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Light scattering characterization of

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Holzforschung 2014; aop

Yong Qian, Yonghong Deng*, Yunqing Guo, Hao Li and Xueqing Qiu*

Light scattering characterization of lignosulfonate

structure in saline solutions
Abstract: The solution behavior and molecular conformation of sodium lignosulfonates (NaLS) in saline solution
has been studied by means of static and dynamic light scattering (LSstat and LSdyn). Results show that the salt content
must be larger to eliminate the slow mode in LSdyn analysis of NaLS than that of the theory, and this discrepancy
can only be explained by a modified microgel model. The
higher salt amount is needed for the formation of a strong
ionic gradient field between surface and the inner part
of NaLS, which forces counter ions to penetrate into the
inner part of NaLS to screen the small amount of charges.
The NaLS single molecular shape can be described by an
oblate spheroid based on the absolute molecular weight
Mw and diffusion coefficients D. The best fitting result is
semiaxis a = 1.6nm and axial ratio r = 3.5, D = 5.73 10-7cm2 s-1,
and the corresponding Mw = 1.7 105 g mol-1.
Keywords: calculation of oblate spheroids, conformation
of lignosulfonates, disaggregation, dynamic light scattering, J-aggregates, lignosulfonates, modified microgel
model, molecular aggregation, molecular disperse solution, oblate spheroids, polyelectrolytes, sodium lignosulfonate (NaLS), static light scattering
DOI 10.1515/hf-2014-0105
Received April 3, 2014; accepted September 17, 2014; previously
published online xx

Introduction
Lignosulfonate (LS) is a byproduct from acid sulfite
pulp mills or from sulfite pretreatment for sugar/biofuel
*Corresponding authors: Yonghong Deng and Xueqing Qiu: School
of Chemistry and Chemical Engineering, State Key Lab of Pulp
and Paper Engineering, South China University of Technology,
Guangzhou, Guangdong 510640, P.R. China,
Phone: +86-20-87114722, Fax: +86-20-87114721,
e-mail: yhdeng08@163.com, xueqingqiu66@163.com
Yong Qian, Yunqing Guo and Hao Li: School of Chemistry and
Chemical Engineering, State Key Laboratory of Pulp and Paper
Engineering, South China University of Technology, Guangzhou
510640, China

production (Zhou et al. 2012; Li et al. 2013; Zhou et al.

2013). As a renewable resource, LS and its modified products are widely used in various fields, such as concrete
water-dispersing agents, coal-water slurry additives, and
pesticide dispersants, just to mention a few (Ouyang etal.
2006; Yang etal. 2007; Li etal. 2009). The application performance of LS is closely related to their molecular conformation, the better understanding of which contributes to
high-performance applications of LSs.
LS was first assumed to be a spherical microgel in water
(Rezanowich and Goring 1960), in which the molecule has
charges only on the surface. Goring etal. (1979) proposed a
disc-like microgel model to explain the dimensions of LSs.
This model was accepted, though Myrvold (2008) claimed
three decades later that LSs are randomly branched polyelectrolytes. Vainio etal. (2008) proposed oblate spheroid
shapes based on small-angle X-ray scattering (SAXS). This
model is very similar to the disc-like microgel model, but
it is one order of magnitude smaller. Clearly, further investigations are needed to ensure the molecular conformation of LSs. In this context, the solution behavior of LSs is
one of the key parameters. If aqueous solutions of sodium
lignosulfonate (NaLS) are investigated by dynamic light
scattering (LSdyn), a fast mode and a slow mode dispersion can be differentiated (Qian etal. 2013a). The former
is attributed to the presence of single NaLS molecules, and
the latter to NaLS aggregates, which are large temporal
molecular associations with Coulomb interactions as the
active force (Qian etal. 2013b). Actually, LSs are never completely dissolved as molecular disperse solutions in water.
Different dissolution methods result in different degree of
aggregation (Qian etal. 2013a; Qian etal. 2014). The main
challenge of molecular shape investigation is to obtain a
molecular disperse solution and this problem has been
partly ignored in previous works.
In the present paper, NaLS molecular disperse solution was prepared under monitoring the solution by
dynamic light scattering (LSdyn) to calculate the spheric
parameters of the LS. The absolute Mw of the NaLS single
molecules should be measured by static light scattering
(LSstat) and the diffusion coefficients D should be measured by LSdyn. Both spherical and oblate spheroid shapes
should be fitted based on Mw and D results to be able to
describe the shape of NaLS molecules.

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2Y. Qian etal.: Structure of NaLS molecules

Materials and methods

The raw sodium lignosulfonate (NaLS), recovered from pulping liquor of poplar wood (Populus tomentosa Carr), was supplied by Shixian Papermaking Co. Ltd (Jilin, China). The raw NaLS was carefully
purified by filtration, ultrafiltration, chromatographic separation,
and dialysis. NaLS fractions with low polydispersity index were
obtained through gel permeation column (GPC) chromatographic
separation as described by Ouyang etal. (2010). The NaLS fractions
were further treated by GPC with ultrapure water as eluting solvent to
remove salt (Ouyang etal. 2011b). The ultrapure water (resistivity > 18
Mcm-1) used here was obtained from the Millipore water purification system (Millipore, Billerica, MA, USA). Sodium poly(styrene sulfonate) (NaPSS) standards for GPC were supplied by Sigma Aldrich
(Shanghai, China). Other chemicals such as NaCl were all analytical
grade products purchased from Sinopharm Chemical Reagent Co. Ltd
(Shanghai, China) and used directly without further purification.
The molecular weights and their distributions of NaLS were determined by GPC with Ultradrogel 120 and Ultradrogel 250columns. The
0.10 mol L-1 NaNO3 aqueous solution with pH 8 served as the eluent at
a flow rate of 0.5mL min-1. The effluent was monitored at 280nm with
a Waters 2487 UV Absorbance Detector (Waters Corp., Milford, MA,
USA) at a flow rate of 1.0mL min-1. NaPSS with a low polydispersity
index was employed as the standard for GPC calibration.
LSstat and LSdyn experiments were performed on a commercial
light scattering instrument (ALV/CGS-3; ALV, Langen, Germany)
equipped with a multi-t digital time correlator (ALV-7004; ALV,
Langen, Germany) and a solid-state He-Ne laser (JDS-Uniphase,
output power = 22 mW, at = 632.8 nm). Reduced Rayleigh ratios were
obtained for the angular range 30150. The effect of fluorescent
emission on the light scattering of NaLS was eliminated by inserting a high performance laser-line bandpass filter between the sample
solution and the detector unit (Dong and Fricke 1993). All the experiments were performed at 25C over a range of concentrations and
detection angles. The derivative refractive index increment (dn/dc)
was measured by the DnDc-2010 differential refractometer from WGE
Dr. Bures (Kerpen, Germany).
The content of functional groups in NaLS was determined by
the potentiometric titrator (809 Titrando; Metrohm Corp., Herisau,
Switzerland) according to Lin and Dence (1992). NaLS needed to be
acidized by ion-exchanging before determining the content of sulfonic group. The determination of phenolic and carboxylic groups
was performed in DMF with tetra-n-butyl ammonium hydroxide and
p-hydroxybenzoic acid as titrant and internal standard, respectively.

(Ouyang etal. 2011a). NaLS contains sulfonic, carboxylic,

and phenolic groups. It is charged to a different degree
depending on the amount of functional groups. Thus,
the charge of isolated NaLS fractions may be also different (Ouyang etal. 2011a). In the present work, the NaLS in
focus has a weight-average molecular weight (Mw) around
30,000 and a narrow polydispersity of 1.3. It contains 9.1%
sulfonic acid, 1.5% OHphen, and 2.6% COOH groups.
The dynamic laser light scattering (LSdyn) permits the
calculation of diffusion coefficient (D) and hydrodynamic
radius (Rh). Figure 1 is the normalized intensity-intensity
autocorrelation function g(2)(t) of NaLS versus decay time t,
measured at different angles. Based on the data in Figure1,
a CONTIN analysis of the LSdyn measurement shows a
bimodal decay rate distribution corresponding to a fast
mode and slow mode dissolution (Figure 2a). The diffusion coefficients of the fast mode (Df ) and the slow mode
(Ds) are calculated to be 5.22 10-7 and 4.54 10-8cm2 s-1 from
the slope of the decay rate versus q2 (Figure 2b). For polyelectrolytes, the origin of the fast mode is attributed to the
translational self-diffusion of NaLS molecules, but that
of the slow mode is still in debate, but probably Coulomb
interactions are one of the main driving forces behind
it (Frster et al. 1990; Nystrm et al. 1993; Sedlk 1993;
Sedlk 1995). Aggregate formation by means of hydrophobic interaction or hydrogen bonding (Qiu etal. 2010; Yan
etal. 2010; Myrvold 2013a) is also in discussion.
To prepare the NaLS single molecular solutions,
multichain domain or aggregates must be removed from
the solution. An effective way to do this is adding sufficient salt to inhibit the Coulomb interactions, and then
filtering the solution by a syringe filter equipped with a
suitable pore size membrane to remove the aggregates
(Myrvold 2013b; Qian et al. 2013a). Figure 3 shows the

1.0

Detector angle
30
50
70
110
150

0.8
0.6
g2 (t)

Results and discussion

NaLS was carefully purified by filtering, ultrafiltration,
GPC separation, and then fractions with a low polydispersity index were obtained. Raw NaLS usually contains
various salts that affect the properties significantly,
so each NaLS fraction was further treated by GPC with
ultrapure water as eluent for salt removal. After elution
and dialysis against the Milli-Q water, the final NaLS
samples had a very low conductivity of about 15 s cm-1

0.4
0.2
0
1E-5

1E-4

1E-3

0.01

0.1
t (ms)

10

100

Figure 1Typical normalized intensity-intensity autocorrelation

functions of 0.8 g l-1 sodium lignosulfonates versus decay time,
measured at different detector angles.

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Y. Qian etal.: Structure of NaLS molecules3

b
1.0

G ()

0.8
0.6

10-4 (s-1)

Detector angle
30
60
90
120
150

0.4

Fast mode

0.2
Slow mode
0

0.01

0.1

1
-1 (ms)

10

100

1.5

3.0

4.5

6.0

7.5

q210-10 (cm-2)

Figure 2Calculation of diffusion coefficients of NaLS in water solutions.

(a) Typical CONTIN analysis of 0.8 g l-1 sodium lignosulfonates solution measured by LSdyn at different detector angles, where a fast and a
slow relaxation modes appear. (b) Variation of the decay rate of the fast and slow modes as a function of q2.

b
1

Concentration of NaCl
(mol/l)

g2 (t)

Concentration
0.5 of NaCl
(mol/l)

c b

0.1

a 0.01
b 0.20
c 0.50
d 1.00

1E-4

1E-3

0.01
0.20
0.50
1.00

a
A (t)

a b

g2 (t)

1.0

0
0.01

0.1

10

100

0.01

0.1

10

t (ms)

t (ms)

Figure 3LSdyn measurement of 0.8 g l-1 sodium lignosulfonates (NaLS) with different salt concentrations, measured at a detector angle of
90.
(a) Typical normalized intensity-intensity autocorrelation function of NaLS versus decay time. (b) Typical CONTIN analysis of NaLS solutions,
where the fast mode has little change, but the slow mode is suppressed with increasing salt concentrations.

plot of the correlation function and the corresponding CONTIN analysis for different salt contents. In case
of higher salt content, the correlation function reaches
zero more rapidly. The decay rate peak for the fast mode
does not change much, but the peak for the slow mode is
suppressed. It decreases gradually with increasing NaCl
concentration, and finally disappears when the NaCl concentration reaches 1 mol l-1. The interpretation is that the
Coulomb interactions are eliminated around this NaCl
concentration and only a fast mode peak is present, that
is, the aggregates are destroyed.

A modified microgel model

According to the contents of sulfonic, carboxylic, and phenolic groups of NaLS, the theoretical NaCl concentration

to eliminate the Coulomb interactions was calculated to

be about 1.4 10-3 mol l-1. It is obvious that the actual salt
content must be much larger than this theoretical value.
This phenomenon cannot be explained by the conformations randomly branched polyelectrolyte model (Myrvold
2008) and a microgel model (Rezanowich and Goring
1960). In the former case, the theoretically required
amount of NaCl would also be about 1.4 10-3 mol l-1. In
the second case, the molecule has charges only on the
surface, and it is unlikely that thousands times more salt
is needed to inhibit the Coulomb interactions within the
LS. Of course, the penetration of the hydrated counterions into the inner part of the molecules with a compact
microgel structure should be more difficult than that into
a branched or linear charged polymer. To facilitate the
penetration, the inner layers shall have small amount of
charges (Yan etal. 2010). Thus, we adopt this suggestion

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4Y. Qian etal.: Structure of NaLS molecules

and propose a modified microgel model, in which the

inner layers are less charged, while most of the charged
groups are randomly distributed on the surface. For such
a molecule, essentially, more salt is needed to form a
strong ionic gradient facilitating salt penetration.
The exact molecule shape of the modified microgel
model is unclear. Rezanowich and Goring (1960) and
Goring et al. (1979) suggested a spherical shape in solution and a disk-like shape at the interface. Because of their
spherical structure, LSs tend to lose their charge at about
40C in 0.1 mol l-1 NaCl (Kontturi etal. 1992). Our experiments also proved that LSs have a minimum Zeta potential
at about 38C (Qian etal. 2013b). Vainio etal. (2008) suggested an oblate spheroid shape of LSs in solutions. The
disc-like shape can be considered as an oblate spheroid,
in which one dimension is much smaller than the other
two.
As demonstrated by Kato et al. (1999a,b, 2007), the
J-aggregates of the merocyanine dyes have an elliptical
molecular shape at the air-water interface, and the dye
molecules are oriented along the long axis of the elliptical
domain. Deng etal. (2012) found that the charge-free aromatic groups in LS tend to form oriented - stacking with
the spectroscopic characteristics of J-aggregates, in which
the charge free groups converge to each other to minimize
entropic loss, while the charged groups try to extend into
water to keep molecules stable. In aqueous solutions,
the tilted card-pack assembly with tilt angle < 54.7 is
the most possible arrangement for the aromatic groups
in J-aggregates (Deng etal. 2012). In the presence of salt,
molecular shrinkage is significant for all charged groups
because of charge screening, but the charge-free aromatic
groups in J-aggregates do not shrink. The preferred orientation of the aromatic rings in such molecules force the LS

b
1.0

Detector angle
30
60
90
120
150

G ()

0.6
0.4

Figure 4a shows CONTIN analysis of 0.8 g l-1 NaLS in

1.0 mol l-1 NaCl solution at different detector angles. Obviously, the slow mode peak mentioned above is suppressed
at all detector angles. The diffusion coefficient D of the
NaLS single molecules is calculated to be 5.73 10-7cm2 s-1
from the slope of the decay rate vs. q2 (Figure 4b). The
hydrodynamic radius Rh of NaLS is estimated to be 4.5nm
according to the Stokes-Einstein relation.

Determaination of absolute Mw
GPC mol mass determination is usually calibrated by
NaPSS. Because NaLS has a more compact structure than
NaPSS, the GPC estimation of Mw of lignins are several
times higher than NaPSS standards at the same elution
time (Pellinen and Salkinoja-Salonen 1985). LSstat is suitable for an absolute Mw determination of of NaLS, but the
polyelectrolyte and aggregation effects may lead to overestimated Mw data (Forss etal. 1976).
For a safe Mw determination by LSstat, enough NaCl
is added into the NaLS solutions for inhibition of polyelectrolyte effects, and syringe filter with a suitable pore
size membran is used to remove the aggregates (Qian
etal. 2013a). Figure 5 shows the relationship between the

0.2
0
0.01

Determination of the diffusion coefficient D

3
10-4 (s-1)

0.8

molecules to adopt a non-spherical oblate spheroid shape.

For estimating the probability for the spherical or oblate
spheroid shapes, both possibilities will be fitted based on
the molecular weight (Mw) and the diffusion coefficients
(D) in the following section.

0
0.1

1
-1 (ms)

10

100

1.5

3.0

4.5

6.0

7.5

q210-10 (cm-2)

Figure 4Calculation of the diffusion coefficient of NaLS molecules.

(a) Typical CONTIN analysis of 0.8 g l-1 NaLS in 1.0 mol l-1NaCl solution measured by LSdyn at different detector angles, where the slow
relaxation modes disappear. (b) Variation of the decay rate as a function of q2.

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Y. Qian etal.: Structure of NaLS molecules5

non-spherical particles scattered more densely than

sphere particles of the same volume did (Le Bell 1984);
therefore, a non-spherical model (e.g., an oblate ellipsoidal model) might be more fitted to the Mw (or the scattered
light intensity). As more and more evidence is provided
that shows the molecular conformation of LSs may be an
oblate ellipsoid (Goring etal. 1979; Vainio etal. 2008), this
model was adopted for both Mw and D data.
According to Perrins (1934), Eq. the Stokes-Einstein
relation for oblate ellipsoids is

1.42

KC/R106

KC/R106 (mol/g)

1.40
1.38

q2*10-14

2
0.2

0.4

0.6

0.8

D=

C (g/l)

Figure 5Concentration dependence of KC/R for sodium lignosulfonates (NaLS) solutions in water. Inset: KC/R vs. q2 for 0.8 g l-1 NaLS
solution in water. Mw calculated from the extrapolation of
KC/R to C0.

scattered light intensity of the molecular solutions and the

detector angles (insert picture), and that between the scattered light intensity and concentration. Because the particle size is less than /20, the scattered light intensity has
no angle dependence. As a result, Mw values of the NaLS
single molecules can be obtained by the concentration
dependence, which is calculated to be 1.7 105 g mol-1.

Molecular conformation calculation

If the current NaLS in saline solution can be described by
a model of spherical particles, its volume is calculated by
the Eq.: V = 4 (Rh)3/3. The Mw can be calculated by Eq. (1):
M 0.18 M w 1
V = w +
H O N A
SL
2

(1)

where, V is the volume of a single NaLS molecule in water,

NA is the Avogadros number, the mass density of NaLS
(SL) is 1.63 g ml-1 (Goring etal. 1979), and density of water
(H O) is 1.00 g ml-1. For a realistic NaLS volume in solution,
the water content in a swollen NaLS molecule has to be
taken into account, which is assumed to be 0.18 g g-1 of dry
NaLS (Wang 1954).
The fitted result is a sphere with Rh = 4.5 nm,
D = 5.73 10-7cm2 s-1, and Mw = 2.9 105 g mol-1. The Mw value
of NaLS spherical molecule is larger than the actual Mw
obtained by LSstat (1.7 105 g mol-1), and much larger than
that obtained by GPC (3.0 104 g mol-1).
The question is whether a non-spherical model is
suited for a better explanation of the solution behavior of NaLS in saline solutions. It was reported that

G( r ) =

kBT
G( r )
6 a
arctan

(2)

r 2 -1

(3)

r -1
2

where kBT is the Boltzmann energy, and is the solvent

viscosity.
The volume of a NaLS oblate ellipsoid can be obtained
by
4
4
V = a( ar )( ar ) = a 3r 2
3
3

(4)

The best fit for an oblate ellipsoid model is: semiaxis

a = 1.6nm and axial ratio r = 3.5, D = 5.73 10-7cm2 s-1, and the
corresponding Mw is 1.7 105 g mol-1. A schematic oblate
ellipsoid model of NaLS single molecules and its possible
relationship with - stacking of C9 units in NaLS is presented in Figure 6.
The axial ratio r obtained from this light scattering
fitting is in good agreement with the result reported by
SAXS fitting (Vainio etal. 2008). A similar result about nonspherical shape has been reported by Goring etal. (1979).
These authors detected that NaLS particles appeared on the

- Stacking

r=b/a=c/a=3.5

OH

L=Lignin fragment

Figure 6Schematic oblate ellipsoid model of NaLS single molecules and its possible relationship with - stacking of charge-free
aromatic groups in NaLS. Here, the mode of - stacking of chargefree aromatic groups in NaLS is J-aggregation of the intramolecular
aromatic rings.

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6Y. Qian etal.: Structure of NaLS molecules

carbon film of TEM as a spots about 10nm in diameter with

an average thickness of about 2 nm, and then proposed a
disc-like microgel model to explain the dimensions of LSs
at interfaces. Obviously, the experimental results and calculation presented above corroborate the early suggestion
that the NaLS have a non-spherical molecular shape.

Conclusions
The NaLS single molecule solution was prepared under
monitoring of dynamic light scattering (LSdyn), where
the slow mode diffraction peak was removed by adding
enough salt to inhibit the Coulomb interactions, and by
filtering with syringe filter to remove the aggregates. Perrin
formations were used to fit the ellipsoid model of the NaLS
molecules based on the absolute molecular weight and
diffusion coefficient of NaLS single molecules. The best-fit
result is an oblate ellipsoid with a semi axis of a = 1.6nm
and an axial ratio of r = 3.5, D = 5.73 10-7 cm2 s-1, and the
corresponding Mw is 1.7 105 g mol-1. A possible reason for
explaining oblate ellipsoid model of the NaLS molecules is
that the aromatic groups of NaLS tend to form oriented -
stacking with the spectroscopic characteristics of J-aggregates. The presence of J-aggregates accompanied with
molecular shrinkage of NaLS in saline solutions induces a
nonspherical molecular shape.
Acknowledgments: The authors are grateful for the financial support of National Basic Research Program of China
(973 Program) (2012CB215302), and the National Natural
Science Foundation of China (21374032). Yong Qian would
like to acknowledge the China Scholarship Council (CSC)
for supporting his visit at McMaster.

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