate the nucleotide content of the
enzyme and then analyzed by FT-IR spectroscopy (O173). The
interaction between superoxide dismutase and dipalmitoylphos-
phatidylglycerol bilayer was studied with FT-IR spectroscopy
(O174). The structure, water absorbability, and mechanical
properties of the blend membranes of regenerated silk fibroin in
poly(vinyl alcohol) were studied by FT-IR spectroscopy (O175).
The detection and structure of water molecules inserted in
biomembranes by FT-IR spectroscopy is discussed and an example
is given of the study of the structures of the two main types of
water molecules that are found in leaf cuticles (O176). The use
of isotope-enhanced FT-IR spectroscopy and ESR spin-labeling to
examine the conformation of the 23-residue peptide of the
N-terminal fusion peptide of the HIV-1 gp41 protein were examined
(O177). FT-IR spectroscopy was used to study the effects of
Triton X-100 treatment on the purple membrane of Halobacterium
halobium ET1001 (O178). FT-IR and optical spectroscopy have
been used to characterize the binding of NO to the oxidized form
of the heme cd1 nitrite reductase from Pseudomonas stutzeri JM300
(O179). FT-IR spectroscopy was used to study thermally induced
H exchange in RNase A, RNase T1, and various RNase T1 mutants
in relation to the melting transition of the protein (O180). FT-IR
and surface plasmon resonance spectroscopy were used to study
the interaction of C-reactive protein from Limulus polyphemus with
phosphorylcholine groups both in aqueous solution and im-
mobilized on solid supports (O181). FT-IR spectroscopy is shown
to be a rapid method for the identification of Candida at the species
level (O182). FT-IR has been used to study the thermotropic
phase behavior of mixed vesicles made up by lipopolysaccharides
and phospholipids (O183). The FT-IR difference spectra of
4-amidinophenylmethanesulfonyl-thrombin and -trypsin com-
plexes are discussed (O184). The interaction of cisplatin and its
analogues with the phospholipid molecules of human erythrocyte
membranes was studied using IR and NMR methods (O185). The
authors discuss a method for the classification of biological FT-
IR spectra prior to quantitative analysis (O186). The secondary
structure of calmodulin from Brassica campestris pollen was
studied by FT-IR spectroscopy and the CD method (O187). The
application of IR to an analysis of yeast cytochrome oxidase is
discussed (O188). This review with four references discusses a
study of enzyme-ligand binding of chymotrypsin with amino acid
derivatives using infrared spectroscopy (O189). The thermally
induced denaturation of three chymotrypsin complexes, acyl-
enzyme cinnamoyl chymotrypsin, phenylmethylsulfonyl chymo-
trypsin, and proflavin chymotrypsin, was examined (O190). Short
linear peptides were synthesized and studied to investigate the
150R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
influence of conformational equilibrium of the matrixes on excited-
state processes, which in turn can provide information on the
structure and dynamics in solutions of these materials (O191).
FT-IR spectroscopy was used to investigate the kinetics of
secondary structure formation during refolding of small globular
proteins triggered by temperature jump or fast denaturant dilution
(O192). FT-IR difference spectroscopy was used to study the
behavior of native rhodopsin and its mutants expressed in DOS
cells solubilized in dodecyl maltoside and reconstituted into lipids
(O193). FT-IR spectroscopy has been used to study the thermally
induced exchange characteristics of those backbone amide
protons which persist in H-D exchange at ambient conditions in
RNase A, in wild-type RNase T1 and some of its variants, and in
the histone-like protein Hbsu (O194). This review with 51
references is of the development over the past thirty years of IR
spectroscopic investigations of natural and synthetic melanins
(O195). Vibrational CD and FT-IR methods for prediction of
protein secondary structure are systematically compared using
selective regression analysis (O196). FT-IR spectra were obtained
for mammalian calmodulin and two of its fragments produced by
limited proteolysis (O197). The authors investigated Raman and
IR spectra of the Watson-Crick type of the guanine‚cytosine base
pair and of the individual guanine and cytosine nucleic acid bases
by ab initio Hartree-Fock theory (O198). The effect of the nature
of the third-strand sugar on the geometry and stability of triple
helixes with a pyrimidine motif was studied by FT-IR spectroscopy
(O199). FT-IR was used to study the proper orientation of
membranes containing nicotinic acetylcholine receptors on crys-
tals (O200). FT-IR spectroscopy has been used to investigate the
secondary structure, disulfide reduction, and thermal behavior of
recombinant human granulocyte-macrophage colony-stimulating
factor in aqueous solution (O201). This review with 149 refer-
ences is of applications of FT-IR spectroscopy to the structural
study on the function of bacteriorhodopsin (O202). High-
resolution two-dimensional NMR complemented by FT-IR and CD
has been employed for the elucidation of three-dimensional
solution structure of several synthetic peptides corresponding to
the calcium binding domains of the 148 residue protein calmodulin
(O203). IR spectra of helical poly(β-phenethyl-L-aspartate) in
1,1,2,2-tetrachloroethane were observed as a function of temper-
ature (O204). This paper discusses the selective enhancement
and subsequent subtraction of atmospheric water vapor contribu-
tions from FT-IR spectra of proteins (O205). The conformation
of puroindoline-a and -b, two basic lipid-binding proteins isolated
from wheat seedlings, has been studied for the first time by IR
and Raman spectroscopy (O206). FT-IR spectroscopic studies of
hydration of such as phosphatidylcholines are discussed (O207).
FT-IR spectra of collagen films set in a vacuum chamber have
been measured as a function of time (O208). Resonance Raman
and FT-IR spectra are reported for free-base tetraphenylbacterio-
chlorin and its isotopomers (O209). FT-IR has been used to
quantitatively examine the secondary structure of imprinted
proteins in anhydrous media (O210). This review with 135
references discusses the IR spectroscopy of lipids (O211). The
metastability of dimyristoylphosphatidylethanolamine has been
studied by FT-IR spectroscopy, both in the absence and in the
presence of R-tocopherol (O212). Structural changes in the
complex formation between transducin and metarhodopsin II, the
activated form of photolyzed rhodopsin, in the visual transduction
process were analyzed by FT-IR spectroscopy (O213). The
photooxidation of the primary electron donor in several photo-
system I-related organisms has been studied by light-induced FT-
IR difference spectroscopy (O214). FT-IR spectroscopy was used
to quantitatively assess the secondary structure of proteins in
aqueous-organic mixtures ranging from pure water to a pure
solvent (O215). The influence of hydration and hydrostatic
pressure on the conformation and local interactions of phosphati-
dylinositol has been investigated using IR spectroscopy (O216).
The FT-IR spectra of photocycle intermediates of sensory rhodop-
sin II from Natronobacterium pharaonis were measured (O217).
FT-IR spectra indicate that the pressure-induced liquid crystal-to-
gel transition of dioleoylphosphatidylglycerol involves a confor-
mational change making the glycerol Csn-1-Csn-2 bond more
parallel to the bilayer surface and resulting in increased carbonyl
group hydrogen bonding (O218). FT-IR spectroscopy has been
used to characterize Langmuir-Blodgett films of purple mem-
branes deposited on Ge crystals at different surface pressures
(O219). The secondary and tertiary structures of the choline-
dependent major pneumococcal autolysin LytA amidase and of
its COOH-terminal domain have been investigated by CD and FT-
IR spectroscopy (O220). A selective solubilization process of
behenic acid in mixed Langmuir films by 2-propanol was demon-
strated by IR spectroscopy (O221). A review with 24 references
focuses on FT-IR and Raman spectroscopies in the study of
proteins and other biological molecules (O222). This paper
discusses the IR analysis of protein unfolding caused by disulfide
reduction (O223). Infrared studies of the types of coordination
of the side-chain carboxylate anion to a metal cation have been
studied for protein-metal interactions (O224). The authors
discuss the first systematic structural and conformational char-
acterization of a complete family of diribonucleotide analogues in
aqueous solution by Raman and IR spectroscopies (O225). The
authors studied the spectral variation of mixed and separated
homopolymeric RNA and DNA systems under conditions that lead
to conformational variation using FT-IR and CD (O226). Hydrogen-
bonding formation between guanine and cytosine was studied by
vibrational spectroscopy (O227). Fluorescence and FT-IR spec-
troscopic studies were used to define the role of the disulfide bond
in the calcium binding in the 33-kDa protein of photosystem II
(O228). Light-induced FT-IR difference spectra of P840 upon its
oxidation have been measured with the reaction center complex
from the green sulfur bacterium Chlorobium tepidum (O229). Mid-
IR spectra of pure sucrose solutions and of biological solutions
containing sucrose and potassium ions were investigated by
principal component analysis (O230). Conformational disorder
in liquid alkenes and in the L R and H phases of some unsaturated
phospholipids has been monitored by FT-IR spectroscopy (O231).
Upon the removal of water, proteins undergo a major, reversible
rearrangement of their secondary structure, as revealed by FT-
IR spectroscopy (O232). The hydration of 1,2-dioleoyl-sn-glyc-
erophosphoethanolamine has been studied by FT-IR spectroscopy
applied to macroscopically oriented films in comparison to related
phospholipids (O233). FT-IR (ATR) was used to probe the
kinetics of hydrogen/deuterium exchange in Manduca sexta
apolipophorin-III (O234). IR spectroscopy was applied to the
investigation of normal and oxidatively modified hepatic nuclei
(O235). This review is of structures of cell surface polysaccha-
rides as determined by FT-IR spectroscopy (O236). A review has
been written of the use of IR spectroscopy in identifying the base
composition of nucleic acids, polymorphism of duplex DNA, etc.
(O237). A review with references has been written of various
applications of FT-IR spectroscopy to the study of hydrated lipid
assemblies and biomembranes (O238). This review is of a
computational IR procedure for simulating the amide I band
envelopes in globular proteins, transition dipoles, etc. (O239). A
review with 75 references is presented on the use of FT-IR
spectroscopy for the study of enzyme systems (O240). This
article is the first one of a series aimed at determining the
numerous interaction configurations adopted by water molecules
in macromolecular systems using FT-IR spectrometry (O241).
Model systems for the hydrogen-bonded chain in the active center
of maltodextrinphosphorylase are synthesized and studied by FT-
IR spectroscopy (O242). FT-IR was used with other analytical
techniques to analyze the structural organization and thermal
stability of two spermhesins (O243). A study was undertaken of
the interaction of the Mg ion with the anionic phosphatidylglyc-
erol, and FT-IR was used to identify the Mg(II) binding sites
(O244). FT-IR and site-directed isotope labeling has been used
as a probe of local secondary structure in the transmembrane
domain of phospholamban (O245). The experimental and theo-
retical investigation of the vibrational spectra of cytosine and
protonated cytosine was performed (O246). IR spectroscopy has
been used to determine gel-state miscibility in long-chain phos-
phatidylcholine mixtures (O247). FT-IR and EXAFS spectroscopic
techniques have been used to characterize Cu and Zn complexes
with deoxycholate, a derivative of deoxycholic acid which is an
important physiological bile acid (O248). FT-IR spectroscopy was
applied to investigate the conformational aspects of synthetic
polynucleotides upon binding of berenil and pentamidine (O249).
FT-IR spectra have been recorded both as a function of time and
after prolonged exposure to buffer to study the structural changes
that lead to both the ligand- and lipid-dependent channel-inactive
states of the nicotinic acetylcholine receptor (O250). FT-IR
spectroscopy was used to investigate interactions of the cryopro-
tective agents glycerol and DMSO with Bradyrhizobium japonicum
(O251).
Gas chromatography/Fourier transform infrared spectroscopy
was used to examine a selection of 42 monosaccharides and
related compounds obtaining unambiguous identification (O252).
The results of an international trial proficiency test are described.
Compounds relevant to the Chemical Weapons Convention were
analyzed in rubber, paint and two soil samples using GC, GC/
MS, and GC/FT-IR (O253). Direct-deposition GC/FT-IR, along
with GC/MS, was used to identify trace components of plant
substances (O254). GC/FT-IR, along with other chromatography
techniques, was used to identify R-phenylethylamine in judicial
samples (O255). Purge-and-trap PLOT capillary GC/FT-IR was
used to identify volatile organic compounds in blood samples
(O256). The use of GC/FT-IR of methylsilyl ethers of disaccha-
rides to positively identify disaccharides is reported (O257). This
paper examines the photochemical transformations of dichloro-
prop and 2-naphthoxyacetic acid in aqueous solution by combined
GC/MS and GC/FT-IR analyses (O258).
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 151R
 This paper focuses on the time-resolved infrared and steady-
state Fourier transform infrared spectroscopy of native and mutant
reaction centers of R. sphaeroides (O259). Time-resolved FT-IR
spectroscopy was used to characterize the structure and dynamics
of the last step in the photocycle of the light-driven proton pump
bacteriorhodopsin (O260). Two bathointermediates of the bac-
teriorhodopsin photocycle were distinguished by nanosecond time-
resolved FT-IR spectroscopy (O261). Rapid-scan FT-IR spectros-
copy and time-resolved single-wavelength IR spectroscopy have
been applied to study the mechanism of the photochemical release
of ATP from its P3-[1-2-nitrophenyl)ethyl] ester (caged ATP)
(O262). Infrared absorbance changes of the sarcoplasmic reticu-
lum Ca2+-ATPase arising from three partial reactions of its Ca2+-
pumping cycle were triggered by the photochemical release of
ATP from caged ATP and were followed in real time using rapid-
scan FT-IR spectroscopy (O263). Changes in the vibrational
spectrum of sarcoplasmic reticulum Ca2+-ATPase in the course
of its catalytic cycle were followed in real time using rapid-scan
FT-IR spectroscopy (O264). This paper details a comparative
analysis of the refolding kinetics of RNAse A by time-resolved
FT-IR spectroscopy (O265). This review and discussion focuses
on fast events in protein folding initiated by laser-induced tem-
perature jump and probed by time-resolved infrared spectroscopy
(O266). Time-resolved FT-IR difference spectroscopy was used
to characterized the amplitude, frequency, and kinetics of the
absorbance changes induced in the IR spectrum of sarcoplasmic
reticulum Ca2+-ATPase by Ca2+ binding at the high-affinity
transport sites (O267).
A review and discussion has been written that covers applica-
tions to biological membranes and to surface chemistry (O268).
ATR was used to investigate the structure of purified P-glycopro-
tein functionally reconstituted into liposomes. A quantititative
evaluation of the secondary structure and kinetics of 2H/H
exchange of the P-glycoprotein were performed both in the
presence and in the absence of Mg-ATP, Mg-ATP-verapamil, and
Mg-ADP (O269). Examination of intact living bacterial cells was
made by ATR spectroscopy. Typical examples demonstrate that
ATR FT-IR spectroscopy makes it possible to classify and dif-
ferentiate between microorganisms in vivo (O270). ATR was used
to elucidate the hydration behavior and molecular order of
phospholipid/ganglioside bilayers (O271). A method of measur-
ing fecal lipids by ATR that requires no solvents was developed
using partial least squares (O272). The secondary structure and
orientation of the viral fusion protein hemagglutinin reconstituted
in planar members was found to assume a tilted conformation
during membrane fusion as determined by ATR (O273). Polarized
attenuated total internal reflectance was applied to study the IR
dichroism of the amide I transition moment in gramicidin A in a
supported phospholipid monolayer and Ac-Lys2-Leu24-Lys2-amide
in oriented multibilayers (O274). ATR was used to investigate
the secondary structure of the plasma membrane H+-ATPase of
corn roots and compare it to the FT-IR spectra of the Neurospora
crassa plasma membrane H+-ATPase and the H+-ATPase and the
H+/K+-ATPase from hog stomach (O275). This paper describes
a new analytical technique for the study of adsorption of sarco-
sinate surfactants on live human skin as evidenced by the presence
of spectral bands at frequencies characteristic of C-D bonds from
the deuterio surfactant upon examination by ATR IR (O276). ATR
152R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
difference spectroscopy was combined with the step-scan tech-
nique and compared to conventional transmission spectra of
biological matter (O277). ATR FT-IR was used to study the effect
of phosphatidylglycerol on the percutaneous penetration of drugs
through the dorsal skin of guinea pigs in vitro and analysis of the
molecular mechanism (O278). The secondary structure of fi-
bronectin (FN) adsorbed to polymer surfaces was investigated in
a quantitative manner using FT-IR ATR techniques (O279).
Amide hydrogen/deuterium exchange rates were recorded on thin
lysozyme films by ATR FT-IR spectroscopy as a function of the
pH of the solution from which the films were prepared (O280).
The stratum corneum structure was examined by ATR FT-IR and
X-ray scattering after prolonged in vitro iontophoresis. ATR FT-
IR studies showed that iontophoresis induced an important and
reversible increase in the hydration of the outer layers of stratum
corneum, but no increase in lipid fluidity could be detected
(O281). Representative values for amide I absorptivities were
obtained for 15 different films of globular proteins spread from
water solutions (O282). Attenuated total reflection FT-IR spec-
troscopy was used to follow the adsorption of the globular protein
lysozyme from aqueous (D2O) solution onto a silicon surface
(O283). This paper discusses and illustrates amide hydrogen/
deuterium exchange kinetics in protein films recorded by attenu-
ated total reflection infrared spectroscopy (O284). An ATR FT-
IR spectroscopic technique was developed for the estimation of
the methoxy poly(ethylene glycol) 5000 content of the methoxy
poly(ethylene glycol) 5000-modified protein bovine copper-zinc
superoxide dismutase (O285). Attenuated total reflectance FT-
IR difference spectroscopy was used in the study of the formation
of metarhodopsins (O286). A combination of ATR and FT-IR was
used to measure the bacteriorhodopsin photocycle (O287). This
paper discusses the influence of gangliosides on phospholipid
model membranes as studied by ATR FT-IR spectroscopy and the
structural information obtained (O288). ATR FT-IR, along with
angle-dependent XPS and AFM, was used to investigate mussel
adhesive protein adsorption on polystyrene and poly(octadecyl
methacrylate) (O289). ATR FT-IR was used to investigate the
effects of 10 phospholipids on the in vitro percutaneous penetration
of prednisolone through the dorsal skin of guinea pigs (O290).
The sorption of the plasma proteins human serum albumin (HSA)
and human fibrinogen (FIB) onto hemodialysis cellulose sub-
strates was investigated by the surface sensitive ATR FT-IR
spectroscopy (O291). The effects of pH and the presence of metal
ions An2- and Cd2+ on the conformation of bovine serum albumin
were investigated using ATR FT-IR spectroscopy (O292). Fourier
transform IR horizontal-attenuated total reflectance (FT-IR/IR/
H-ATR) spectroscopy was employed to determine the diffusion
coefficients of sodium p-aminosalicylate (PAS) in sheep nasal
mucosae and dialysis membranes (O293). Attenuated total
reflection FT-IR spectroscopy in conjunction with statistical
methods has been used as a new approach to rapidly discriminate
three isogenic strains of Pseudomonas aeruginosassusceptible, less
susceptible, and highly resistant to imipenemsand to follow the
structural modifications related to an outer membrane imperme-
ability (O294).
DRIFTS was used as an in situ detection method for the
qualitative and quantitative analysis of heroin, cocaine, and codeine
after separation by thin-layer chromatography (O295). DRIFTS,
along with scanning electron microscopy and other chemical
analyses, was used to study the fungal degradation of Eucalyptus
grandis (O296). Fourier transform powder diffuse reflectance
infrared spectroscopy was used to evaluate particle size of bulk
powders in pharmaceutical preparations (O297). This study
reports a quantitative correlation between specific FT-IR absorp-
tion peak intensity of phenytoin to its particle size in the bulk as
well as in powder blends of pharmaceutical preparations (O298).
This paper reports the use of DRIFTS to determine the concentra-
tions of surface-adsorbed organics present as mixtures on ben-
tonitic clays (O299). DRIFTS was used to rapidly identify
Streptococcus and Enterococcus species (O300). This paper
describes the quantitation of cefepime‚2HCl dihydrate in cefepime‚
2HCl monohydrate by DRIFTS and powder X-ray diffraction
techniques (O301).
A review with 140 references has been written of biomedical
applications of FT-IR and Raman microspectroscopy, spectral
imaging, and mapping (O302). Fourier transform IR microscopy
was used to monitor spatial variations in the quality and quantity
of the mineral phase in calcified turkey tendon (O303). A method
has been developed to obtain large red crystals of cytochrome
bc1 complex from beef heart mitochondria and the structure of
the complex by micro-FT-IR spectroscopy has been investigated
(O304). Synchrotron FT-IR microspectroscopy has been used for
in situ characterization of β-amyloid in human Alzheimer’s disease
tissue (O305). Fourier transform IR microspectroscopy was
applied to in situ detection of cholesterol ester stored in athero-
sclerotic plaques in New Zealand white rabbits (O306). This paper
details the FT-IR microspectroscopy of three distinct types of plant
tissues, nutshells, bamboo, and potato tubers (O307). The ability
of FT-IR microscopy to analyze crystal deposits in tissues,
especially in biopsy samples, was test and reported (O308). This
paper details the use of FT-IR microscopy to study solute (drug
and protein)/polymer interactions that affect solute diffusion in
and subsequent release from swellable dosage forms based on
environmentally responsive, pH-sensitive polymer networks (O309).
A newly developed microscopic FT-IR spectrometry combined
with differential scanning calorimetry has been used to investigate
simultaneously the thermal response and IR spectral changes in
protein structure in porcine stratum corneum after pretreatment
with skin enhancers (O310). FT-IR microspectroscopy has been
used to study the changes in mineral and matrix content and
composition replicate biopsies of nonosteoporotic human osteonal
bone (O311). Using FT-IR microspectroscopy, the average
translational diffusion coefficients of bile salt-lecithin mixed
micelles diffusing in amylopectin gel of varying concentration were
measured (O312). FT-IR microscopy was used to detect mineral
changes in a mouse model of osteogenesis imperfecta, an
inheritable disease characterized by skeletal deformities and brittle
bones (O313). FT-IR microscopy has been used to deduce the
role of type X collagen in endochondral ossification (O314).
This paper reports a completely noninvasive measurement of
blood glucose using near-infrared waves (O315). In this article,
near-IR spectroscopic measurements of hemoglobin concentration
in whole blood, which are potentially useful in a pulse oximeter
modified for noninvasive hemoglobinometry, are presented (O316).
This paper discusses the hemoglobin content of whole blood being
measured with a simple light-transmittance procedure using a
single-term derivative ratio calibration (O317). The authors of
this paper discuss their investigation of the development of a
sensor suitable for continuous noninvasive monitoring of blood
glucose concentrations in diabetic patients (O318). This paper
focuses on selective calibration models generated for glucose over
the 1-20 nM concentration range by use of partial least-squares
regression analysis of near-IR spectra from 5000 to 4000 cm-1
(O319). Calibration models have been generated and evaluated
for the measurement of glucose, glutamine, ammonia, lactate, and
glutamate in aqueous solutions by near-infrared spectroscopy
(O320). The authors of this article describe a multivariate
calibration procedure that is based on the use of a genetic
algorithm to guide the coupling of band-pass digital filtering and
partial least-squares regression (O321). This paper explores the
complications of determining the concentration of glucose in vivo
by near-IR spectroscopy due to the effects of optical changes
caused by fluctuations in temperature, tissue water content, and
concentration of other analytes. An investigation was conducted
to determine the magnitude of the changes in diffuse reflectance
and transmittance from changes in glucose (O322). A variable
selection method that reduces prediction bias in single factor
partial least-squares regression models was developed and applied
to near-IR absorbance spectra of glucose (O323).
Near-IR reflectance spectra of numerous frozen sections of
carcinomatous tissue and frozen sections of normal surrounding
fibroglandular tissue from patients with breast cancer are pre-
sented and discussed (O324). The authors of this study demon-
strate the possibility of using near-IR absorption and excitation
spectroscopy as accurate and rapid techniques to distinguish
between normal and cancer breast tissues (O325). This paper
illustrates how near-IR spectroscopy can discriminate between
normal and carcinomatous human breast tissues (O326). In this
study, the authors have attempted to use near-IR reflectance to
map the variability in water content across the stratum corneum
in vivo (O327). A new NIR technique based on a pseudorandom
modulation/correlation method is being developed for noninvasive
tissue diagnosis applications (O328). This paper discusses the
characterization of biological tissues using Fourier transform near-
infrared spectroscopy. Changes in the skin due to sunlight and
other environmental factors are reported (O329). The results of
this study clarify the influence of probe geometry on near-infrared
spectroscopic measurements obtained from the surface of a turbid
biological tissue (O330). This paper focuses on determining the
feasibility of near-IR analysis for quantitating urea, creatinine, and
protein in urine (O331).
Using continuous near-IR spectroscopy, the oxygenated state
of hemoglobin and the redox state of cytochrome c oxidase in
the cerebral tissue of newborn piglets were studied (O332). This
paper examines noninvasive methods for determination of the
hemoglobin content of arterial blood and the water content of skin
(O333). The authors of this paper used near-IR spectroscopy to
study noninvasive changes in cerebral hemoglobin oxygenation
in the frontal and parietal cortex during performance of a verbal
fluency task in patients with Alzheimer’s disease (O334). Acute
responses of brain oxygenation were studied during postural
change using near-IR spectroscopy. NIRS is shown to be useful
to monitor cerebral oxygenation during postural change in
humans (O335). This paper focuses on the use of a combination
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 153R
of near-IR spectroscopy and discrete wavelength near-IR imaging
to noninvasively monitor the forearm during periods of restricted
blood outflow and interrupted blood inflow (O336). A review has
been written that discusses the relationship between spectral data
and β-lipoprotein content determined by routine turbidimetry
(O337). The objective of this study was to explore whether
measurements in the near-IR spectral region can be related to
hemoglobin content of the human whole blood (O338). This
paper focuses on a clinical study comparison where near-IR spectra
and analyte reference data were collected on serum samples from
a mixed diabetic/nondiabetic population. The objective of the
study was to compare calibrations developed from spectral data
sets collected by different operators under the same experimental
conditions but separated in time (O339). This investigation
focuses on the availability of oxygen in the human vastus medialis
muscle and the tympanic, skin forehead, quadriceps, and rectal
temperatures during exercise test and postexercise with nonin-
vasive near-IR spectroscopy (O340). Near-IR was used to study
noninvasively the influence of aging on changes in the local
concentration of oxygenated hemoglobin, reduced hemoglobin,
and total hemoglobin during activation of brain function (O341).
This study focuses on the assessment by near-IR on the consump-
tion of oxygen for the vastus medialis muscle that works
supporting the weight of the human body (O342). The authors
of this paper have used second-differential near-IR spectroscopy
of water to determine the mean optical path length of the neonatal
brain (O343). This report outlines the use of near-IR spectroscopy
to measure cerebral hemoglobin oxygenation after hepatic trans-
plantation (O344). The aim of this study was to evaluate the
efficiency, validity, and practicability of near-IR reflectance analysis
compared with standard methods for measurement of fecal
carbohydrates (O345). This paper describes a novel, noninvasive
method for measuring peripheral venous oxygen saturation in
newborn infants using near-IR spectroscopy with venous occlusion
(O346). The principle and possibility of bone tissue analysis by
near-IR spectroscopy are described (O347). This paper explores
the potential of near-IR spectroscopy in the clinical laboratory.
Potential in vitro applications of NIR spectroscopy include analysis
of serum, whole blood, plasma, breast milk, feces, bone, urine,
cerebrospinal fluid, and tissue for analytes. In vivo applications
of NIR spectroscopy include measurement of brain and tissue
oxygenation and cerebral blood volume and flow characteristics,
oximetry measurements, quantitation of cytochrome, and body
fat composition. The possibility of measuring blood analytes
noninvasively is also discussed (O348). Investigation of rapid
near-IR spectroscopy in combination with fiber optics for biomedi-
cal sensing is presented in this paper (O349). This review with
16 references focuses on biological and medical applications of
near-IR spectrometry (O350). This paper describes functional
brain mapping using multichannel NIRS by applying motor
stimulation in humans (O351). The authors of this paper studied
cerebral oxygen metabolism during hypoxia to demonstrate
whether the redox state of cytochrome aa3, as measured by near-
IR spectrophotometry, reflects the brain energy level (O352). FT-
NIR spectra have been measured for native and thermal denatured
pepsin in a solid state to find a marker band for the secondary
structure of proteins (O353). Near-IR spectroscopy has been
investigated as a tool for determining the amount of nitrogen in
154R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
feces since the well-known Kjeldahl method is rather complex,
time-consuming, and expensive (O354). The purpose of this study
was to determine whether the initial rate of hemoglobin and
myoglobin deoxygenation during immediate postexercise is-
chemia, a reflection of muscle O2 consumption, can be a quantita-
tive measure of muscle oxidative metabolism (O355). This paper
compares three methods for fecal fat measurement in the presence
of long- and medium-chain triglycerides and fatty acids (O356).
This paper describes a method for estimating the cerebral blood
volume and transit time in neonates from quick oxygen increases
measured by near-infrared spectrophotometry (O357). The
authors of this paper describe the use of second derivative near-
IR spectroscopy to measure absolute deoxyhemoglobin concentra-
tions in tissue (O358).
The authors of this paper explore the potential sources of
discrepancies between living tissue near-infrared spectroscopy
algorithms (O359). The analytical strategies are described for
the ferrylmyoglobin/ABTS radical monocation assay for measur-
ing total antioxidant activity, which is a measure of the collective
H-donating abilities of the antioxidants in the samples and is based
on the interaction between antioxidants in the sample with the
2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical mono-
cation, which is highly chromogenic (O360). Asparagine and
glutamine concentrations were determined in binary aqueous
solutions with near-IR absorption spectroscopy and are described
in this paper (O361). This paper explores structure-base
calculations of the optical spectra of the LH2 bacteriochlorophyll-
protein complex from Rhodopseudomonas acidophila (O362).
Conflicting patterns of change in cytochrome c oxidase redox
status have been obtained between different near-IR spectropho-
tometers when measurements were made during tissue ischemia.
This study identifies possible sources of error that could be the
cause of the discrepancy (O363). The potential of near-IR
reflectance spectroscopy for nondestructively probing structural
changes in protein during the process of denaturation was
investigated (O364).
This review with 111 references focuses on the photobiological
application of nonlinear visible/NIR spectroscopic techniques,
exemplified by the primary processes of bacterial photosynthesis
(O365). A multichannel reflectance measurement system was
developed that uses near-IR measurements for topographic imag-
ing inside biological tissue (O366). Near-IR reflectance spectros-
copy has been used for rapidly and reproducibly measuring the
NIR spectra of mainstream smoke collected on Cambridge filter
pads and quantifying the chemical composition from the spectral
data (O367).
The authors continuously measured hepatic absorbance of
indocyanine green using near-IR spectroscopy after iv bolus
injection in rabbits and their study suggests the advanced utility
as a comprehensive liver function test (O368). The aim of this
study was to examine the possibility for predicting purine nitrogen
and total nitrogen content as a marker of microbial protein in
duodenal digesta samples of sheep by near-IR spectroscopy
(O369). To examine the feasibility of optical monitoring of cellular
energy states with tissue-transparent near-IR light, the absorptions
and fluorescence characteristics of Rhodamine 800 in isolated rat
liver mitochondria and hepatocytes were investigated (O370). This
paper focuses on the simultaneous prediction of the concentrations
of glucose, glutamine, lactic acid, ammonia, and antibody in the
culture broth of mouse-mouse hybridoma by near-infrared
reflectance spectroscopy (O371). The objective of this work was
to determine whether the Dy content of ruminal digesta samples
labeled by pulse-dosing intraruminally with Dy-labeled forages
could be determined by near-IR reflectance spectroscopy (O372).
Rat carcass characteristics were determined by classical chemical
analyses, near-IR reflectance, and total body electrical conductivity,
with the aim to establish a rapid, reliable, and soft method for
numerous body composition predictions (O373). Near-IR spec-
troscopy was applied to rat liver allografts for assessing nitric oxide
synthesis and tissue oxygenation as a means of monitoring the
refection response following liver transplantation (O374). In this
study, near-IR spectroscopy was applied to the prediction of the
concentration of nutrients and products in culture broth of a
mouse-mouse hybridoma (O375). Near-IR transmission spec-
troscopy has proven to be a more efficient and convenient
analytical method for the determination of poly(ethylene glycol)
used as a flow rate marker for the liquid phase in rumen digestion
kinetics studies (O376). Cortical spreading depression (CSD) has
been implicated in the migraine aura and in stroke. This study
demonstrates near-IR spectroscopy for the first time as capable
of noninvasive on-line detection of CSD in the pentobarbital-
anesthetized rat (O377). A continuous-wave near-IR spectroscopy
system co-operated with an NMR spectrometer has been devel-
oped for the regional correlation of nitrosyl hemoglobin formation
in gerbil head under hypoxia (O378). Near-IR, in conjunction with
measurement of cerebral blood flow, was used in rabbits with
experimental bacterial meningitis to determine whether there was
evidence for cerebral energy depletion and alterations in the
cerebral vascular bed with infection (O379). Cortical spreading
depression was monitored noninvasively by near-IR spectroscopy
in male Wistar rats (O380). The authors of this paper have shown
that an inexpensive dual wavelength near-IR tissue oxygen monitor
may be very useful to detect myoglobin oxygenation in a volume
of tissue as small as the isolated buffer-perfused rat heart (O381).
The paper discusses near-IR depth-resolved measurement of
drug concentrations during diffusion through a matrix (O382).
This paper is a description of the analytical applications of near-
IR spectroscopy in the pharmaceutical industry (O383). A study
was performed on the pharmaceutical components in tablets. Near-
IR spectroscopy was shown to measure with satisfactory accuracy
and reliability within the validity limits of calibration (O384). Near-
IR spectroscopy was used for the on-line measurement of moisture
during granulation and drying of pharmaceuticals (O385). Near-
IR spectroscopy was used to qualitatively assess the homogeneity
of a typical direct compression pharmaceutical powder blend
consisting of hydrochlorothiazide, Fast-flo lactose, croscarmellose
sodium, and magnesium stearate (O386). The authors of this
paper discuss a calibration line adjustment to facilitate the use of
synthetic calibration samples in near-infrared spectrometric analy-
sis of pharmaceutical production samples (O387). Near-IR
spectrometry was used to quantify metoprolol succinate in
controlled-release tablets (O388). The viability of using principal
component analysis and soft independent modeling of class
analogy analysis of the near-IR reflectance spectra of illicit
methaqualone tablet formulations as an aid in sample differentia-
tion was investigated (O389). This investigation focused on the
possibility of applying near-IR reflectance spectrometry to the
control of the production cycle of ranitidine hydrochloride tablets
(O390). Investigation of rapid near-IR spectroscopy in combina-
tion with fiber optics for biomedical sensing is investigated (O391).
This review with 15 references was written on reflection and
transmission NIR spectrometry direct analyses of pharmaceuticals
without the need of forming aqueous solutions (O392). This paper
demonstrates the use of near-infrared reflectance spectroscopy
to identify pharmaceutical products by the direct measurement
of tablets or capsules in a blister packing (O393). The authors
demonstrate the use of near-IR spectroscopy for assessing the
progress of reactions leading to compounds for evaluation as
antituberculosis drugs (O394).
This overview is given of the use of near-IR spectrometry for
screening characteristics of corn and soybean (O395). Near-IR
transmission spectroscopy was explored for single-seed oil de-
termination of meadowfoam (Limnanthes spp.) (O396). The
mimosine contents of Leucaena foliage, Acacia tannins, and total
phenols from leaf, bark, and pod were analyzed by a near-IR
reflectance spectrophotometer (O397). The purpose of this study
was to investigate whether near-IR reflectance spectroscopy and
chemometric methods can be used as a rapid and simple
procedure to predict the leachability of pesticides from soil
samples (O398). A near-IR spectroscopic assay has been devel-
oped for in situ monitoring of lipolysis in water-in-oil microemul-
sions stabilized by soybean lecithin (O399). The authors of this
paper describe a method of control of fermentations by means of
on-line near-infrared spectrometry (O400).
The authors of this paper describe the applications of near-IR
spectroscopy to fermentation process analysis (O401). By use
of near-IR spectroscopy, simultaneous, multiple-constituent estima-
tion of important bioprocess parameters can be obtained in a time
frame that was previously unattainable (O402). This article
discusses the potential use of near-IR spectroscopy for analyzing
strongly absorbing highly light scattering samples for bioprocess
analysis (O403). The dynamics of electronic and thermal relax-
ation of the heme in myoglobin have been determined from
subpicosecond time-resolved near-IR absorbance spectra of pho-
toexcited myoglobin (O404). Near-IR is used to determine
cerebral blood volume and cerebrovascular CO2 reactivity (O405).
Light-induced release of ADP and ATP from respective caged
nucleotides produced small distinct difference IR spectra of
creatine kinase (CK), indicating that ADP and ATP binding to
CK promoted different structural alteration (O406). FT-IR differ-
ence spectroscopy has been used to probe structural changes in
membrane proteins (O407). The effects of both neutral and
anionic lipids on the structure of the nicotinic acetylcholine
receptor have been probed using IR difference spectroscopy
(O408). This paper examines FT-IR difference spectra of tyrosine
D oxidation and plastoquinone QA reduction in photosystem II
(O409). Redox FT-IR difference spectroscopy using caged
electrons reveals contributions of carboxyl groups to the catalytic
mechanism of heme-copper oxidases (O410). FT-IR difference
spectroscopy and 13C-labeled bicarbonate techniques investigate
bicarbonate binding to the none-heme iron of photosystem II
(O411). The photocycle of 124-kDa phytochrome A from Avena
sativa was studied by FT-IR at low temperatures. Difference
spectra between the parent and the intermediates were obtained
Analytical Chemistry, Vol. 70, No. 12, June 15, 1998 155R
and show characteristic spectral features which allow a clear
distinction between the different intermediates (O412). The
tyrosine D radical FT-IR difference spectrum obtained in photo-
system II membranes has been compared to FT-IR difference
spectra of tyrosine and phenol radicals generated by UV irradiation
at low temperature (O413). The photocycle of bacteriorhodopsin
(BR) regenerated with all-trans-9-demethylretinal was investigated
by time-resolved rapid-scan FT-IR difference spectroscopy (O414).
A review with 54 references has been written of light-induced FT-
IR difference spectroscopy of the quinone vibrations in protein/
quinone interactions in the bacterial photosynthetic reaction center
(O415). FT-IR difference spectroscopy was used to investigate
Z,E isomerization of the R-84 phycoviolobilin chromophore of
phycoerythrocyanin from Mastigocladus laminosus (O416). Light-
induced FT-IR difference spectroscopy was used to investigate
protein and bacteriopheophytin response to QA reduction in
photosynthetic bacterial reaction centers from R. sphaeroides and
Rhodopseudomonas viridis (O417). Difference FT-IR spectra were
recorded for the formation of the photointermediates and isor-
hodopsin from octopus rhodopsin at low temperatures (O418).
Time-resolved FT-IR difference spectroscopy was used to char-
acterize the amplitude, frequency, and kinetics of the absorbance
changes induced in the IR spectrum of sarcoplasmic reticulum
(SR) Ca2+-ATPase by Ca2+ binding at the high-affinity transport
sites (O419). Low-temperature FT-IR difference spectroscopy has
identified a pH-dependent polarity change at the heme-copper
binuclear center of the aa3-type cytochrome c oxidase from R.
sphaeroides (O420). Molecular reaction mechanisms of proteins
have been monitored by nanosecond step-scan FT-IR difference
spectroscopy (O421). This paper details the light-induced QA/
QA FT-IR difference spectrum of the photoreduction of the
primary quinone (QA) in reaction centers from R. spaeroides
(O422). An infrared difference spectroscopy investigation was
conducted of the conformational changes of arginine kinase
induced by photochemical release of nucleotides from caged
nucleotides (O423). FT-IR spectroscopy has been used to assess
the bonding interactions of the quinone carbonyls of QA (asym-
metric binding) and QB (more symmetric) and compared to those
proposed in the X-ray structures (O424). A combination of protein
electrochemistry and spectroscopy was used to determine the
midpoint potentials of the cofactors and the redox-induced
difference spectra of cyt b and cyt c1 (O425). The authors of this
paper report the first TyrDo/TyrD FT-IR difference spectrum
obtained in spinach PS II membranes (O426). RNA/diethylstil-
bestrol interactions were studied by FT-IR difference spectroscopy
(O427). This paper examines the analysis of the polymer/
antibody/antigen interaction in a capacitive immunosensor by FT-
IR difference spectroscopy (O428). This review has been written
with many references related to light-induced FT-IR difference
spectroscopy of the primary electron donor in photosynthetic
reaction centers (O429).
This review with references is of techniques and applications
of ultrafast IR spectroscopy to biomolecules, pulse-probe methods
in biology, etc. (O430). This article discusses the rapid advances
in the generation of intense tunable ultrashort mid-IR laser pulses
which allow the use of ultrafast IR pump-probe and vibrational
echo experiments to investigate the dynamics of the fundamental
vibrational transition of CO bound to the active site of heme
156R Analytical Chemistry, Vol. 70, No. 12, June 15, 1998
proteins (O431). An ultrafast laser apparatus was developed that
allows time-resolved UV-visible and IR spectroscopy to be
performed with a time resolution of 200 fs (O432). The authors
of this paper present data from mutated photosynthetic reaction
centers where a change in the energetics of the special pair P
leads to a speed up of the electron-transfer step away from P
(O433). Picosecond IR vibrational echo experiments on a protein,
myoglobin-CO, are described in this article (O434, O435). In this
article, picosecond IR vibrational echo experiments on a mutant
protein, H64V myoglobin-CO, are described and compared to
experiments on wild-type myoglobin-CO (O436). The authors of
this paper discuss the application of step-scan FT-IR spectroscopy
with nanosecond time resolution to the photocycle of carbonyl-
Hb (O437). A nanosecond step-scan FT-IR investigation of the
KL to L transition in the bacteriorhodopsin photocycle is discussed
in this article (O438). Femtosecond IR spectroscopy of low-lying
excited states in the reaction center of R. sphaeroides are discussed
in this paper (O439). These authors discuss femtosecond IR
studies of photosynthetic reaction centers (O440). The authors
of this paper present transient absorbance spectra of the reaction
centers from the bacterium R. sphaeroides (O441).
Marianne L. McKelvy is a Research Leader in the Spectroscopy Group
of the Analytical Sciences Laboratory of the Dow Chemical Co., U.S.A.
She received her B.S. degree from the University of Detroit, Detroit, MI
(1979) and the M.S. (1982) and Ph.D. (1985) degrees in polymer
chemistry from Polytechnic University, Brooklyn, NY. She joined the Dow
Chemical Co. in the Analytical Sciences Laboratory in 1984, where she
is involved in solving polymer problems using infrared spectroscopy. Her
research interests involve the characterization of polymers using vibra-
tional spectroscopy and infrared microspectroscopy. She is a member of
the Coblentz Society, the Society for Applied Spectroscopy, and the
American Chemical Society.
Thomas R. Britt is a Project Leader in the Analytical Science Group
of the Louisiana Division of Dow Chemical Co., U.S.A. He received his
B.S. (1976) from Millsaps College, Jackson, MS, M.S. (1981) from the
University of Southern Mississippi, Hattiesburg, MS, and the Ph.D. (1981)
from the University of Southern Mississippi, Hattiesburg, MS. He joined
Dow in 1982 and has worked in new polymer development and on-line
analyzer development. For the past 9 years, he has worked in the
Instrumental Analysis group, applying FT-IR and FT-Raman spec-
troscopies in the solution of production and research problems. His
interests are polymer characterization and the application of FT-IR and
FT-Raman microspectroscopies to understanding polymers and their
processes.
Bradley L. Davis is a Research Leader in the Materials Science Group
of the Analytical Sciences Laboratory, The Dow Chemical Co., U.S.A.
He received a B.A. degree from Rice University in 1972 and a M.A. from
The University of Texas at Austin in 1974. He joined Dow in 1974 where
he has been involved primarily in the application of infrared spectroscopy
toward solving production and research problems. His research interests
include polymer characterization, determination of molecular structure,
and characterization of polymer surfaces. He is a member of the Society
for Applied Spectroscopy and the Coblentz Society.
J. Kevin Gillie is a Research Scientist in the Research and Development
group at AET Films, located in New Castle, DE. His current responsibili-
ties include directing the analytical sciences laboratory at AET Films.
Since joining AET Films, he has focused on applying a variety of analytical
techniques to the complex development, manufacturing, and application
of oriented polypropylene films. He received a B.S. in chemistry from
James Madison University in 1983 and a Ph.D. in physical chemistry
from Iowa State University in 1989. Prior to joining AET Films, he
worked in the Analytical Sciences Laboratory for The Dow Chemical Co.
He has eight years of experience applying vibrational spectroscopy to solve
complex industrial and materials problems.
Felicia B. Graves is a Research Specialist in the Molecular Spectros-
copy Group with The Dow Chemical Company, U.S.A. She received her
B.S. from Jackson State University, Jackson, MS in 1982, and M.S.
(1988) and Ph.D. (1991) from the University of Southern Mississippi,
Hattiesburg, MS. She joined the Dow Chemical Co. in the Separation
Sciences group in 1991 and, in 1993, joined the Molecular Spectroscopy
group, where she has been involved primarily in applications of infrared
and UV-visible spectroscopy. Her research interests included the develop-
ment and applications of GC-IR-MSD for materials characterization.
She is a member of the American Chemical Society, the Society for Applied
Spectroscopy, and the National Organization for the Professional Ad-
vancement of Black Chemists and Chemical Engineers.
L. Alice Lentz retired from the Analytical Sciences Laboratory, The
Dow Chemical Co., U.S.A. on December 31, 1997, with the title of
Research Associate. She received a B.A. in chemistry from Rice University
in Houston, TX and joined Dow in 1961. Her career was focused on the
fields of infrared and ultraviolet spectroscopy. While at Dow, her interests
included polymer analysis and the use of hyphenated techniques (gas
chromatography/FT-IR and liquid chromatography/FT-IR) for the elu-
cidation of molecular structure. In 1995, she received the Richard A.
Nyquist Award from Dow for long-term contributions to analytical
chemistry. She is a member of the American Chemical Society, the Society
for Applied Spectroscopy, and the Coblentz Society.
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