Copyright © 2019 American Scientific Publishers Journal of

All rights reserved Computational and Theoretical Nanoscience

Printed in the United States of America Vol. 16, 1–7, 2019

Density Functional Theoretical Studies of Some Novel

Divalent Cation-Peptide Hybrid Models
K. Rajeshwaran and B. Karthikeyan∗
Department of Chemistry, Annamalai University, Annamalainagar 608002, India

The hybrid system consisting of Zn2+ ions interacting with 3,5-Bis(Trifluoro methyl)benzylamine
Tyrosine peptide molecule through non-covalent binding forces were modelled. Geometry minization
of an isolated tyrosine peptide molecule showed an energetically unfavorable single-point geometry
in course of its potential energy surface with an intra-molecular H-bonding. Rather it preferred an
extended geometry which could possibly be accounted for its strong tendency to forming a tubular
nano-structures in solution. Similarly, the potential Lewis-base anchor points were identified and
the maximum Lewis base pair occupancies of 1.95 and 1.97 were found on the N and O-atom
of the –NH2 and –CO groups, respectively. From these active sites, the chosen peptide able to
bind metal ions like Zn2+ in solution through non-covalent interactions was proposed. Finally it has
been concluded that the charge-solvated Zn2+-Peptide hybrids could be the major contributing ‘non-
covalent’ structures in aqueous solution. The other including cation- interacting hybrid models
seemed to be less favorable in neutral condition.
Keywords: Cation- Hybrids, Charge-Solvated Hybrids, NBO Analysis, Tyrosine Peptide.

1. INTRODUCTION
Unique electronic properties of metal ions coupled with
functionalized bio-molecules and its mimics can serve
as the emergence of novel hybrid systems which in
turn became a formidable tool for various biological and
nano-biotechnological applications [1–4]. Metal ions can
enhance the absorbance of the substrates with suitable
chromophore [5–6] and also cases where the exact oppo-
site can also be happen. Nevertheless both the properties
can be trapped fruitfully in the field of sensing [7–8]. How-
ever, optical detection and sensitivity are primarily rely on
the nature of molecular interactions, as well as the intrin-
sic metallic character. In case of the metallic nano parti-
cles, it depends strongly on the size, shape factors [9–10]
and surface plasmon resonance [11–12]. In other cases, the
metal ions itself can virtually be detected in the optical
region of an electromagnetic spectrum. Especially, the late
transition heavy metal ions viz. Zn2+ , Cd2+ and Hg2+ ions
in aqueous solution should be traced. These metal ions
could be sensed and detected through a mutant absorp-
tion behavior of a suitable substrate to which the former
can easily be adhered or chemisorbed. It is well known
that the heavy metals and metalloids such as Hg, Cd,
As, Pb are highly toxic and often found to bind with
enzymes having a thiol group in a living system [13].
∗
Author to whom correspondence should be addressed.
RESEARCH ARTICLE
For example, the word “Mercaptan” itself means “Cap-
turing Mercury” is well known. Other potential functional
moieties viz. –NH2 , –COOH, –OH and aromatic rings
can also interact directly with these toxic metals. Espe-
cially, amino acids and peptides containing an aromatic
ring is known to be involves in a cation- interaction with
these metals. These cation- interaction is recognized as
an important non-covalent binding force exists in biolog-
ical systems [14–18]. The investigation of these interac-
tions thus has the potential to provide valuable information
about those non-covalent forces in solution and the chem-
ical behavior of these ions from which it can be deter-
mined/sensed qualitatively. In this context, small peptide
fragments with discrete electronic states exhibiting unique
structure dependent absorption in the UV-Visible range are
the suitable candidate to bind with these metal ions in
solution. In fact, peptide nanotubes forming hybrids with
metal ions viz. Zn2+ and Cu2+ substantially extend and
enhance optical absorption of pure peptideas shown in
the experimental studies by our group [19]. Following the
above outline, Tyrosine base C-terminal derivatized pep-
tide fragment called 3,5-Bis(Trifluoro methyl)benzylamine
Tyrosine peptide (BTTP) is chosen and it is known for
its tendency to forming nanotubes via. – stacking’s of
aromatic ring much similar to Phe–Phe nanotubes [20–21].
It is presented here DFT results on the optimization and
structural aspects of BTTP. It provides fundamental insight

J. Comput. Theor. Nanosci. 2019, Vol. 16, No. xx 1546-1955/2019/16/001/007 doi:10.1166/jctn.2019.8089 1

 Density Functional Theoretical Studies of Some Novel Divalent Cation-Peptide Hybrid Models
into the binding modes from which the BTTP can exert
weak non-covalent interaction with the group VII-B metal
ions in solution. Furthermore, the possible divalent metal
ion-peptide model systems are proposed from the outcome
of NBO analysis of BTTP. The choice of these mod-
els serve to outline and propose perspective features is
highlighted.
2. COMPUTATIONAL METHODS
The structural and optical properties of the aqueous phase
BTTP and M2+ -BTTP hybrid systems have been ana-
lyzed using Density Functional Theory and its Time-
Dependent version (TD-DFT) by using Gaussian-09
quantum-chemical software package [22]. Becke’s Three-
parameter non-local exchange functional together with
the Lee-Yang-Paar gradient corrected correlation func-
tional, B3LYP [23–24] and its coulomb-attenuated ver-
sion, CAM-B3LYP [25] have been employed to analyze
the structural properties of the system. For all atoms
Triple-Zeta split valence plus polarization atomic basis set
6-311++G (dp) have been used Ref. [26].
3. RESULTS AND DISCUSSION
Both gaseous and aqueous phase approach on small pro-
totype peptide fragment is meaningful, since it allows the
theoretical and experimental study of well-defined sys-
tems while considering the involved surrounding chemi-
RESEARCH ARTICLE
cal environments. First, it is addressed that the detailed
structural aspects of BTTP through geometry minimiza-
tion [27–28] and Natural Bond Orbital (NBO) analy-
sis [29]. For this, we choose CAM-B3LYP/6-31G (dp) is
chosen. Aqueous environment is created by means of Polar
Continuum Model [30–31] (PCM). From NBO analysis,
the Lewis base anchoring points to which these toxic metal
ions can possibly bind are determined. Subsequently, the
Fig. 1. Optimized geometry of BTTP (a) aqueous phase (b) gas phase.
2 J. Comput. Theor. Nanosci. 16, 1–7, 2019
Rajeshwaran and Karthikeyan
possible Zn2+ -BTTP hybrid models in aqueous solution
are proposed.
3.1. Minimization
Finding a Stationary Point in the PES of 3,5-Bis(trifluoro
methyl)Benzylamine Tyrosine Peptide (BTTP).
The molecular geometry minimization of Tyrosine
derivative is performed in Gaussian 09 quantum-chemical
software program, using the model chemistry RB3LYP/6-
31G (dp) in both gaseous and aqueous phase, beginning
from the structure that is pre-optimized by the semi-
empirical method [32]. After 59 steps of minimization pro-
cess in aqueous phase, the stationary point was found with
a total energy of about −1554.62 Hartrees. The iterative
nature of the optimization process is clear from the conver-
gence plot as the energy and the number of steps oscillate
above and below its final value in the course of optimiza-
tion. Also, it is evident that the PES of Tyrosine derivative
looks very shallow except for the conformer at step 20
which has a destabilizing intra-molecular H-bonding inter-
action and the plot showed a very flat potential surfaces
when nearing the bottom of the valley.
All other single point geometries prefers an extended
conformation without any intra-molecular interaction
which is more unlikely for a short peptide in solution.
The optimized structures are shown in the Figures 1(a)–(b)
and these geometries are verified as a local minima by the
frequency calculations. Frequency calculations take into
account the nuclear vibrations in their equilibrium states.
The presence of one imaginary frequency indicates the
structure is a transition state and not a local or global
minima. In this case, there are no such imaginary frequen-
cies which confirmed that the stationary point is found for
the molecular system BTTP at aforementioned theoreti-
cal model. It is an unlike characteristics of a short pep-
tides which usually prefers an intra-molecular interactions
Rajeshwaran and Karthikeyan Density Functional Theoretical Studies of Some Novel Divalent Cation-Peptide Hybrid Models
Fig. 2. Single point geometry BTTP showing an intra-molecular H-bonding.
in a bipolar zwitterion form through an H-bond [33].
It preferred an extended geometry throughout its potential
energy well with an exception of one conformer (step 20).
It seems BTTP expected to have a lot many conforma-
tional degrees of freedom under physiological conditions.
Out of 59 single point geometries, the minimization step
20 is located with a geometry of having an intra-molecular
H-bonding with total energy of −1554.4366 Hartrees.
The single point geometry of the conformer at step 20 is
shown in Figure 2 and it is found relatively less stable
when compared to all other conformers in solution as it
was evident from the convergence plot is having a very
steep peak at step 20 with an energy of 185 millihartrees
(≈116 kcal) higher than that of the optimized structure in
solution. In conformer 20, H-bonding interaction is seems
to be a destabilizing interaction and could be due to the
steric over-crowding. Also, the BTTP lacks a C-terminal
carboxyl group for the formation of zwitterion in solu-
tion. Both these phenomenon can be potential contributor
towards the formation of BTTP nanotubes in solution as
demonstrated by our earlier work.
Notice the energies reported by the DFT model in two
different phases are different as expected. Here, the energy
difference in gaseous and aqueous phase is 177.0 Hartrees,
corresponding to about 1.1 × 105 kcal/mol. For minimiza-
tion and the total energy calculations, the overall indica-
tion from the literature is that B3LYP6-31G* calculations
are giving excellent results and pBP/DN* calculation gives
reasonably good results [34–35].
As expected for tyrosine derivative, the studies fur-
ther shows that the BTTP molecule is highly polar and
hydrophilic due to the presence of phenolic OH and tri-
fluoromethyl substituents on the aromatic ring. And it
J. Comput. Theor. Nanosci. 16, 1–7, 2019
looks overall, the BTTP molecule gains stabilization by
means of solute-solvent interactions through its polar sub-
stituents in aqueous solution. DFT model further esti-
mated a stabilization energy of about 12.4 kcal/mol for the
optimized structure of BTTP in solvent. Furthermore, the
phenolic OH group show co-planarity with the ring and
RESEARCH ARTICLE
thereby maximizes the orbital overlap for effective bond-
ing and also for an extended conjugation. The amide moi-
ety shows restricted flexibility due to its –NH–CO– bond
and expected to have some double-bond character arising
from resonance stabilization. This model predicted a bond
length which is intermediate between the C–N single and
C N double bond for the scissile peptide bond [36]. Also
as expected the structure shows a trans-configuration for
the scissile bond with dihedral angle of about 178.5 and
the cis-amide bonds are rare in natural peptides.
3.2. NPA and NBO Analysis
For NBO calculation, BTTP is treated in aqueous phase
at aforementioned DFT level, RB3LYP/6-31G (dp). This
triple split-valence basis set consists of 500 AOs (15 AOs
each on C, N, O, F and 4 on each H-atoms) extended
by 344 atomic orbitals (AOs) beyond the minimum basis
level. The purpose of the study is mainly focused on the
identification of potential binding spot pertaining to the
interaction of BTTP with the selected metal ions in solu-
tion through non-covalent forces.
3.2.1. Natural Population Analysis (NPA)
In general, NPA gives the detailed information about
the atom to which the natural atomic orbital (NAO) is
attached, angular momemtum, orbital type, occupancy and
energy. The occupancies of the Rydberg (Ryd) NAOs
3
 Density Functional Theoretical Studies of Some Novel Divalent Cation-Peptide Hybrid Models
are typically much lesser than those of the Core (Cor)
and Valence (Val) NAOs of the Natural Minimum Basis
(NMB) set, reflecting the dominant role of the NMB
orbitals in describing molecular properties. Whereas the
residual “Natural Rydberg Basis-NRB” of extra-valence
NAOs plays practically no significant role in the NBO
analysis. Table I gives the summary of the NMB and NRB
population for BTTP. As stated above, it is well predicted
by the model that the 344 Rydberg orbitals of the NRB
set contributes only 0.25% of the electron density, whereas
156 NMB functions account for remaining 99.74% of the
total.
From the NAOs population, it is predicted that carbonyl
O-atom possessing maximum valence 2s orbital Lewis pair
occupancy of about 1.70 and can be a potent active-site
during any chemical interactions with a suitable reactive
species like acidic metal ions in solution. Since oxygen
has have only 4 electrons in its 2p orbitals. There is obvi-
ously more than 4 electrons in its valence orbital. This
extra population may originate from pi-bond delocalization
of carbonyl C-atom which should have 3 electrons in its
2p orbitals and in fact it shows a depletion of about 16%
in its valence 2p electron density. Similarly the phenolic
O-atom also has a more valence 2s orbital occupancy of
about 1.65 which makes it as a potent contender during
any chemical interaction in solutions. The same is found
to have more valence 2p electron density than originally
it should have. This extra population may come from the
less electronegative H-atom which is evident from the 1s
RESEARCH ARTICLE
orbital occupancy of only about 0.53 and gives explana-
tion to the Bronsted acidity of phenolic OH group in solu-
tion. Likewise, amide NH proton also suffered from a huge
depletion of electron density due to an inherent tautomeric
effect which operates on the amide bond. The population
study further reveals the other possible active-site is cen-
tering on the 1 N-atom of the NH2 group, with valence
2s orbital occupancy of about 1.43. On the other hand, the
amide N-atom has only one half of its original occupancy
in the 2s orbital which make it as a good Lewis donor
towards molecular interaction. The summary of molecu-
lar charge distribution in terms of NPA charges is shown
in Figure 3. Natural atomic charges pointed out that an
electron density on the 1 N-atom of NH2 group which
seems to be much higher than that of the rest which can
make it as an electron-rich donor atom towards molecular
interaction despite of its slightly lower valence 2s orbital
Lewis pair occupancy. It is noteworthy to mention that
all six Fluorine atoms are invariably has full of electrons
Table I. Summary of the NMB and NRB population.
S. no Type Total population
1 Core 99.97% of 56
2 Valence 99.66% of 152
3 Natural minimal basis 99.74% of 208
4 Natural rydberg basis 0.26% of 208
4 J. Comput. Theor. Nanosci. 16, 1–7, 2019
Rajeshwaran and Karthikeyan
owing to its greater electronegativity and sucks out the
electron density away from the C-atom to which they are
bonded to.
3.2.2. Natural Bond Orbital Analysis (NBO)
The search for a natural Lewis structure of BTTP molecule
through NBO analysis is performed using an in-built NBO
3.1 calculation in Gaussian quantum-chemical software
package and it has been predicted that the molecule con-
tains 48 and 28 Lewis type 2-Centered bond pair and
1-Centered lone pairs, respectively. No 3-Centered bonds
are also observed as expected. Moreover, the valence
NBOs contributes only 97% of its total electron density to
the natural Lewis structure which is slightly lesser than the
expected value. The valence Non-Lewis NBOs, contributes
about ∼1.9% (NBOs 449-500). In other words, the anti-
bonding orbital 499 to 500 has a significant occupancy in
the natural Lewis structure.
3.2.2.1. NBO Characteristics of the Scissile CO–NH
Bond. As given in the NBO 7, the C–N bond has valence
Lewis 2-Centered NBO occupancy of 1.990 e’s. Also the
NBO 7, suggesting a C–N bond with a larger polarization
co-efficient of 0.792 for the more electronegative N-atom.
The C–N NBO is formed from a sp213 hybrid (67.92%
p-character) on carbon interacting with a sp168 hybrid
(62.6% p-character) on Nitrogen and the wave equation
describing the valence Lewis structure for a C–N can be
represented in the form,
C–N = 06105sp213C + 07920sp168N (1)
The NHO of C–N is the linear combination between
the NAOs of Carbon hybrid, hC and that of Nitrogen
hybrid, hN . Here, the C-hybrid of the C–N bond has largest
co-efficient for the 2nd, 5th, 7th and 9th NAOs, corre-
sponding to the approximate description in terms of the
valence NBOs of the C-atom,
hC ≈ 056512sC − 055872px C − 025462py C
− 054902pzC (2)
Similarly, the N-hybrid has the largest co-efficient for the
same 2, 5, 7 and 9th NAOs corresponding to,
hN ≈ 061132sN + 050702px N + 022652py N
+ 056352pzN (3)
The NHO in the bonding of CO group is defined by the
NBO 8 and 9 with an occupancy of 1.994 and 1.991 for
a C–O and C–O bond, respectively. Here, the pi-bond is
equally populated like a -bond which ruled out the pos-
sibility for any non-Lewis like delocalized structure. Here,
the C–O NBO is formed from an overlapping of sp213
hybrid (67.92% p-character) on Carbon NHO with a sp139
hybrid (57.9% p-character) on the Oxygen.
C–O = 03877sp213C + 08091sp168N (4)
Rajeshwaran and Karthikeyan Density Functional Theoretical Studies of Some Novel Divalent Cation-Peptide Hybrid Models

Fig. 3. Molecular charge distribution in terms of NPA charges.

Similarly, the C–O bond can be written as,
C–O = 05328p1C + 08462p1O
From the NAO co-efficient on the respective atoms, it
is evident that each py orbitals on C and O contribute sig-
nificantly towards the pi-bonding overlap between them.
Finally, the NBO search finds the amide N–H bond
(NBO 14) of an expected Lewis structure with an occu-
3.2.2.2. Natural Hybrid Orbital Analysis (NHO). In the
present case, Nitrogen hybrid of N–H bond represent by
(5) the NBO 2 and 3 is bent away from the axis of N–H bond
by 5.2 and 5.0 , respectively. Whereas both hydrogen
NHO are approximately aligned with the bond axis (within
1 threshold). Similarly, the NHO of chiral C-atom shows
a deviation of 4.3 from the C–H bond axis (NBO 6).
The NHO of phenolic O-atom also experiences an angular
deviation of 5.5 from the axis of O–H bond.

RESEARCH ARTICLE
pancy of about 1.98 and formed from the overlapping of 3.2.2.3. Perturbation Theory Energy Analysis. All pos-
N (sp25 ) hybrids with 1s-orbital of Hydrogen. Likewise, sible interactions between “filled” donor Lewis-type NBOs
the NBO search finds the two 1 N–H bonds (NBOs 2,3), and “unfilled” acceptor Non-Lewis type NBOs with an
the O–H bond (NBO 29), the amide N–H bond (NBO 14), energy E2 associated with delocalization of electron den-
the six C–F bonds (NBOs 47 to 52), Nitrogen lone pairs sity during each transitions are presented in Table II.
(NBOs 81,82) and Oxygen lone pairs (NBOs 83-86) of Higher the energy, higher will be the stabilization, arises
the expected Lewis structure. It should be noted that the from that particular charge transfer of electron density.
Lewis lone pair occupancy of NBO 82 is only about 1.69. As given in the table, the energy value suggests the
Whereas the Lewis pair occupancy of NBO 81 is 1.95.
The Lewis lone pair on the N1-atom seems to be involved
Table II. Energies associated with delocalization of electron density
in hybridization and forming the corresponding NBO 81 using the second order Perturbation theory.
with 79% p-character. On the other hand, the lone pair
on the N5 -atom is purely residing on the 2px orbital with Donor Acceptor E(2) Ej − Ei F i j
S. no NBO (i) NBO (j) kcal/mol a.u a.u
NAO co-efficient of about 0.9083 and can easily involve
in the overlapping with the adjacent CO group and make 1 BD(2)C7–C12 BD∗ (2)C8–C9 2217 0.28 0.070
it as a weak Lewis donor unlike the former. 2 BD(2)C7–C12 BD∗ (2)C10–C11 1836 0.27 0.064
3 BD(2)C8–C9 BD∗ (2)C7–C12 1743 0.29 0.064
The NBO’s 449 to 500 represent the residual valence 4 BD(2)C8–C9 BD∗ (2)C10–C11 2189 0.28 0.071
Non-Lewis orbitals of low occupancy i.e., valence anti- 5 BD(2)C10–C11 BD∗ (2)C7–C12 2189 0.30 0.072
bond of principal chemical interest. It is important to 6 BD(2)C10–C11 BD∗ (2)C8–C9 1726 0.29 0.063
note a significant occupancy of some Non-Lewis valence 7 BD(2)C15–C20 BD∗ (2)C16–C17 2216 0.28 0.071
anti-bonds. The NBO 457 represent the  ∗ anti-bond of 8 BD(2)C15–C20 BD∗ (2)C18–C19 2049 0.28 0.068
9 BD(2)C16–C17 BD∗ (2)C15–C20 1836 0.29 0.066
carbonyl group, with polarization co-efficient of 0.8462 10 BD(2)C16–C17 BD∗ (2)C18–C19 2242 0.28 0.071
and −0.5328 for C and O respectively, having the occu- 11 BD(2)C18–C19 BD∗ (2)C15–C20 2049 0.29 0.070
pancy of 0.3015. Similarly, the other  ∗ anti-bond NHO 12 BD(2)C18–C19 BD∗ (2)C16–C17 1887 0.29 0.066
of phenyl rings belonging to NBOs 465, 467, 472, 483, 13 LP(1)N5 BD∗ (2)C3-O6 7073 0.27 0.123
485 and 490 are also invariably having the occupancy of 14 LP(2)O6 BD∗ (1)C3-N15 2354 0.73 0.119
15 LP(2)O13 RY∗ (2)C10 215 2.25 0.064
about ∼0.35.

J. Comput. Theor. Nanosci. 16, 1–7, 2019 5

 Density Functional Theoretical Studies of Some Novel Divalent Cation-Peptide Hybrid Models
Fig. 4. (a) Optimized structure showing aquated metal ion anchoring through carbonyl O- and amino N-atoms (b) Through tyrosinate O-atom
(c) cation- assisted by N-atom (d) cation- assisted by both O- and N-atom.
RESEARCH ARTICLE
delocalization arises due to the electron density displace-
ment from the valence Lewis electron pair on donor N5
to non-Lewis type  ∗ anti-bond C3 –O6 NHO with a stabi-
lizing energy of about 70.73 kcal/mol. Also the transition
will make bond order to get reduced from its original mag-
nitude to somewhat an intermediate value between a C–O
∗
single and double bond. In other words, the nN5 – CO tran-
sition should facilitate keto-imine tautomerism in solution.
∗
On the other hand, nO6 − c3–N5 transition is less favorable
(stabilizing energy of about 23.54 kcal/mol which sug-
gested that the keto form looks preferably to be exist in
∗
solution as an enolate ion). Similarly, the nO13 − c10–C11
interaction between the oxygen lone pair (NBO 86) and
∗
c10–C11 anti-bonding orbitals yields stabilization energy
of 28.88 kcal/mol. Other stabilizing interaction are mostly
arises from the – ∗ delocalization of phenyl ring as
expected and the nF − c–F∗
transition also contribute to the
overall stabilization due to charge delocalization.
From the NPA and NBO analysis, the potent Lewis
base pair anchoring points are found to be located on the
O- and N-atoms of BTTP. The N5 lone pair (NBO 82)
is seen to be having the lowest occupancy (1.699) among
the other valence type donor electron pairs and also gets
involved in charge transfer to remote NBO 48 in addition
to other possible geminal and vicinal delocalization. The
maximum Lewis base pair occupancies of 1.99 and 1.97
are found on the O-atom of the –OH and –CO groups,
6 J. Comput. Theor. Nanosci. 16, 1–7, 2019
Rajeshwaran and Karthikeyan
respectively. Similarly, the N-atom of the –NH2 group also
possess a Lewis base pair occupancy of about 1.95. From
these active sites, BTTP can able to bind the heavy metal
ions viz. Zn2+ , Cd2+ and Hg2+ ions in solution through
non-covalent interactions. According to HSAB principle,
these metal ions acts as a borderline acids in solution
from which they can establish weak interactions with the
donor N- and O-atoms of BTTP. On the basis of forego-
ing discussion, the M2+ -BTTP hybrids are modelled and
proposed. These proposed Zn2+ -BTTP hybrid systems are
shown in Figure 4.
The different hybrid models containing metal ions
through non-covalent interactions are categorized as; Metal
ion anchored via carbonyl O- and amino N-atoms, the
cation- interaction through anchoring through the same
O- and N-atoms and the one with metal ion interacts with
tyrosinate O-atom. Here, the existence of hybrid model
involving the tyrosinate ion is less favorable in neutral
solution. The phenolic OH of tyrosine is ionizable only
under suitable pH conditions. The pKa is reported to be
10.3; Thus at high pH levels it would be expected to be
primarily in the ionized state.
4. CONCLUSION
The hybrid systems consisting of Zn2+ ion interacting with
BTTP molecule through non-covalent binding forces were
modelled and the density functional theoretical studies
Rajeshwaran and Karthikeyan Density Functional Theoretical Studies of Some Novel Divalent Cation-Peptide Hybrid Models
were performed on the structural aspects of the M2+ -BTTP
hybrid system in solvent using Gaussian 09 quantum-
chemical calculations. Not much experimental studies
were carried out on such hybrid systems involving a
small peptide fragment having strong tendency to form
nanotubes in solution which in turn can acts as a
probe molecule to detect some toxic heavy metal ions.
The combined theoretical and experimental work serves
as an important pre-requisite for proposing such suit-
able molecule for applications like sensors, Bio-markers,
removal of ions etc. The geometry optimization by adopt-
ing the CAM-B3LYP hybrid DFT model for an iso-
lated BTTP molecule showed an energetically unfavorable
single-point geometry in course of its potential energy sur-
face with an intra-molecular H-bonding. Rather the BTTP
molecule preferred an extended geometry which could
possibly be accounted to its strong tendency for forming a
tubular nano-structures in solution. Also, it seems that the
BTTP molecule could get heavily solvated in water which
gained support from its stabilization energy of about 1.1 ×
105 kcal/mol. Similarly, the potential Lewis-base anchor
points on BTTP molecule were identified from the NBO
analysis. The maximum Lewis base pair occupancies of
1.99 and 1.97 are found on the O-atom of the –OH and
–CO groups, respectively. Similarly, the N-atom of the
–NH2 group also possess a Lewis base pair occupancy of
about 1.95. From these active sites, BTTP can able to bind
the heavy metal ions viz. Zn2+ , Cd2+ and Hg2+ ions in
solution through non-covalent interactions was proposed.
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Received: 30 October 2018. Accepted: 9 December 2018.
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