Colloids and Surfaces B: Biointerfaces 122 (2014) 512–519

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Colloids and Surfaces B: Biointerfaces

journal homepage: www.elsevier.com/locate/colsurfb

Intrinsic viscosity and conformational parameters of xanthan in

aqueous solutions: Salt addition effect
Cristina-Eliza Brunchi ∗ , Simona Morariu, Maria Bercea
“Petru Poni” Institute of Macromolecular Chemistry, 41-A Grigore Ghica Voda Alley, 700487 Iasi, Romania

a r t i c l e i n f o a b s t r a c t

Article history: The intrinsic viscosity and conformational parameters of xanthan in aqueous solutions were investigated
Received 24 April 2014 at 25 ◦ C as a function of salt nature (NaCl and KCl) and concentration (up to 3 × 10−1 mol/L). The visco-
Received in revised form 11 July 2014 metric parameters were evaluated by applying semi-empirical equations proposed by Rao and Wolf. The
Accepted 14 July 2014
results show that the new model proposed by Wolf provides accurate intrinsic viscosity values com-
Available online 21 July 2014
parable with those obtained by using traditional methods. The experimental data were modeled with
Paper dedicated to the 65th anniversary of Boltzmann sigmoidal equation. The stiffness parameter, hydrodynamic volume and viscometric expan-
“Petru Poni” Institute of Macromolecular sion factor were determined and discussed. With increasing salt concentration, the hydrodynamic volume
Chemistry of Romanian Academy, Iasi, and the viscometric expansion factor decrease and the critical overlap concentration increases, reaching
Romania. limiting values above a given salt concentration. The high Huggins constant values suggest the existence
of aggregates for salt concentrations above 5 × 10−2 and 3 × 10−3 mol/L for NaCl and KCl, respectively.
Keywords: Stiffness parameter was determined by Smidsrød and Haug method as being 5.45 × 10−3 , indicating a
Xanthan rigid conformation for xanthan macromolecules in solution.
Intrinsic viscosity © 2014 Published by Elsevier B.V.
Salt addition
Polyelectrolyte effect
Conformational parameters.

1. Introduction (self-interaction or with other macromolecules or low molecules)

Polysaccharides are macromolecular compounds with a large
variety of structures and chain conformations in solutions, such
as coils, semi-flexible chains, stiff chains and helical chains
(single, double and triple helical chains) which provide remark-
able physicochemical and biological properties (biocompatibility,
biodegradability and bioadhesivity) [1–3]. Among them, xanthan
is one of the most intensively studied polysaccharides due to its
unique properties, i.e., good solubility in hot or cold water, capabil-
ity to give highly viscous solutions even at very low concentrations,
stability over a wide range of temperatures and pHs, ability to mod-
ify the surface activity, the rheological properties of the system
in which is added, etc. [4]. This heteropolysaccharide of microbial
origin produced by the bacterium Xanthomonas campestris plays
an important role in different food [5,6] and non-food industries
(paints and inks, ceramics, pharmaceuticals, pulp and paper, tex-
tile, cosmetics, wastewater treatment, oil recovery) [7–9]. In these
uses, xanthan is employed as solution, gel, suspension or emulsion.
Due to its structure, it can generate different types of interactions
∗ Corresponding author. Tel.: +40 232 217454; fax: +40 232 211299.
E-mail addresses: brunchic@icmpp.ro (C.-E. Brunchi), smorariu@icmpp.ro
(S. Morariu), bercea@icmpp.ro (M. Bercea).
and hence, nano- and microstructures [10–12].
It has been shown that the primary structure of xanthan con-
sists of a linear main chain of ␤-(1–4)-d-glucose substituted at
every C3 second glucose residues by charged trisaccharide side
chain namely a d-glucuronic acid unit between two d-mannose
units. One d-mannose unit is linked to the main chain and con-
tains an acetyl group at position O6 and the other one contains
a pyruvic acid residue linked via keto group to the 4 and 6 posi-
tions [5] (Fig. 1); content of pyruvyl groups ranging from a few
fractions to 1. Each side chain carried one carboxyl group from the
␤-d-glucuronic acid unit. The secondary structure of xanthan of
double-helix is dependent on temperature and salinity conditions
[13–15].
In distilled water, at room temperature, the backbone is dis-
ordered and highly extended due to the electrostatic repulsions
exhibited between charged groups that belong to the side chains.
The high extended structure favors the hydrogen bonding and a
randomly broken helix is formed. As the temperature increases, a
transition to coil conformation occurs; the macromolecules are dis-
sociated and, as a consequence, rheological properties are changed
[16]. At 25 ◦ C, in the presence of salts, the side chains collapse
down onto the backbone due to charge screening effects and a
disorder–order transition take place when the xanthan chains tend
to adopt a stabile helical conformation.

http://dx.doi.org/10.1016/j.colsurfb.2014.07.023
0927-7765/© 2014 Published by Elsevier B.V.
 C.-E. Brunchi et al. / Colloids and Surfaces B: Biointerfaces 122 (2014) 512–519
Fig. 1. Primary structure of xanthan.
Paradossi and Brant [17] suggested that interactions between
the trisaccharide side chains and backbone might cause a greater
conformational constraint in xanthan as compared to other highly
substituted cellulose.
Norton et al. [18] have found that the ordered conforma-
tion of xanthan in aqueous solutions occurs in the presence of
3.5 × 10−2 mol/L NaCl. Based on optical rotation studies, Muller
et al. [19] have shown that a sharp conformational transition
occurs in salted solutions of 1 × 10−2 mol/L NaCl; the macro-
molecular chains of xanthan in 2 × 10−3 mol/L NaCl solution are
partially ordered and in 4 × 10−2 mol/L NaCl solution are com-
pletely ordered. Rochefort and Middleman [16] considered for a
single chain the coexistence of ordered and disordered regions up
to 1 × 10−2 mol/L NaCl and above this salt concentration the con-
formation is completely ordered. Also, they pointed out that the
secondary structure of xanthan depends on the sample character-
istics, the treatment during and after fermentation [19], solvent,
salinity and temperature [13,14].
In comparison with other polysaccharides, xanthan is quite
rigid. Tinland and Rinaudo [20] discussed the chain rigidity and
they found analogies between the conformations of xanthan with
DNA. As it was mentioned above, the presence of ionizable groups
located to the trisaccharide side chains, which dissociate in polar
solvents, can seriously affect the solution properties of xanthan and
the thermodynamic investigation of xanthan in solution has to be
done very carefully. The most used method to assess the behavior of
polymer in dilute solutions is the viscometry. For polyelectrolytes,
the interpretation of the experimental viscometric data requires
adequate evaluation methods due to their limits in application.
Starting from the realistic assumption that viscosity of dilute solu-
tions constitutes a function of state, Wolf [21] developed a new
approach which is able to describe the evolution of the viscos-
ity as a function of polymer concentration. During last years, this
model has been applied successfully for salt-free aqueous solu-
tions of poly(N-butyl-4-vinylpyridinium bromide) with different
quaternization degree [21], aqueous and salted solutions of sodium
polystyrene sulfonate [22,23], peripherically charged dendronized
poly(methyl methacrylate) [24], carboxymethyl guar [25], cationic
polyelectrolytes based on dextran in salt-free or salted aqueous
solutions [26], chitosan in solvents with different ionic strength
[27] and anionic polysaccharides in the presence or absence of
extra salt [28]. In addition, accurate values of the intrinsic vis-
cosity were reported for neutral polymers in solution: poly(vinyl
513
alcohol) in water [29], polyacrylonitrile [30,31] and its mixtures
with poly[N-(4-carboxyphenyl)-maleimide] [32] in dimethylform-
amide, for (co)polymers in good solvents [33,34] and in solvent
mixtures [35,36].
In this paper, we apply the Wolf model to investigate the
viscometric behavior of dilute aqueous xanthan solutions in the
presence/absence of monovalent salts, NaCl and KCl. The chain con-
formation and excluded volume effect are discussed as a function
of counterion nature and salt concentration. One motivating factor
behind this study is a better understanding of xanthan behavior
in water and in the presence of monovalent extra salt. The Wolf
approach is adequate to explain how the chain conformation and
the solution viscosity are influenced by polymer and salt concentra-
tion. On the other hand, the knowledge of the dependence between
chain flexibility for this polysaccharide and the type and salt con-
centrations is of high interest in practical applications.
2. Materials and methods
2.1. Materials
Commercial xanthan was supplied by Sigma-Aldrich as
powder and was used as-received without further purifica-
tion. The viscometric molecular weight of xanthan sample,
Mv = 1.165 × 106 g/mol, was evaluated by means of the relationship
proposed by Milas et al. [37]:
[] = 1.7 × 10−6 Mv1.14 (dL/g) (1)
The intrinsic viscosity, [], of xanthan in 1 × 10−1 mol/L NaCl
solution at 25 ◦ C was determined as being 13.99 dL/g (Table 1) by
using Rao method [38] which will be discussed in Section 3.1.
Inorganic monovalent salts (NaCl and KCl) purchased from
Sigma-Aldrich were used as-received.
2.2. Preparation of xanthan solutions
Highly purified deionized water obtained from a Mili-Q PF
(Millipore, Switzerland) apparatus was used for the solutions
preparation. The concentrated stock solution of xanthan in water
was prepared by dispersing dry polymer in water and its dissolu-
tion under magnetic stirring at room temperature (for 4 h). Salted
xanthan solutions were prepared by mixing of concentrated stock
solutions of xanthan with those of salt as to achieve the desired
concentrations. In order to prevent degradation of xanthan macro-
molecules, the homogeneous solutions were kept overnight at 5 ◦ C
in the refrigerator and thermostated at 25 ◦ C before the viscometric
measurements.
2.3. Viscosity measurements
The viscometric measurements of dilute polymer solutions
were carried out at 25 ◦ C (±0.01 ◦ C) using an Ubbelohde capillary
viscometer for dilution sequences of type I (Schott-Geräte) and
capillary diameter of 0.63 mm in combination with an automatic
viscosity measurement system (LAUDA LMV 830 Instrument). Flow
time for each solution was measured at least five times, until the
errors in its determination were lower than 0.1 s.
3. Results and discussion
3.1. Intrinsic viscosity of xanthan solutions in water and in the
presence of salts
Viscometry is one of the most used methods and appropri-
ate to explore the behavior of polymer chains in solution. The
514 C.-E. Brunchi et al. / Colloids and Surfaces B: Biointerfaces 122 (2014) 512–519

Table 1
Values of the intrinsic viscosity determined according to Eqs. (3) and (4), the parameters bW and []• from Eq. (4), the critical overlap concentration and kH from Eq. (2) for
xanthan in aqueous salt free solutions and in the presence of salts.

csalt (mol/L) []R (dL/g) Eq. (3) []W (dL/g) Eq. (4) bW Eq. (4) []• (dL/g) Eq. (4) c* (g/dL) kH Eq. (2)

Water
No salt 57.14 49.20 1.94 20.76 0.020 –
NaCl
1 × 10−5 45.05 44.06 1.80 23.86 0.023 –
1 × 10−4 43.67 41.30 1.82 22.95 0.024 –
6 × 10−4 27.25 27.50 0.12 0 0.036 0.424
1 × 10−2 16.31 16.00 0.08 0 0.063 0.482
5 × 10−2 15.06 15.02 0.009 0 0.067 0.635
1 × 10−1 13.99 13.75 –0.04 0 0.073 0.774
3 × 10−1 14.62 14.54 –0.02 0 0.069 0.676
KCl
1 × 10−5 38.46 40.55 2.16 20.45 0.025 –
6 × 10−5 43.67 43.66 0.87 16.62 0.023 –
3 × 10−3 17.12 16.84 0.04 0 0.060 0.544
5 × 10−2 14.86 14.90 0.05 0 0.067 0.558
1 × 10−1 14.29 14.33 0.004 0 0.070 0.661
3 × 10−1 14.25 14.04 –0.04 0 0.071 0.698

experimental data give access to intrinsic viscosity from which
useful information can be evaluated about polymer–polymer inter-
actions, excluded volume effects governed by polymer–solvent
interactions, chain stiffness and some hydrodynamic parameters
of macromolecular chain in solution. Generally, the intrinsic vis-
cosity, for many polymers in solution can be determined using the
Huggins equation:
This equation, previously applied to polyelectrolyte solutions
[40], has allowed the linearization of the viscometric data and cal-
culation of intrinsic viscosity in the dilute regime (for r < 2) for all
studied aqueous xanthan solutions (Table 1).
The new approach proposed recently by Wolf [21] allows a more
accurate determination of the intrinsic viscosity polyelectrolytes in
aqueous solutions in the absence or presence of salts:

sp c[]W + bW c[]W []•

= [] + kH []2 c (2) ln r = (4)
c 1 + bW c[]W

where sp /c is the reduced viscosity (sp = r − 1), kH represents cNaCl (mol/L)
(a) 60
the Huggins constant which offers information about the polymer no salt
interactions and the solvent quality and c is the polymer concen- -5
ηsp/c (dL/g))

1x 10
tration in solution. 50 -4
1x 10
Fig. 2 presents the plots of the reduced viscosity as a function 1x 10
-2
of xanthan concentration for different concentration of NaCl and 40 1x 10
-1
KCl in aqueous solutions. The plots obtained in pure water and in
the presence of very low salts concentration (csalt ≤ 5 × 10−4 mol/L)
show a nonlinear shape, behavior typical to polyelectrolyte solu- 20
tions, i.e., a continuous increase in the reduced viscosity with
dilution. The determination of the intrinsic viscosity employing
the extrapolation of zero-divided-by-zero type for these solutions 15
becomes not possible. This problem can be solved either by addi-
tion a sufficient amount of salt in polymer solution, or by using 0.00 0.01 0.02 0.03 0.04
of adequate equations. When a sufficient amount of salt is added,
c (g/dL)
the repulsion electrostatic interactions between ionized groups are
screened and the reduced viscosity decreases linearly with dilution
allowing for the determination of the intrinsic viscosity by Eq. (2). cKCl (mol/L)

In our case, this behavior was evidenced for xanthan solutions in (b) 60 no salt
-5
the presence of salts at concentrations higher than 3 × 10−3 mol/L, 1 x 10
as can be seen in Fig. 2. -3
3 x 10
ηsp/c (dL/g)

In order to linearize the experimental data for the correct eval- 50 -2

5 x 10
uation of the intrinsic viscosity, different semi-empirical equations
are available [39]. Among these methods, in the present study for
the evaluation of the experimental results, by taking into account 40
the macromolecular swelling and the interactions between poly-
mer and solvent in dilute solution, Rao method (Eq. (3)) [38] was
used:
20
1 1 a−1
= − (3)
1/2
2(r − 1) c[]R 2.5
0.00 0.01 0.02 0.03 0.04

where []R is the intrinsic viscosity determined by the Rao method,

r represents the relative viscosity and a is a constant for a given
polymer solvent defined as reciprocal of the maximum volume
fraction to which particles can pack.
c (g/dL)
Fig. 2. Dependence of the reduced viscosity as a function of the polymer concen-
tration for xanthan solutions in water and in aqueous solutions with different salts
content: (a) NaCl and (b) KCl.
 C.-E. Brunchi et al. / Colloids and Surfaces B: Biointerfaces 122 (2014) 512–519 515

(a) 1.8
0.6 [η ] Csalt =0

log [η] (dL/g)

lnηr
ip
1.6 cKCl

0.4 cip
NaCl
cNaCl (mol/L)
no salt 1.4
-4
1 x 10
-4
0.2 6 x 10
-2
[η ] Csalt →∞
1 x 10 1.2
-1
1 x 10

0.0
0.00 0.01 0.02 0.03 0.04
1.0
c (g/dL)) -6 -5 -4 -3 -2 -1 0
log csalt(mol/L)

Fig. 4. Double-logarithmic plot of the dependence of the intrinsic viscosity as a

(b)
function of the salt concentration: full triangle—NaCl; full circle—KCl. The full line
0.6 represents the best fit of Boltzmann sigmoid.
lnηr

to Eq. (4); for salt-free aqueous solutions of xanthan and in the

0.4 cKCl (mol/L)
no salt
-5
1 x 10
-4
0.2 1 x 10
-3
3 x 10
-1
3 x 10
0.0
0.00 0.01 0.02 0.03 0.04
c (g/dL)
Fig. 3. Dependence of the natural logarithm of the relative viscosities as a function of
xanthan concentration in water and in aqueous solutions with different monovalent
salts content: (a) NaCl and (b) KCl.
where []W is the intrinsic viscosity determined by Wolf method,
bW represents an interaction parameter and []• is the specific
characteristic hydrodynamic volume.
According to Eq. (4), [] can be determined from the initial slope
of the dependence ln r as a function of concentration, c, at suffi-
ciently low shear rates and polymer concentrations. Fig. 3 shows
the evaluation of the experimental data from Fig. 2 according to the
Wolf model.
One can observe that all calculated curves according to Eq. (4)
(lines from Fig. 3) coincide well with the experimental data and
this fact confirms that Wolf approach is appropriate to describe
the viscometric behavior of xanthan in water as well as in salted
aqueous solutions.
Table 1 summarizes the values of viscometric parameters for
xanthan solutions evaluated by using Eqs. (3) and (4) and the critical
concentration at which polymer coils begin to overlap, c*, deter-
mined as 1/[]W [40].
The analysis of the intrinsic viscosity values given in Table 1
reveals the following aspects:
(i) the highest value of the intrinsic viscosity was obtained for
xanthan solution in pure water and, as the salt content in solutions
increases, the values of intrinsic viscosity decreases;
(ii) for xanthan in KCl solutions the values of the intrinsic vis-
cosity are slightly lower than those obtained in NaCl solutions.
The slightly higher affinity of K+ for xanthan macromolecules as
compared with the Na+ counterions leads to a more compact con-
formation of the chains and thus the intrinsic viscosity is reduced;
(iii) for the salt concentrations higher than 1 × 10−2 mol/L, the
values of the intrinsic viscosity obtained by using Eq. (3) are in good
agreement with those determined from the initial slope according
presence of low content of monovalent salts, the accuracy of the
Rao method in determining [] decreases.
According to Rochefort and Middleman [16], in aqueous solu-
tions at 25 ◦ C, the backbone of xanthan is extended but disordered
or partly ordered in the form of a randomly broken helix, due to
the electrostatic repulsions interactions between COO– groups on
the side chains allowing them to align and associate by hydrogen
bonding and to form a weakly structured material. The small dif-
ferences between the values of intrinsic viscosity in water and in
the presence of low salt concentration could be due to the repul-
sion electrostatic interactions which are still effective and the chain
conformation of xanthan does not differ very much. As the salt
concentration increases, Na+ and K+ counterions screen the ionic
interactions, xanthan chains adopt a more compact conformation
in solution and thus, the intrinsic viscosity value decreases [41].
The macromolecular chain conformation in solution is reflected in
values of the critical overlap concentration, c*, which separates the
dilute–semidilute regimes. c* presents very low values in water
and in solutions with low salt content (Table 1) due to expanded
conformation of xanthan chains [42,43]. By increasing the salt con-
centration in aqueous xanthan solutions, the electrostatic repulsion
interactions are diminished and c* increases and reaches a constant
value above 5 × 10−2 mol/L of monovalent salt.
For a better quantification of the salt effect on the intrinsic
viscosity of xanthan solutions, in Fig. 4 it was represented the
dependence of the intrinsic viscosity on salt concentration of solu-
tion in a double logarithmic plot. The curve was calculated by
adjusting the parameters of the Boltzmann sigmoid, as proposed
by Eich and Wolf [44]:
log []csalt =0 − log []csalt →∞
log[] = log []csalt →∞ + (5)
ip
1 + exp{log(H(csalt /csalt ))}
where []csalt =0 is the intrinsic viscosity determined for xanthan
solution without salt, []csalt →∞ is the intrinsic viscosity determined
ip
for xanthan solution with large amount of salt, csalt represents the
inflection point of the dependence log[] as a function of logcsalt
and H is an adjustable parameter.
As it was also shown in previous investigations of polycations
[26] and polyanions [28,45], for xanthan solutions, the value of H
was equal to 1. The point of inflexion of the Boltzmann sigmoid
can be considered as the salt concentration for which the intrinsic
viscosity of the charged macromolecule becomes most sensitive to
the changes in salt concentration [26,44].
516 C.-E. Brunchi et al. / Colloids and Surfaces B: Biointerfaces 122 (2014) 512–519
In Fig. 4, the upper dot-dashed line indicates the intrinsic viscos-
ity of aqueous solution determined in the absence of salt ([]csalt =0 )
and the lower one indicates the limiting value of the intrinsic
viscosity resulting from the modeling the viscometric data for
solutions of xanthan in the presence of a large amount of salt
([]csalt →∞ ). The log[]W − logcsalt curve demonstrates that the salt
effect on the specific hydrodynamic volume of polymer is higher in
the range of very low salt concentrations.
The influence of extra salt on the viscometric behavior of dilute
xanthan solutions can also be discussed by means of the parameters
bW and []• from Eq. (4) which determine the curvature of ln r as a
function of polymer concentration; their values resulted from mod-
eling of the experimental data are listed in Table 1. The parameter
[]• is an adjustable parameter in Eq. (4) required for expressing the
behavior of polyelectrolytes aqueous solutions [21,22,24,25,45–47]
and it has the same dimension as []; for neutral polymers in
organic solvents, it becomes zero [32,35,36]. The values of []• pre-
sented in Table 1 show its sensitivity to salt in aqueous solution; for
very low salt concentrations, when xanthan in solution behaves as
a polyelectrolyte, this parameter has a value comparable with those
obtained in water. With increasing salt concentration in aqueous
xanthan solutions (cNaCl ≥ 6 × 10−4 mol/L and cKCl ≥ 3 × 10−3 mol/L)
[]• becomes zero.
The parameter bW from Eq. (4) represents a measure of pair
polymer–polymer segment interaction [24]. bW presents posi-
tive values for almost all uncharged polymers [35,36,45,46] and
expresses the typical behavior in thermodynamically good solvents
when the polymer–solvent contacts are preferred. At the opposite
side, there are unfavorable thermodynamic solvents for which bW
takes negative values. In such cases, the polymer–polymer contacts
are preferred and the coils are considerably shrunken [24].
In the case of polyelectrolyte solutions, bW represents
the contributions of Coulombic (bWCoulomb ) and non-Coulombic
(bWnon−Coulomb ) interactions [24,47], according to Eq. (6):
bW = bWCoulomb + bWnon-Coulomb
For the studied xanthan solutions, the values of bW vary in a
large domain, from positive values in water and in the presence of
a low content of salts, to negative ones for high content of NaCl or
KCl (Table 1). In the presence of a low quantity of salt, the contri-
bution of non-Coulombic interactions to bW is very small (it ranges
typically from −0.3 to +0.3 [47]) as compared with the contribu-
tion of electrostatic interactions. The occurrence of electrostatic
interactions leads to large and positive bW values and bWCoulomb
contribution is significant. Considering that the term bWCoulomb
is positive and bWnon−Coulomb is negative [24], in the presence of
increasing quantities of Na+ or K+ ions in solution, the Coulom-
bic interactions are counterbalanced by the non-Coulombic up to
bW becomes zero (csalt varies from 6 × 10−4 to 5 × 10−2 mol/L). For
high csalt concentrations, the values of bW become negative which
means that the non-Coulombic interactions are preponderant and
lead to an aggregation of the macromolecular coils which is visi-
ble macroscopically. bW has the same physical meaning as Huggins
coefficient from Eq. (2). In our study, it was possible to evaluate
the kH value only for csalt ≥ 6 × 10−4 mol/L in NaCl solutions and
csalt 3 × 10−3 mol/L in KCl solutions when the linear dependences
of sp /c as a function of concentration were obtained. The val-
ues of Huggins coefficient are given in Table 1. kH values below
0.5 indicate the existence of the preponderant polymer–solvent
interactions, whereas the values higher than 0.5 suggest the forma-
tion of macromolecular aggregates due to the stronger interactions
between polymer segments as compared with polymer–solvent
interactions. Tinland and Rinaudo [20] also found that for a salt con-
centration of 3 × 10−1 mol/L, the macromolecular chains of purified
xanthan undergo an aggregation process (“pseudogel” formation).
2.5
no salt
2.0
bW
1.5
1.0
b =0
0.5
0.0
-5 -4 -3 -2 -1 0
log csalt(mol/L)
Fig. 5. Dependence of bW parameter as a function of the salt concentration from
solvent; open symbols: full triangle—NaCl; full circle—KCl. The full line is to guide
eyes.
In our case, for a commercial unpurified xanthan sample, the
aggregation was observed for lower salt concentration: 5 × 10−2
and 3 × 10−3 mol/L for NaCl and KCl, respectively, showing that
KCl is a more suitable salt for aggregation. Between these monova-
lent cations, potassium will form stronger gels than sodium, since
potassium is more effective than sodium in promoting gelation
stabilizing junction zones.
According to Sworn [48], the salt effect on the solution vis-
cosity is influenced by xanthan concentration. For low-polymer
concentrations, below 0.25 g/dL, the addition of a small quantity
of monovalent salts (up to 1.7 × 10−2 mol/L NaCl) determines the
decrease in the solution viscosity, whereas for polymer concentra-
tions above 0.25 g/dL, the viscosity increases with salt addition (up
to 1.7 × 10−2 mol/L NaCl). For csalt > 1.7 × 10−2 mol/L NaCl the vis-
(6) cosity plateau is reached and further salt addition has a little effect
on viscosity.
Fig. 5 shows that the dependence of bW on salinity of aqueous
solutions looks very similar to that of the intrinsic viscosity as pre-
sented in Fig. 4; the dotted upper line represents the bW parameter
for xanthan in pure water and the lower one indicates the limiting
value of bW obtained by modeling the data for a large amount of salt.
In the region of very small concentration of salt, the errors in eval-
uation of bW were very high and for csalt → ∞ they were found very
small. The substitution of NaCl with KCl remains without significant
consequences for the interaction parameter bW .
3.2. Stiffness parameter
Because the extrapolation procedures which use the intrinsic
viscosity in good solvent conditions in order to obtain the unper-
turbed dimensions for neutral polymers were not applicable to
polysaccharides [49], Palas and Hermans [50] proposed to assess
the conformation of polyelectrolytes by means of stiffness param-
eter S. Its value is given by the slope of the linear dependence
between the intrinsic viscosity and reciprocal of the square-root
of the ionic strength:
[] = []∞ + SI −1/2 (7)
where []∞ represents the intrinsic viscosity at infinite ionic
strength and I is the ionic strength of the solution.
This method was able to estimate the conformation for poly-
mers of the same molar mass and in identical solvent conditions.
Smidsrød and Haug [51] removed these restrictions by introducing
 C.-E. Brunchi et al. / Colloids and Surfaces B: Biointerfaces 122 (2014) 512–519
20
[η ] Csalt →∞= 13.96 ± 1.08 dL/g
[η]W (dL/g)
S = 0.168 ± 0.013
18
16
14 NaCl
KCl
12
0 4 8 12 16
-1/2 -1/2
I (mol/L)
Fig. 6. Dependence of the intrinsic viscosity as a function of I−1/2 for xanthan solu-
tions.
a new parameter, B, as a measure of the response of [] to a fixed
ionic strength (i.e., 1 × 10−1 mol/L):
S in the absence of shear, which is influenced by nature of the poly-
B=
([]0.1 )
where []0.1 is intrinsic viscosity at 1 × 10−1 mol/L ionic strength, 
was found to vary between 1.2 (polyphosphate) and 1.4 (DNA). In
the present paper, an average value of 1.3 was considered.
Fig. 6 shows the plot of intrinsic viscosity as a function of I−1/2
for xanthan solutions.
The value of B was determined as being 5.45 × 10−3 which is in
agreement with the value of 5.25 × 10−3 reported for xanthan by
Tinland and Rinaudo [20]. This value for parameter B suggests a stiff
conformation for xanthan in solution, as for double-stranded DNA
for which B = 5.5 × 10−3 was reported by Smidsrød and Haug [51].
Dextran sulfate, amylose xanthate and poly(vinyl alcohol sulfate)
are at the opposite side with high B value (approx. 2.3 × 10−1 ) which
means very flexible polymer chain, whereas carboxymethylcellu-
lose is known as a semiflexible polymer being characterized by B
value of approx. 4.5 × 10−2 –6.5 × 10−2 [51]. Recently, for chitosan
with the acetylation degree of 26%, a value of 6.3 × 10−2 [27] was
reported for B and for oxypullulan of 9.21 × 10−2 [28].
The intercept of the extrapolation at infinite ionic strength
of linear dependence between [] and I−1/2 from Fig. 6 gives
[]∞ = 13.96 dL/g. For chitosan solutions [27], it was considered
that the repulsion electrostatic interactions between protonated
amino groups in chitosan are largely suppressed at infinite ionic
strength and thus []∞ could be interpreted as the viscosity under
theta conditions ([] ). It is well known that the theta condition
cannot be easily established because the excluded volume interac-
tions exist between both like and unlike segment pairs. In addition,
polysaccharides often form aggregates in solution that can mask the
behavior of individual macromolecules [2]. Previously, for xanthan
solutions at infinite ionic strength at 25 ◦ C, Tinland and Rinaudo
[20] found that the second virial coefficient is zero. In our case,
in the studied domain of salt concentrations, it is assumed that
the value of []∞ approximates the intrinsic viscosity under theta
condition.
By adding salt in aqueous solutions, the xanthan chains undergo
some changes which are reflected in a decrease in the chain rigidity,
persistence length and intrinsic viscosity. Based on AFM mea-
surements, Camestano and Wilkinson [43] have found that the
persistence length decreases, when salt was added, from 417 nm, in
water, at 370 nm, in 1 × 10−2 M KCl, and 141 nm, in 1 × 10−1 M KCl;
this evolution of the persistence length in KCl solutions is in agree-
ment with the observed one in ammonium acetate solutions by
517
Stokke et al. [52,53]. They considered that these changes in the per-
sistence length are due to differences in the helical structure of the
xanthan molecules. In water or at very low salt concentrations, the
xanthan chains exist as a single helix (corresponding to a disordered
conformation), while by the addition of a sufficient quantity of salt
the macromolecular chains are forced to adopt a helical conforma-
tion which promotes the intermolecular rather than intramolecular
associations [54,55]. In a concentrated salt solution, the xanthan
chains exist as a double helix (corresponding to an ordered confor-
mation) [43]. In our study, by means of Eq. (5), it was determined
the upper limit of the salt concentration, namely the inflection
ip
point noted as csalt , for which we suppose that the isolated poly-
ip
mer coils are as a single helix; csalt = 0.81 × 10−3 mol/L NaCl and
0.47 × 10−3 mol/L KCl which corresponds to []of 26.19 dL/g for
20
xanthan aqueous solution in NaCl and 25.51 dL/g in KCl.
3.3. Conformational properties of xanthan in water and in the
presence of salts
The intrinsic viscosity is a measure of macromolecular chain
conformation and dimension in the limit of infinite dilution and
(8)
mer, the thermodynamic quality of the solvent and temperature.
In order to obtain information concerning the conformation of the
xanthan chain in aqueous solutions with different salt contents, the
hydrodynamic volume of an individual macromolecule induced by
the presence of other macromolecules, {}/[], was calculated as
follows:
{} 1 + 2rb(c[]) + rb2 (c[])2
= (9)
[] 1 + 2b(c[]) + b2 (c[])2
where {} represents the specific hydrodynamic volume at a given
polymer concentration, [] is the specific hydrodynamic volume
at infinite dilution, r = []• /[] and c[] is a dimensionless reduced
concentration.
Fig. 7 shows the dependences {}/[] as a function of c[]
obtained by means of Eq. (9) and the parameters given in Table 1
for the studied xanthan solutions.
One can observe that all curves start from {}/[] = 1 at c[] = 0,
when {} = [], and decrease as c[] increases. The decrease in
{}/[] with increase in c[] is faster for the xanthan in water
and in solvents with csalt = 1 × 10−5 –6 × 10−4 mol/L than in sol-
vents with csalt ≥ 1 × 10−3 mol/L and reflects the solvent salinity. By
increasing salt content in xanthan aqueous solutions, the progres-
sive screening of the electrical charges takes place and the chains
shrink. The screening effect is more pronounced in the presence of
K+ than in the presence of Na+ ions and so the reduced segmen-
tal repulsion lead to a more compact configuration and a dramatic
reduction in hydrodynamic volume of the xanthan macromolecule.
Moreover, starting from a certain concentration of salt, the polymer
coils shrink steadily as the polymer concentration rises. In the case
of xanthan in NaCl salt solution, when NaCl concentration exceeds
5 × 10−2 mol/L the influence of polymer concentration on {}/[]
vanishes; for xanthan in KCl salt solution, this situation occurs for
csalt > 3 × 10−3 mol/L (Fig. 7). These findings are in agreement with
those found for other systems [21,22,25].
Modification in dimension of the xanthan chains as a function
of the aqueous solutions salinity is reflected by the viscometric
expansion factor, ˛3 , a dimensionless parameter which is defined
as:
[]
˛3 = (10)
[]
518 C.-E. Brunchi et al. / Colloids and Surfaces B: Biointerfaces 122 (2014) 512–519

to about unity. Generally, ˛3 becomes unity in two circumstances:

(a) 1.0
first at theta conditions when the interactions polymer–polymer
counterbalances those of polymer–solvent and the dimension of
the chain reaches the unperturbed value (valid in our case), and sec-
0.8 ond, at the limit of such a low molecular weight that the interactions
{η}/[η]

between segments of the same chain are not possible.

4. Conclusion
0.6

The thermodynamic properties of high molecular weight xan-

than in aqueous solutions at 25 ◦ C were investigated as a function of
0.4 monovalent salt content, counterion nature and polymer concen-
tration. A new model proposed by Wolf [21] was applied in order
0.0 0.2 0.4 0.6 0.8 1.0
to describe the viscometric behavior of xanthan solutions in pure
cx[η] water and in the presence of extra salts. From the dependence of
the logarithm of relative viscosity on polymer concentration, three
characteristic parameters, intrinsic viscosity, hydrodynamic inter-
(b) 1.0 action parameter and characteristic specific hydrodynamic volume,
were determined and discussed.
The intrinsic viscosity decreased by salt addition due to the
0.8 enhancement of the non-Coulombic interactions. The effect of salt
{η}/[η]

on the intrinsic viscosity and the viscometric interaction param-

eter was well described by modeling the experimental data with
Boltzmann equation.
0.6
The conformation of xanthan coil was discussed by means of
the reduced specific hydrodynamic volume and the viscometric
expansion factor as a function of the salt concentration in aqueous
0.4 solutions. The present investigation demonstrates that the viscos-
0.0 0.2 0.4 0.6 0.8 1.0
ity measurements offer multiple possibilities to characterize the
solutions of polysaccharides in unperturbed and perturbed state.
cx[η]

Fig. 7. Dependence of the reduced specific hydrodynamic volume as a function of

Acknowledgements
the reduced polymer concentration for xanthan solutions in pure water and in the
presence of different salt contents: NaCl (a) and KCl (b). This work was supported by a grant of the Romanian National
Authority for Scientific Research, CNCS-UEFISCDI, project number
PN-II-ID-PCE-2011-3-0199, contract 300/2011.
where the subscript  corresponds to unperturbed state; the
value of the viscosity under theta conditions ([] ) was considered
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