Colloids and Surfaces A: Physicochem. Eng.

Aspects 407 (2012) 1–8

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Review

New insight into “polyelectrolyte effect”

Hu Yang a , Qiang Zheng b,∗ , Rongshi Cheng a,c,∗∗
a
Key Laboratory for Mesoscopic Chemistry of MOE, Department of Polymer Science & Technology, School of Chemistry & Chemical Engineering,
Nanjing University, Nanjing 210093, China
b
Department of Polymer Science and Engineering, Key Laboratory of Macromolecule Synthesis and Functionalization of MOE, Zhejiang University, Hangzhou 310027, China
c
Polymer Institute, College of Material Science and Engineering, South China University of Technology, Guangzhou 510640, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 A new insight into “polyelectrolyte

effect” is proposed.
 The interface effect results in the
abnormal viscosity of polyelec-
trolyte.
 The “abnormal” viscosity data con-
tain a lot of structural information on
polymer.

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

Article history: A new insight into “polyelectrolyte effect” which referred to the reduced viscosity of polyelectrolyte
Received 30 January 2012 upon dilution resulting from the intra-molecular electrostatic repulsion was proposed, depending on
Received in revised form 18 May 2012 the results by the authors concerning the viscosity theory of polymer solutions through theoretical and
Accepted 21 May 2012
experimental methods. The results reveal that the abnormal viscosity behaviors of polyelectrolytes as well
Available online 30 May 2012
as neutral polymers in dilute solution region are ascribed to the interface effects. The polymeric solutes
are readily adsorbed on the viscometer capillary wall surface, which greatly influences the viscosity
Keywords:
measurement of polymer solutions, and results in apparent abnormal viscosity behavior. It is suggested
Polyelectrolytes
Abnormal viscosity behaviors
that the so-called “abnormal” viscosity data, difficult to deal with and ignored by previous researchers,
Polyelectrolyte effect are not actually abnormal, but contain a lot of structural information on polymer both on the capillary
Interface effect wall and in solutions. In the present article, recent progresses in the studies on the viscosity behaviors
of various polyelectrolytes are summarized, mainly depending on the findings of the authors and their
collaborators involving synthetic polyelectrolytes, natural polyelectrolytes and amphoteric proteins.
© 2012 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Theoretical model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Synthetic polyelectrolytes [20] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. Derivatives of poly-2-vinylpyridine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.2. Sodium polystyrene sulfonate (NaPSS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

∗ Corresponding author.
∗∗ Corresponding author at: Key Laboratory for Mesoscopic Chemistry of MOE, Department of Polymer Science and Technology, School of Chemistry and Chemical
Engineering, Nanjing University, Nanjing 210093, China.
E-mail addresses: zhengqiang@zju.edu.cn (Q. Zheng), rscheng@nju.edu.cn (R. Cheng).

0927-7757/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2012.05.031
2 H. Yang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 407 (2012) 1–8

4. Natural polyelectrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
5. Amphoteric proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5.1. Gelatin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5.2. Casein . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

1. Introduction the capillary viscometer in the process of viscosity measurement,

while the downward bending is due to transition of flow mode
Polyelectrolyte is a type of polymer with positive or negative from the viscous flow to slip flow. Accordingly, structural infor-
charges on its repeating units, and may dissociate in water or mation of polymer in solution and on capillary interface could be
lower alcohol, forming a charged poly-ion surrounded by an atmo- obtained through analyzing the viscosity data of dilute polymer
sphere of small, mobile counter ions. On the basis of the types solution. This is undoubtedly an inspirational effect on accurate
of charge, polyelectrolyte can be divided into anionic, cationic understanding of various issues such as the pathogenesis of cardio-
and amphoteric polyelectrolyte. Bearing both features of polymer vascular disease and so on. On the other hand, in-depth study on the
and electrolyte molecules, polyelectrolytes have very extensive adsorption behaviors of polyelectrolytes on glass substances may
and important applications in various fields, for example, sewage, give some inspiration to explore the mechanisms of the layer-by-
sludge treatment agents, as well as oil, paper, paint, and food addi- layer technology of polyelectrolytes further [14–16]. Additionally,
tives. Moreover, polyelectrolytes play a unique role in biomedical the authors have systematically studied the abnormal viscosity
area of drug delivery, tissue cell culture as well as the immobilized behaviors of polyelectrolytes in dilute solutions, including syn-
enzyme [1–4]. However, application of polyelectrolyte materials thetic polyelectrolytes, natural polyelectrolytes and amphoteric
has been mostly conducted in solutions, and it is undoubtedly proteins, and found that the viscosity behaviors of polyelectrolytes
significant to understand the properties of polyelectrolyte solu- could be well described by the proposed theory, and owed the
tion well for further expanding their applications. However, people nature of “polyelectrolyte effect” to the interface effect.
have known less about polyelectrolytes than neutral polymers
up to date. Early in the 1940s Fuoss [5] defined a phenomenon 2. Theoretical model
called “polyelectrolyte effect”, i.e. reduced viscosity of polyelec-
trolyte solutions increases as the solution is diluted, which is totally According to this principle, Cheng et al. have corrected the
different from that of neutral polymers. As is shown in Fig. 1, apparent relative viscosity data from Einstein viscosity equation
most researchers have believed that the more dilute the solution, on the basis of the interface effect on polymer viscosity measure-
the stronger intra-chain electrostatic repulsion is, which results in ment for dilute solution through the Langmuir adsorption model. A
chain extension and increase of reduced viscosity upon dilution. quantitative expression to describe experimental viscosity (r,exp )
This viewpoint has been generally accepted by researchers over is given by [17]
the world for more than 60 years, and has been cited by a large
t(C)

k·C

number of literatures and included in many textbooks. r,exp = · 1+ (1)
It is interesting that in viscosity measurement for neutral poly- t0 Ca + C
mer solution, the reduced viscosity deviates from the Huggins where t0 and t(C) are the efflux time for pure solvent before the
equation and could not linearly follow the plotting reduced vis- adsorption of polymer and each solution with different concen-
cosity versus concentration in the lower concentration region, and tration (C) in the viscometer respectively. [1 + ((k·C)/(Ca + C))] is
viscosity curve appears upward or downward bending [6–10]. The expressed as the contribution to relative viscosity of polymer solu-
present authors [11–13] systematically studied the abnormal vis- tions. Ca is the concentration at which half of the active sites of
cosity behaviors of neutral polymers in extremely dilute solutions, the viscometer capillary wall surface are adsorbed by the polymer.
and confirmed that those phenomena are ascribed to interface The parameter k in Eq. (1) accounts for the maximum fractional
effect, and the upward bending is caused by adsorption occurring in change of flow time of solvent due to solute adsorption defined as
k = (t0 (l) − t0 )/t0 , where t0 (l) is the effective flow time of pure solvent
as all of the active sites of the capillary wall surface are saturated
with adsorbed solute molecules. However, the parameter k may be
either positive or negative depending on whether the flow time of
the solvent is increased or decreased after the adsorption of the
polymer, where k is positive indicating the adsorption model; k is
negative for the slip flow model [11–13]. Under slip flow model,
Ca is equal to 0 since no solute is adsorbed on the capillary wall
surface. Furthermore, the effective thickness of the adsorbed layer
(beff ) could be evaluated from the parameter k coupled with the
known capillary radius as R:
 
1
beff = R · 1 − (2)
1/4
(1 + k)
Furthermore, according to Cluster theory [18], true relative viscos-
ity of polymer solution can be expressed as
t(C)
Fig. 1. Reduced viscosity of neutral polymer and polyelectrolyte solutions versus = 1 + [] · C + 6 · KM · [] · C 2 (3)
concentration. t0
 H. Yang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 407 (2012) 1–8 3

and
sp
= [] + 6 · KM · [] · C (4)
C
where KM is the molar self-association constant. Based on Eq. (4)
and traditional Huggins viscosity equation, the dimensionless Hug-
gins constant KH can be expressed by
KH · []
KM = (5)
6
However, the physical meanings of KM and KH are quite differ-
ent. The Huggins slope constant is dimensionless, while the molar
self-association constant of KM reveals the tendency of inter-chain
cohesion induced by chain penetration in solution, by which the
dynamic contact concentration proposed by Qian [19] could be
evaluated.
The experimental relative viscosity can be deduced from Eqs.
(1) and (3)
 C

r,exp = (1 + [] · C + 6 · KM · [] · C 2 ) · 1 + k · (6)
Ca + C
The inter-chain aggregations of polyelectrolyte is absent in the
dilute solution because of the coulomb repulsion force, which
results in KM = 0. Hence, Eq. (6) can be further simplified as
 k·C

r,exp = [1 + [] · C] · 1 + (7)
Ca + C
The reduced viscosity can be expressed as
sp [1 + [] · C] · [1 + ((k · C)/(Ca + C))] − 1
= (8)
C C
From Eqs. (7) and (8), the viscosity behaviors of polyelectrolyte in
dilute solution can be described only by three parameters, [], k,
and Ca , reflecting the structural state of polymer in solution and at Fig. 2. The plots of reduced viscosities of poly-2-vinyl-N-methylpyridinium bro-
the capillary wall, respectively. The following parts take synthetic mide (A) and poly-2-vinyl-N-n-butyl pyridinium bromide (B) solutions versus
polyelectrolytes, natural polyelectrolytes and amphoteric proteins concentrations in various solvents (, , , and : experimental data; –: theoretical
as examples, respectively, to discuss in details. lines).

3. Synthetic polyelectrolytes [20] Maclay and Fuoss also fitted their data according to an empirical
formula [22], as given in Eq. (9) by
3.1. Derivatives of poly-2-vinylpyridine sp A
= √ +D (9)
C 1+B C
Maclay and Fuoss [21] prepared polyelectrolytes through par-
tial quaternization of poly-2-vinylpyridine with methyl and n-butyl in which B is a measure of the intensity of electrostatic interac-
bromide, respectively. It is found that the salt of the former in water tion and (A + D) is a measure of the volume of the polyion at zero
and methanol and the latter in water, methanol, ethanol and nitro concentration, i.e. intrinsic viscosity ([]) as shown below [21,22]
methane, respectively, all exhibit an increase in reduced viscosity sp
[] = =A+D (10)
upon dilution, the typical “polyelectrolyte effect”, as shown in Fig. 2. C C→0
It is widely accepted by most researchers as mentioned above that It can be seen from the fitting results that the experimental
this phenomenon is ascribed to the increase of the intra-chain elec- data were also consistent with the theoretical lines, but the val-
trostatic repulsion of polymer with the decrease of concentration. ues of parameter A by extrapolation in various solvents seems
However, from the theory of interface effect as introduced mostly infinite [21]. Based on Eq. (10), most of [] are also infi-
above, Maclay’s and Fuoss’ data have been fitted according to Eq. nite and could not be obtained, indicating that the Fuoss empirical
(8), as shown in Fig. 2 also. The experimental data are consistent formula is unreasonable. However, from the viewpoint of interface
with the theoretical lines very well, indicating that the upward effect, the model not only fits the experimental data very well, but
bending of reduced viscosities may be due to polymer adsorption also gives unambiguous physical meaning of every parameter and
on the capillary wall. Moreover, the glass capillary wall contains a
large number of Si OHs which are facile to interact with the polar
Table 1
groups on the polymer backbone, and polyelectrolytes are available
Viscosity parameters of the derivatives of poly-2-vinylpyridine in various solvents.
for absorption on the glass surface. On the other hand, parameters
of [], k, and Ca for the derivatives of poly-2-vinylpyridine in various Polymer Solvent [] (mL/g) Ca (mg/mL) k beff /R
solvents can be obtained from the fitting results and summarized Water 118.6 0.149 0.224 0.0493
Methyl salt
in Table 1. According to Eq. (2), the ratio of the effective adsorp- Methanol 62.9 0.201 0.075 0.0179
tion thickness beff to the capillary radius can be calculated and Water 96.4 0.310 0.197 0.0440
listed in Table 1 also. The relevant parameters are different in var- Methanol 74.8 0.214 0.055 0.0133
Butyl salt
ious solvents, which may result from different polarity of various Ethanol 41.2 0.130 0.028 0.0069
Nitromethane 65.5 0.335 0.149 0.0341
solvents.
4 H. Yang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 407 (2012) 1–8

Fig. 3. The plots of reduced viscosities of various NaPSS aqueous solutions versus
Fig. 4. The plots of the ratio beff /R of polystyrene () and NaPSS () samples versus
concentration (, , , ♦ and 夽: experimental data; –: theoretical lines).
the intrinsic viscosity, respectively.

reasonable values including [], k, Ca , and beff , which indicates that

the theoretical model based on interface effect is valid. larger than that of neutral polymer. In addition, for higher molec-
ular weight samples, bads as well as be is apparently larger, and beff
3.2. Sodium polystyrene sulfonate (NaPSS) increases with molecular weight of sample, correspondingly.

As mentioned above, the derivatives Poly-2-vinylpyridine are 4. Natural polyelectrolytes

a class of cationic polyelectrolytes, and the applicability of the
theoretical model have also been tried to a class of anionic poly- Some studies on viscosity behaviors of natural polyelectrolytes
electrolytes, sodium polystyrene sulfonate (NaPSS). NaPSS samples have been carried out. Chitosan [24–26] and sodium alginate
were synthesized from a series of polystyrene samples with nar- [27–29] have been chosen, respectively, since chitosan is a kind of
row molecular weight distribution, which were obtained by anionic natural weak cationic polyelectrolyte, soluble in dilute acidic solu-
polymerization using n-BuLi as initiator. The sulfonation degree tions but insoluble in water, and –NH2 groups on the C-2 position
(SD) can be detected by 1 H NMR spectroscopy. The detailed infor- of the d-glucosamine repeating units are facile to accept a proton
mation of these various NaPSS samples is listed in Table 2. It is found and converted to –NH3 + , while sodium alginate is a kind of strong
that the sulfonation degree of various NaPSS is roughly similar, anionic polyelectrolyte. The following section will discuss the vis-
ranging between 90 and 104%. cosity behaviors of the two natural polyelectrolytes taking opposite
All viscosity measurements were carried out with Ubbelohde- charges.
type glass viscometers. The concentration dependence of the Fig. 6 presents the concentration dependence of reduced vis-
measured reduced viscosities of various NaPSS in aqueous solu- cosities of 1% acetic acid solutions of chitosan and sodium alginate
tions is given in Fig. 3. It seems that NaPSS had similar viscosity aqueous solutions at various temperatures, respectively. It is found
behaviors to those of the derivatives of poly-2-vinylpyridine, i.e. that the viscosity behaviors of sodium alginate show a typical fea-
the reduced viscosities increase as concentration decreases. The ture of polyelectrolyte, i.e. the reduced viscosity increases with
experimental data also fit well, according to Eq. (8) as given in concentration decrease, and exhibit little change under different
Fig. 3. The theoretically simulated curves as thin solid lines fitted temperatures. On the contrary, the downward bending of reduced
the experimental data in a fairly good way, which indicates that the viscosities upon dilution, fully opposite to ordinary polyelec-
theoretical model based on interface effect is suitable to describe trolyte, has been observed in 1% acetic acid solutions of chitosan.
the viscosity behaviors of various NaPSS in aqueous solutions, and
the abnormal viscosities are caused by the solute adsorption on the
capillary wall.
Meanwhile, the relevant parameters of NaPSS obtained from
simulation are listed in Table 2. [], reflecting the hydrodynamic
volume of polymer single chain in an extremely dilute solution,
increases with the increasing molecular weight of NaPSS, which is
ascribed to the fact that higher molecular weight of certain polymer
would have larger hydrodynamic volume in the same solvent. From
Table 2, it is seen that Ca has no significant molecular weight depen-
dence. In addition, it is interesting that parameter k, reflecting the
degree of adsorption, increases with the molecular weight, and
effective thickness of the adsorbed layer (beff ) calculated by Eq. (2)
exhibits a similar molecular weight dependence to k. Furthermore,
from the numerical value of NaPSS, beff appears much greater than
the thickness of absorbed layer of its precursor neutral polystyrene
(PS) [23] as shown in Fig. 4. With regard to polyelectrolyte adsorp-
tion on the capillary wall, in addition to the swollen adsorbed solute
layer (bads ), there still existed an electrostatic exclusion layer (be ),
which is generally much larger than bads . Fig. 5 gives the calculated Fig. 5. Schematic presentation for the interface effects of polyelectrolyte and neutral
beff consisting of bads and be . Hence, beff of polyelectrolyte is much polymer solutions in the capillary flow.
 H. Yang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 407 (2012) 1–8 5

Table 2
Viscosity parameters of various NaPSS in aqueous solutions.

NaPSS Mn (NaPSS) (×10−4 g/mol) SD (%) [] (mL/g) Ca (mg/mL) k beff /R

1 85.4 96 170.0 1.05 10.54 0.457

2 39.5 90 106.0 0.61 6.931 0.404
3 21.4 102 87.0 0.80 0.873 0.145
4 8.9 100 29.4 2.29 0.310 0.065
5 4.9 92 27.2 0.86 0.199 0.044

Table 3
Different relevant parameters for 1% acetic acid solutions of chitosan and sodium alginate aqueous solutions averagely.

M␩ (×10−4 g/mol) K [] (mL/g) Rh (nm) Thickness observed under AFM (nm) beff (␮m)

Chitosan a
29.60 >0 ∼2200 ∼250 ∼100.0 ∼2.0
Sodium alginateb 6.50 >0 ∼700 ∼200 ∼40.0 ∼20.0
a
The degree of deacetylation is about 90.5% quoted from the manufacturer.
b
The M/G ratio is 1.75 estimated by 1 H NMR spectroscopy.

Furthermore, the viscosity behaviors of chitosan show strong tem-
perature dependence. According to Eq. (8), experimental data of
both chitosan and sodium alginate were consistent with theoret-
ical lines. The simulated parameters were summarized in Table 3.
It is indicated that the theoretical model based on interface effect
as described above is also applicable to natural polyelectrolytes.
Moreover, from Table 3, parameter k, reflecting the flow model,
are greater than 0 in both polymer solutions, indicating that either
chitosan or sodium alginate is absorbed on the capillary wall.
Fig. 6. The plots of reduced viscosities of 1% acetic acid solutions of chitosan (A) and
of sodium alginate aqueous solutions (B) versus concentration, respectively, in the
temperatures ranging from 10 to 45 ◦ C. (–: theoretical lines, and the plot inserted
was relative viscosity versus concentration.).
Atomic force microscope is used to study the different mor-
phologies of adsorbed solutes on the glass slides treated by various
polymer solutions directly. A clean slide with glass quality similar
to that of the capillary viscometer is vertically dipped repeatedly in
polymer solution with a concentration of 0.05%, which simulated
the viscous flow of polymer solutions in the capillary. Fig. 7 gives the
AFM images of the glass slides vertically dipped in different natural
polyelectrolyte solutions. Compared to blank slide, the surfaces of
both glass slides dipping in chitosan and sodium alginate solutions,
respectively, adsorb a layer of polymers, which confirms the pre-
sumption from parameter k as mentioned above. However, from
Fig. 6, it can be seen that reduced viscosities of 1% acetic acid solu-
tions of chitosan decrease as concentration decreases, which may
be due to the two opposite effects of solute adsorption on the capil-
lary wall. First, the solute adsorption reduces the capillary radius of
viscometer, which results in the increase of apparent relative vis-
cosity; on the other hand, the actual concentration of the solution
also decreases due to the adsorption, which leads to the decrease
of apparent relative viscosity. Both the reduction of the radius of
the viscometer capillary and the decrease of the solution concen-
tration due to the adsorbed solute on the glass capillary surface
affect the viscosity measurement, and in terms of the two oppo-
site effects on the viscous flow as mentioned above, the effect of
the former is usually more significant in most polyelectrolyte solu-
tions, and exhibits a typical “polyelectrolyte effect”; on the contrary,
the downward bending phenomenon appears. It is believed that
the later effect is dominant, and results in the opposite viscosity
behaviors of chitosan.
Fig. 8 gives temperature dependence of intrinsic viscosity [] of
1% acetic acid solutions of chitosan () and sodium alginate aque-
ous solution () fitted according to Eq. (8), respectively. Based on
Figs. 6 and 8, it can be seen that the viscosity behaviors of two nat-
ural polymer solutions show different temperature dependence,
due to different charge strength of polyelectrolyte. It is noted that
sodium alginate is a kind of strong anionic polyelectrolyte, the stiff-
ness conformation of which has little change for strong intra-chain
electrostatic repulsion, and [] almost shows temperature indepen-
dence in the temperature range measured. As for chitosan, being
a kind of weak cationic polyelectrolyte, the intra-chain hydrogen
bond is dominant in lower temperatures, which makes the local
chain quite stiff and large hydrodynamic volume. With the increase
of temperature, the intra-chain hydrogen bond is broken gradually,
and the stiffness of polymer chains decreases [30], resulting in the
decrease of hydrodynamic volume and intrinsic viscosity.
Furthermore, beff of 1% acetic acid solutions of chitosan and
sodium alginate aqueous solutions under various temperatures can
be calculated according to Eq. (2) and shown in Fig. 9. The beff of 1%
acetic acid solutions of chitosan is around 2.0 ␮m on average which
6 H. Yang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 407 (2012) 1–8

Fig. 8. Temperature dependence of intrinsic viscosity [] of 1% acetic acid solutions

of chitosan () and sodium alginate aqueous solution () fitted according to Eq. (8),
respectively.

from Table 3, for both chitosan and sodium alginate, the thickness
observed directly under AFM is much smaller than the calculated
beff . One reason is that the thickness observed directly through AFM
observation is measured at the dry state, being a condition far dif-
ferent from the swollen state, and the electrostatic repulsion layer
could hardly be observed through AFM.

5. Amphoteric proteins

As discussed above, the abnormal viscosity behaviors of syn-

thetic and natural polyelectrolyte solutions, as well as neutral
polymer, can be ascribed to interface effect. The so-called “abnor-
mal” viscosity data, difficult to be dealt with and ignored by
previous researchers, are not actually abnormal, even contain abun-
dant structural information of the polymer both at the interface
of glass capillary and in solution. Accordingly, amphoteric protein
adsorption behaviors have been studied.

5.1. Gelatin

It is well-known that gelatin is an important biological poly-

mer, and prepared by the partial degradation of the insoluble
fibrous protein collagen [31–33]. The gel point of the sample is
around 23.8 ◦ C. Fig. 10 gives the reduced viscosity of gelatin aque-
ous solutions in the extremely dilute concentration region under
varied temperatures. The experimental data are consistent with

Fig. 7. AFM images of morphologies of glass slides vertically dipped in different

natural polyelectrolyte solutions (A) blank; (B) 1% acetic acid solution of chitosan;
(C) sodium alginate aqueous solution.

is one order of magnitude thinner than that of sodium alginate.

However, from Table 3, it can be seen that the molecular weight,
[], hydrodynamic radius (Rh ) as well as the thickness observed
through AFM of chitosan are all greater than those of sodium algi-
nate. According to the model of polyelectrolyte solution viscous
capillary flow as shown in Fig. 5, beff includes bads and be . On
the other hand, the electrostatic exclusion layer of chitosan has
been eliminated effectively by excessive acetic acid for the charge
Fig. 9. Temperature dependence of the effective thickness of the adsorbed layer beff
screening effect, since chitosan dissolves in acetic acid solutions. of 1% acetic acid solutions of chitosan () and sodium alginate aqueous solution ()
This effect results in a large decrease in beff of chitosan. In addition, calculated according to Eq. (2), respectively.
 H. Yang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 407 (2012) 1–8 7

Fig. 10. The plots of reduced viscosities of gelatin aqueous solutions versus concen- Fig. 12. The plots of the reduced viscosities of casein in dilute NaOH aqueous
tration at varied temperatures (, , , , ♦ and 夽: experimental data; –: theoretical solutions versus the concentration at varied temperatures (, , , , ♦ and 夽:
lines). experimental data; –: theoretical lines).

theoretical lines, indicating that the theoretical model based on the helical structure of gelatin is adsorbed lying flat on glass capillary
interface effect is also applicable to amphoteric protein. wall.
It is interesting that the reduced viscosities of gelatin aqueous
solution, similar to that of the general polyelectrolyte, decrease
5.2. Casein
with concentration increase at temperature above or equal to
20 ◦ C. However, below 20 ◦ C, the concentration dependence of
Besides gelatin, viscosities of casein in NaOH aqueous solu-
the reduced viscosity reverses, which indicates that reversible
tion under varied temperatures have been measured and shown
conformational change of gelatin collagen takes place at lower tem-
in Fig. 12. Casein is the main component of milk, being a white,
perature. It is known that gelatin would undergo thermoreversible
tasteless, and odorless substance [34,35]. The reduced viscosity
gelation below 25 ◦ C, due to the conformational change of polymer.
increases with concentration decrease, and the theoretical lines
It can be expected that the gelatin chain would present in single
based on Eq. (8) fit the experimental data. In addition, Fig. 13
random coil in dilute concentration region at a higher tempera-
presents the fitted [] and beff of casein in NaOH solution under
ture, however, it undergoes reversion from random coil to helix
varied temperatures. Both [] and beff decrease with temperature
with temperature decrease.
increase. However, [] changes quite slightly, from 25 to 20 ml/g
According to Eq. (6), the [] and beff of gelatin aqueous solution
only, which might be due to the amphoteric characteristic of casein,
under varied temperatures are calculated and given in Fig. 11. It is
i.e. the dissociation capability is affected by both cation and anion,
found that [] is large at a low temperature, but decreases quickly
and make the counter ions around macromolecular chain unchange
with temperature increase. Hence, one can confirm the previous
in a certain concentration range, leading to the extension or con-
presumption that the conformational transition of gelatin might
traction margins of molecular chain. Moreover, beff decreases with
undergo from helix to random coil with temperature increase.
temperature increase, indicating that the Brownian motion of the
Moreover, according to the fitting results from Eq. (6), molar self-
polymers is more active in higher temperature, and some adsorbed
association constant KM is unequal to 0 at 15 ◦ C, which is further
solutes on the glass surface are desorbed with the increase of tem-
evidence of the association structures of gelatin chains at low
perature.
temperature. In addition, much smaller beff of gelatin at low tem-
perature as shown in Fig. 11 indicates that the association of rigid

Fig. 13. The plots of the intrinsic viscosity () and effective thickness of the absorbed
Fig. 11. The plots of the intrinsic viscosity [] () and effective thickness of the layer () of casein in dilute NaOH aqueous solutions versus temperature fitted
absorbed layer () of gelatin versus temperature, fitted according to Eq. (6). according to Eq. (8).
8 H. Yang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 407 (2012) 1–8
Furthermore, as compared with the cationic or anionic synthetic
and natural polyelectrolyte as discussed above, the beff of ampho-
teric proteins for not only gelatin but also for casein are much
smaller, which may be ascribed to the presence of amphoteric ions,
and the electrostatic exclusion layer weakened significantly.
6. Conclusion
Based on the investigation into viscosity behaviors of poly-
electrolytes including synthetic polyelectrolytes, natural polyelec-
trolytes, and amphoteric proteins, the nature of “polyelectrolyte
effect” can be ascribed to interface effect in viscous capillary flow.
The viscosity behaviors of dilute polyelectrolyte solutions can be
described only by three parameters, [], k, and Ca , and it is pro-
posed that these parameters reflect the structural state of polymer
in solution and on the capillary wall. Accordingly, it is suggested
that the structure of polymers in solution and at the interface of
glass capillary can be probed by studying their viscosity behaviors
in dilute solutions.
Acknowledgement
This work was supported by the Key Program of the National
Natural Science Foundation of China (No. 50633030).
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