Colloid & Polymer Science Colloid Polym Sci 269:850-854 (1991)

Interaction of sodium and potassium ions with/c-carrageenan

V. P. Yuryev, A. L. Blumenfeld, E. E. Braudo, and V. B. Tolstoguzov

Nesmeyanov Institute of Organoelement Compounds, USSR Academy of Sciences, Moscow, USSR

Summary: N M R and potentiometric methods revealed at least two types of

interactions of Nav and K § ions with/r viz., Coulombic interaction
with polysaccharide sulfate groups, and a coordination one, leading, in the case
of the Na + ions, to formation of nonstoichiometric complexes. The absence of
any correlation between the coordination binding density of the cations and their
promoting effect on gelation process was demonstrated.

Key words: ~-carrageenan; g_elation; N_a+ ions; K + ions

Introduction was described elsewhere [7]. In order to desalt the /~ car-

rageenan sample, the solution was converted to H-form by
dialysis using ion-exchange membranes. The K-form was ob-
It is known that the gelling capacity of/c-car-
tained via the titration of solution with 1 M KOH to pH 7.0.
rageenan in the presence of K +, Rb § and Cs § ions The process, leading to creation of a Na-form, is described
is much higher than that of Li § and Na + ions. elsewhere [7].
Accordingly, the alkaline metal ions are divided The density of the Na + and K § binding to the polyanion
into agents that promote or do not promote the was determined by measuring the ion activity using ion-
selective electrodes. In the case of the Na + ions an N M R
gelation process. The authors of the "domain"
method was additionally used.
model [1] claim that the specificity of the effect of Methods for determining the Na + ion activity coefficient, as
low-molecular ions on this process is attributed to well as calculation of such a coefficient for the counterions, are
the differences in the efficiency of their partici- described in [7]. The activity of the K § ions was determined
pation in the formation of contacts between the using an OP-266 analyzer (Radelkis, Hungary). The activity
coefficients for the Na + and K + ions were determined with an
segments in the double helix conformation. Other
accuracy of + 3 and + 4%, respectively.
researchers put forward the idea of the feasibility The 23Na N M R spectra were recorded by means of an SXP
of the formation of bridge bonds involving ions 4 x 100 impulse spectrometer (Bruker, FRG); the resonance
which promote the gelation process between the/c- frequency of 23Na is 23.302 MHz. All the spectra exhibited a
carrageenan macromolecules in the single helix single line with width 25 Hz. Its shift ( - 0.75 m.p.) in all the
samples under study was the same. It coincided with results
conformation [2, 3], or in the disordered conforma-
obtained in an NaC1 solution.
tion [4-6]. When sodium was present in solution in the bound rather
This study investigates the interaction of /r than in the free ionic form, its resonance line broadened (line-
carrageenan in solution with Na + and K + ions. width more than 5 kHz), presumably because of a strong
It was interesting to trace a correlation between the quadrupole relaxation [8]. Our experimental conditions did
not allow us to detect lines broader than 1.5 kHz. So we can
ability of the ion to promote gelation and its affin-
assume that the experimentally obtained 23Na line was related
ity to the polyanion. to a free form of Na + ions in the studied solutions. The
concentration of the free Na + ions was found from a calib-
ration curve plotted using standard NaC1 solutions. The rela-
Materials and methods tive uncertainty of determining the concentration of the above
ions, assessed by numerical integration, was + 7%.
The study involved the Na- and K-forms of/r The optical rotation of the /c-carrageenan solutions was
isolated from a commercial carrageenan sample (Sigma, USA). measured using a polarimeter (Jouan-Roussel, France) at
The monosaccharide composition of the preparation obtained 436 nm, with a relative error of _+ 2.5%.

GL 878
Yuryev et al., Interaction of sodium and potassium ions with x-carrageenan 851

The limiting viscosity number of the /c-carrageenan at within the entire range of/c-carrageenan concentra-
various ionic strengths was determined using an Ubbelode tion 7Na+/TNa0 + > "]K +/7~ In other words, in an
viscometer at shear gradients 700-1200 s- 1 aqueous salt-free solution the affinity of the rc-
All the measurements were made at 25 ~
carrageenan polyanion to the K + ions is higher
than that to the Na + ions. This can be attributed to
a higher affinity of the tc-carrageenan sulfate groups
for the K + ions.
Results and discussion
One can deduce from the dependence of the
specific optical rotation plotted as a function of
The dependence of the relative counterion activ-
polysaccharide concentration in the same figure,
ity coefficient t) on/c-carrageenan concentration in
that a drop in the FK+/7~ ratio at m p > 1- 10 - 2 g-
an aqueous salt-free solution is shown in Fig. 1.
eq/kg of the solvent is accompanied by a con-
The observed drop in the counterion activity with
formational /c-carrageenan transition. At a fairly
growing polyelectrolyte concentration is typical of
high K + concentration this polysaccharide is
polyelectrolyte solutions [9-11]. It is evident that
known to undergo a conformational coil-helix
transition [1, 5]. In this case the required K + con-
centration is attained by increasing the polyelec-
trolyte concentration (the K-form). The results ob-
1.00 m

tained coincide with the conclusions of Rinaudo

and Rochas [12].
/ o According to [13, 14], the interaction of the Na +
and K + ions with/c-carrageenan in a dilute salt-free
solution is purely Coulombic. From this point of
o~0.80 view, a more profound drop of the 7K+/yO+ ratio,
as compared to the 7Na+/YNa 0 +, can be explained by
an increase in the linear charge density of a
macromolecule, due to the helix formation of
the K-form of/c-carrageenan.
0.60
For a double /c-carrageenan helix the charge
density parameter ~ = 1.740, and the theoretical
value of the relative counterion activity coefficient
v
of a limit-diluted salt-free solution, according to
Manning [14], is equal to 0.35 [7].
I I I I I [Link] 2, A method to establish a non-Coulombic (co-
1.0 3.0 50 monomol
170 ordination) interaction of the counterions with the
.kg-~
polyions was proposed in [14]. It is based on the
~150 comparison of experimental values of the relative
counterion activity coefficient of limit-diluted (with
t_l
respect to the polymer) solutions, with theoretical
130 values calculated as proposed by Manning [15].
The origin of positive deviations from theoretical
110 values, caused by Coulombic interactions, was dis-
cussed earlier in [7]. The negative deviations at
high ionic strengths suggest coordination, i.e., non-
Fig. 1. Dependence of the relative counterion activity co-
efficient and specific optical rotation on/c-carrageenan concen- Coulombic types of the counterion-polyion inter-
tration (rap) in an aqueous salt-free solution at 25 ~ 1 and actions. In the systems under study those are
4 =/c-carrageenan Na-form; 2 and 3 =/c-carrageenan K-form presumably ion-dipole interactions.

1) The relative counterion activity coefficient (71/7 ~ is the ratio between the activity coefficient of the counterion and the
same ion in a low-molecular weight salt solution (chloride) having the same equivalent concentration.
852 Colloid and Polymer Science, Vol. 269 . No. 8 (1991)

1.00 2.6
o Q

o0.80 7
-~2.2
~0.60
,<
0.40 1,8

I I I I I i I I I [
1.0 3.0 5.0 2.0 6.0 10.0
X 1/2

Fig. 2. Dependence of the relative counterion activity coeffi- Fig. 3. Dependence of the ~c-carrageenan Na-form limiting
cient on parameter X = rap/ms, where mp is the/c-carrageenan viscosity number in NaC1 solutions on their ionic strengths at
concentration, g-eq/kg of the solvent; ms is the concentration 25 ~
of a low-molecular weight salt, g-eq/kg of the solvent, at
25~ Solid curve = theoretical dependence of the relative
counterion activity coefficienton parameter X for the helical ~c-
carrageenan conformation. Experimental data: - 9 ~c-car- limiting viscosity number of the K-form of ~c-car-
rageenan Na-form-NaC1; -O-~c-carrageenan K-form-KC1 rageenan when the K + ions exhibit a coordination
binding was not possible because of the irreprodu-
cibility of the viscosity measurements. This may
arise from an aggregation of the helical macromol-
Figure 2 shows a theoretical dependence of the ecules. In the case of the Na-form the viscosity data
relative counterion activity coefficient in/c-carrage- were irreproducible only when the NaC1 concen-
enan solutions on the ratio between the equivalent tration exceeded 0.1 M.
concentrations of the polyelectrolyte and low- The density of the coordination binding of the
molecular weight salt (X) and corresponding cations with K-carrageenan, as calculated accord-
experimental functions obtained in the systems ing to [14], is 6.9 and 0.7 ion per disaccharide unit
containing the Na-form of /c-carrageenan and for the Na* and K § ions, respectively. In the latter
NaC1 [14] and the K-form of K-carrageenan and case it was only possible to estimate the order of
KC1. In both cases the high concentrations of the magnitude, since the deviations of the experimental
low-molecular weight salt were accompanied by 7K+/7~ values from the theoretical ones were
negative deviations from the theoretical curve, small. Note that the Na + binding density is much
which became more significant for the Na-form. higher than the stoichiometric value governed by
Recently, the polarimetry method was used to the content of the anionic groups (a sulfate group
demonstrate that the coordination binding of the per disaccharide unit).
Na + ions to /c-carrageenan involves a conforma- The phenomenon of nonstoichiometric binding
tional coil-helix transition [14]. This was con- of the Na + ions with the /r estab-
firmed by the studies of the dependence of the lished in potentiometric experiments, was con-
limiting viscosity number of the Na-form of /c- firmed by N M R 23Na spectroscopy. The type of
carrageenan in NaCI solutions on the ionic strength dependence of the Na + binding density on /c-car-
(Fig. 3). The chain rigidity parameter B = 0.078, rageenan (Fig, 4) and NaCI concentrations (Table
calculated from these data as proposed by 1) found by either method, was the same, although
Smidsrod and Haug [16], agrees with results ob- the absolute values of the binding density obtained
tained by other authors [17]. by the N M R spectroscopy were smaller than those
The conformational coil-helix transition in the determined potentiometrically. The differences de-
case of the K-form of ~-carrageenan with increas- tected can be attributed to the fact that the mobility
ing KC1 concentration has been demonstrated by of a fraction of the bound Na + ions is close to that
Morris and coworkers [1]. Determination of the of the free ions, so that the two types of ions are
Yuryev et al., Interaction of sodium and potassium ions with K-carrageenan 853

tion (Table 1). Similar patterns were observed in

8.0 the interaction of the Na + ions with methylcellu-
lose and cellobiose [18]. For the above systems it

i
has been possible to measure the maximum binding
6.0 density and to show that the complexes that appear
represent compounds of varying composition.
The dependence of the limiting viscosity number
4,0 of the Na-form of K-carrageenan in NaC1 solutions
on their ionic strengths (Fig. 3) shows that, in the
entire range of NaC1 concentrations, the lc-car-
2.0
rageenan macromolecular charge remains constant
[19]. In other words, the coordination binding of
the Na + ions, the binding density depending on
.-O--
0.01 ~ I
NaC1 concentration (Table 1), does not influence
O0 1.0 20 3,0 4.0 the effective charge of the /c-carrageenan macro-
mp.lO2, monomo[, kg -~ molecule. It was shown [14] that the formation of
Fig. 4. Dependence of the n u m b e r of the Na + ions bound with nonstoichiometric Na+-/c-carrageenan complexes
the /c-carrageenan Na-form disaccharide unit on poly- does not involve the binding of the chloride ions
saccharide concentration. NaC1 concentration = 0.01 g-eq/kg contained in solution. All these data may suggest
of the solvent. - O - by potentiometry; 9 by 2 3 N a N M R an extremely labile character of the Na +-
polysaccharide binding in nonstoichiometric com-
plexes.
A value of the K + binding density agrees with
detected simultaneously, resulting in a lower bind- published data [4] that suggest the maximum den-
ing density than that determined by the former sity as being 1.2 ion per disaccharide unit. In our
method. An alternative hypothesis consists of the first paper [4], we already showed that the density
fact that the helix formation in/c-carrageenan gives of the K + binding with lc-carrageenan is indepen-
rise to microvolumes where the ions remaining in dent of the conformational state of the latter (a
the free state become inaccessible to detection by disordered conformation or a helical one). Hence,
means of the ion-selective electrode. In this case the the problem concerning a degree of correlation
potentiometrically found binding density will be between the process of helix-formation of/c-car-
overrated. rageenan macromolecules and the coordination
The density of the Na + binding with the K- binding of the low-molecular weight ions awaits
carrageenan decreases with polyelectrolyte concen- further examination.
tration (Fig. 4) and increases with NaC1 concentra- Thus, in this study, we have demonstrated the
existence of at least two types of the Na +- and
K + qc-carrageenan interaction:
Table 1. Dependences of the density of the Na + binding with i) a Coulombic-type interaction of the cations
/c-carrageenan on NaC1 concentration mp = 0.245.10 -2 g- with the sulfate groups, and
eq/kg of the solvent ii) a coordination interaction leading, in the case
of the Na § ions, to the appearance of nonstoichio-
NaC1 concentration, Binding density, mol
g-eq/kg of the solvent N a + / g - e q of the K- metric complexes.
carrageenan In case of sole Coulombic interaction, the K +
ions exhibit a higher affinity to the K-carrageenan
Potentiometry 23Na N M R
as compared to the Na + ions and, hence, they are
0.0005 0.09 0.01 more effective in shielding the macromolecule
0.0075 0.32 - charge, which is evidenced by values of relative
0.0100 3.70 1.86 activity coefficients. Charge shielding is a prereq-
0.0200 5.20 - uisite for the helix formation in the macromole-
0.0500 8.50 4.30
cules, as well as their aggregation and creation of
0.1000 10.70
gel network [6].
854 Colloid and Polymer Science, Vol. 269 9 No. 8 (1991)

The density of the coordination Na + ion binding References

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Accordingly, those have the higher affinity to /c- Received October 30, 1989;
carrageenan under the condition that only Coul- accepted October 19, 1990
ombic interactions are operative. For the same Authors' address:
reasons, the K + ions more effectively shield the
E. E. Braudo
charge of the K-carrageenan polyanions, giving rise Nesmeyanov Institute of Organoelement Compounds
to the growth of the stability of the K-carrageenan USSR Academy of Sciences
helical conformation [5]. Moscow, USSR