Viscoelastic properties for kappa- and iota-carrageenan in aqueous NaI from the liquid-like to the solid-like behaviour.

The dynamic mechanical behaviour of a series of concentrations of kappa-carrageenan (KC; 0.35-1.6% w/w) and iota-carrageenan (IC; 0. 2-1% w/w) in 0.2 M NaI has been investigated. The flow behaviour of KC within the concentration range 0.004-0.8% (w/v) was also described. The high intrinsic viscosity of KC in 0.2 M NaI (23.4 dl g(-1)) and the great increase in viscosity with increasing concentration, in comparison with linear flexible polysaccharides, is well consistent with the stiffness of KC helices in NaI. The variation of the 'zero-shear' specific viscosity of KC in 0.2 M NaI with the degree of space-occupancy (c[eta]) displays two critical concentrations at c* approximately 0.09% w/v (c*[eta] approximately 2) and c** approximately 0.4% w/v (c**[eta] approximately 10). Different viscoelastic behaviours were exhibited from the liquid-like to the solid-like depending upon the type of carrageenan. From the application of the time-temperature superposition, classical frequency-temperature master curves could be obtained for KC, but not for IC. Moreover, for KC, a concentration-frequency master curve could be constructed for the concentrations below 1.5%, indicating a 'solution-like' behaviour in this entire concentration range, although systems above 0.8% were visually gel-like. It is proposed that the rigidity of the KC helices is responsible for the slow relaxation rates of the gel-like samples. At higher concentrations (beyond 1.6%) a frequency-temperature superposition was no longer possible. In contrast to KC, IC behaved as a typical viscoelastic gel with a very weak frequency dependence of the storage modulus at all temperatures. This indicates the existence of associations beyond simple entanglements for IC. Creep experiments performed at higher carrageenan concentrations in 0.1 M NaI further corroborated the differences in the viscoelastic behaviour between KC and IC.

Conformation and association of kappa-carrageenan in the presence of locust bean gum in mixed NaI/CsI solutions from rheology and cryo-TEM.

Mixtures of locust bean gum (LBG) with kappa-carrageenan (KC) in 0.1 M aqueous solutions of the mixed salts NaI/CsI were investigated by cryo-transmission electron microscopy (cryo-TEM) and dynamic viscoelastic measurements. Previous studies have shown that as the cesium content is increased in such mixed salt solutions, a transition occurs from molecularly dispersed helices to 'superhelical rods' of KC. We now found that LBG stabilises the superhelical rods, shifting the transition to a lower content of Cs for the mixtures than for KC alone. The formation of superhelical rods was evidenced both by cryo-TEM images and by an onset of thermal hysteresis in the coil helix transition of KC. In the mixtures, the transition temperatures on cooling and heating were insensitive to the proportions of LBG and KC present at all cesium contents. Under conditions where no helix aggregation occurred (no hysteresis) the mixtures showed high tan delta values and low storage moduli. Under aggregated conditions, gels formed, and gels with added LBG had enhanced moduli compared to gels with KC alone. On the basis of these results we propose that LBG associates to the super-helical rods of KC.

Organisation and association of kappa-carrageenan helices under different salt conditions.

Mixtures of the added salts NaI and CsI can be used to gradually 'tune' the propensity of kappa-carrageenan (KC) helices to aggregate in solution. We show that this method can be used to resolve the molecular events by which helix formation, under certain conditions, leads to gelation. We also present an overview of the various states of aggregation and organisation that appear for helical KC (non-degraded or ultrasonically degraded) when the NaI/CsI ratio and the concentration of KC are varied. A transition to rigid, superhelical rods is found above a well-defined fraction of cesium. This transition is reflected in a range of experimental measurements, such as cryo-transmission electron microscopy, optical rotation, viscometry and small deformation oscillatory measurements. The superhelical-rod state also seems essential for the association of KC with locust bean gum, and locust bean gum is found to stabilise this state. Novel states of KC alone have been found at cesium contents below the transition threshold. Non-degraded KC forms weak gels at sufficiently high concentrations (> ca. 1%). In contrast, ultrasonically degraded KC forms a chiral nematic liquid crystalline phase at sufficiently high concentrations (> ca. 5%) under these salt conditions.

Protein partitioning in weakly charged polymer-surfactant aqueous two-phase systems.

The study includes partitioning of proteins in aqueous two-phase systems consisting of the polymer dextran and the non-ionic surfactant C12E5 (pentaethylene glycol mono-n-dodecyl ether). In this system a micelle-enriched phase is in equilibrium with a polymer-enriched phase. Charges can be introduced into the micelles by the addition of charged surfactants. The charge of the mixed micelles is easily varied in sign and magnitude independently of pH, by the addition of different amounts of negatively charged surfactant, sodium dodecyl sulphate (SDS), or positively charged surfactant dodecyl trimethyl ammonium chloride (DoTAC). A series of water-soluble model proteins (BSA, beta-lactoglobulin, myoglobin, cytochrome c and lysozyme), with different net charges at pH 7.1, have been partitioned in non-charged systems and in systems with charged mixed micelles or charged polymer (dextran sulphate). It is shown that partition coefficients for charged proteins in dextran-C12E5 systems can be strongly affected by addition of charged surfactants (SDS, DoTAC) or polymer (dextran sulphate) and that the effects are directly correlated to protein net charge.

On the structure of aggregated kappa-carrageenan helices. A study by cryo-TEM, optical rotation and viscometry.

Cryo-transmission electron microscopy (cryo-TEM), viscometry and optical rotation have been used to study the microstructure of dilute solutions of helical kappa-carrageenan under varied electrolyte composition (0.1 M of NaI, CsI and mixtures of the two salts). Microfibers (300-400 nm in length) were observed above a critical cesium content, while below that no microstructure was seen in the micrographs. A drastic increase in the specific viscosity and an onset of thermal hysteresis in the optical rotation above the same critical cesium content provide clear evidence of aggregate formation. This leads to the conclusion that the observed microfibers are aggregates consisting of several helices. At high proportions of cesium, further aggregation of the microfibers was observed by cryo-TEM.

Surfactant binding and micellisation in polymer solutions and gels: binding isotherms and their consequences.

Transient networks are formed by many pairs of polymer and surfactant that associate into mixed micelles. Generally, for a given polymer concentration, the viscosity or the elastic shear modulus of such mixtures first increases and then decreases with the concentration of added surfactant. We point to the importance of considering the general features of the isotherm for the binding of the surfactant to the polymer when analysing these effects. We argue that a break-down of mixed micellar crosslinks between polymers should typically occur only when the added surfactant dominates in the mixed micelles. At this point, the concentration of monomeric surfactant should be of the same order as the relevant c.m.c. of the surfactant. The relevant c.m.c. is not generally the bulk c.m.c. but, rather, the c.m.c. in the same system but in the absence of those hydrophobic parts of the polymer that are responsible for the interpolymer crosslinking. We use this approach to analyse new and previously published experimental data on a range of ionic and non-ionic hydrophobically modified polymers mixed with surfactants that form spherical micelles, but have widely different c.m.c.s. A consistent picture of the mixed micellar stoichiometries at the point of the maximum viscosity, and at the point of final dissolution of the mixed micellar crosslinks, emerges from this analysis.

87Rb+ spin relaxation in enzymically purified and in untreated iota-carrageenan.

The temperature dependences of the transverse (R2) and longitudinal (R1) n.m.r. relaxation rates of 87Rb+ in aqueous 5% iota-carrageenan have been compared with similar data for a sample purified by treatment with kappa-carrageenase. In each sample, the relaxation rates were sensitive to the conformation (helix or random coil). In the intact sample, the small (less than or equal to 5%) fraction of kappa-carrageenan (which, in its helical state, specifically binds rubidium ions) was solely responsible for the pronounced line-broadening that has been observed hitherto for 87Rb in iota-carrageenan gels. In the purified sample, the effects on the relaxation of 87Rb induced by iota-carrageenan are similar to those found in comparable systems in the absence of site-binding of the ions. Thus, there was a modest enhancement of the relaxation with R1 approximately R2 for the flexible coil conformation and a comparably larger effect, with significant contributions from dynamic processes on the time-scale of the inverse resonance frequency or longer, for the thicker, more highly charged and rigid helix conformation of iota-carrageenan.