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Abstract
We present preliminary results of the investigation of interchain association processes induced by Cs+ ions in -carrageenan aqueous
solution. The solutions contained variable amounts of NaI and CsI, under the condition that the total concentration of 1:1 electrolyte
was 0.1 M. The associative processes were observed by static light scattering under isothermal conditions (at T = 25 C), after cooling
molecularly dispersed solutions obtained at high temperature (80 C). It was found that, under all the investigated conditions of polymer
concentration (from 0.2 to 2 g l1 ) and ionic composition, the onset of time-dependent association fails to lead to an equilibrium, but
proceeds up to physical gelation of the associating system. Depending on the experimental variables, however, the gelation threshold may
take up to several days to be achieved.
2004 Elsevier B.V. All rights reserved.
Keywords: -Carrageenan; Light scattering; Intermolecular association; Gelation
1. Introduction
-Carrageenan is an industrially important anionic
polysaccharide, due to its property to form ionotropic, thermoreversible gels in aqueous environment. A vast literature
has been devoted to the characterisation of the properties
and structure of -carrageenan gels, especially by rheological and microscopic techniques. Among the most interesting results, it was established that -carrageenan gels
possess a fibrillar morphology, analogously to the majority
of physical gels of biological and synthetic nature [1,2].
On the other hand, in spite of notable experimental efforts,
the very basic molecular processes leading to interchain
association and gel formation by -carrageenan have been
a matter of lively debate in the past decades (see refs. [3,4]
and references therein), and several important aspects remain still unclear. Much of such controversy arose from
the discrepancy between experimental findings presented
by different laboratories involved in the research. In our
0141-8130/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ijbiomac.2004.02.001
44
was purified as previously described [6]. Aqueous solutions in mixed NaI/CsI salt (with constant 0.1 M iodide
concentration and varying cesium mole fraction, the latter being defined as XCs = [CsI]/([CsI] + [NaI]) were
prepared according to a standard procedure [6]. A peristaltic pump in a closed circuit was used to filter the
solutions (Millipore membrane, pore size 0.22 m) directly in the light scattering cell. Static light scattering
measurements were performed on a back-scattering set-up
(ALV-NIBS/HPPS, ALV, Langen, Germany), operating at
angle = 173 , at wavelength = 632.8 nm (He/Ne laser,
with output power of 3 mW). The temperature control system of the light scattering apparatus was used to perform a
pre-heating stage before each measurement. The solutions
were heated from 25 to 80 C, kept at 80 C for 1 h and finally cooled to 25 C. The heating and cooling steps lasted
13(1) min and 16(1) min, respectively. The scattered intensity was measured under isothermal conditions (25 C),
every 3 or 10 min depending on the total duration of the
experiment.
45
Fig. 1. Time evolution of the scattered intensity from a sample of -carrageenan, at polymer concentration Cp = 0.6 g l1 and cesium fraction XCs = 0.4.
The onset of large fluctuations of the experimental signal, at t 14 h, denotes the achievement of the gelation threshold.
Fig. 2. Time evolution of the scattered intensity from -carrageenan samples, at different values of polymer concentration ranging from 0.2 to 2 g l1
and at constant cesium fraction XCs = 0.4. The double-log scale has been used for a better collective representation of the several datasets. The inset
shows the data at the lowest polymer concentration (Cp = 0.2 g l1 ) in linear scale.
46
polymer concentration constant, at 1 g l1 , and by decreasing the cesium fraction, XCs , in the range 0.4 to 0.0. In fact,
as noted in the Introduction, a decrease of XCs involves a
reduction of the thermodynamic driving force leading to association of -carrageenan. The results are given in Fig. 4.
They show that a reduction of XCs from 0.4 to 0.3 strongly
affects the kinetics of the association process, although the
gelation threshold is achieved in both cases. However, a further reduction to XCs = 0.2 prevents the occurrence of any
visible time-dependent association on a time scale of about
40 h. Therefore, the three datasets in the range of XCs from
0.0 to 0.2 appear as a flat baseline, denoting the substantial
stability of the systems in these conditions. No intermediate
behaviour appears between the systems at XCs 0.3, where
physical gelation is achieved at the end of the slow association processes, and the systems at XCs 0.2, where no
time-dependent association appears to be detectable at all.
We should note that in a previous study [6] we found evidence for the occurrence of very limited association even at
XCs values of 0.1 and 0.2. The two findings, however, do not
conflict, given the much higher sensitivity to the presence of
very little association offered by the experimental method
used in the previous investigation. With respect to this, it
should be emphasised that the remarkable advantage of the
method presently employed consists in the possibility to
observe continuously, and without introducing any physical
disturbance, the slow evolution of the macromolecular systems in the course of association and physical gelation. From
this viewpoint such an approach, although providing mostly
qualitative information, offers unique advantages compared
to any other commonly used experimental technique (e.g.
rheology, ultracentrifugation, fractionation techniques, etc.).
Fig. 3. Gelation time vs. polymer concentration, at constant XCs = 0.4. The inset shows the data in double-log scale.
47
Fig. 4. Cesium fraction dependence of the associative behaviour of -carrageenan, at constant polymer concentration Cp = 1 g l1 .
The observation of the data in Fig. 4 leads to two important considerations: (i) the ionic composition plays a critical
role in the associative behaviour of -carrageenan. The increase of XCs produces a sharp transition from conditions
of no (or very little) association to conditions of extensive
association, with long time dependence eventually leading
to physical gelation. Such a transition takes place within a
narrow range of ionic composition (from XCs = 0.2 to 0.3
in the present conditions of Mw , polymer concentration,
ionic strength and temperature). This result is in agreement
with our previous findings [6] and partially confirms the observations of other investigators [12,16]. (ii) Also in the case
of the cesium fraction dependence, we failed to find suitable
conditions for the associative processes to attain an equilibrium without involving physical gelation of the systems.
This is in analogy to the case of the polymer concentration
dependence (Fig. 2). When significant time dependence
appears, in fact, intermolecular association unavoidably
proceeds up to the achievement of the gelation threshold.
As a final comment, it should be noted that even the gel
phase produced at the gelation threshold certainly does not
constitute an equilibrium state, since the achievement of
the connectivity transition merely represents an intermediate state in the evolution of the associating systems. The
very presence of slow fluctuations of the speckle pattern
denotes the continuous internal evolution and structural
rearrangement of the gel network. Through very slow dynamics, indeed, the system attempts to approach a truly
thermodynamically stable state, which remains, however,
unattainable on an experimentally relevant time scale.
Acknowledgements
H.R. and F.C. are indebted to FWO-Vlaanderen, INTAS
(00-243) and the Catholic University of Leuven for supporting this research and for a research grant (F.C.).
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