Effect of water structure on gelation of agar in glycerol solutions and phase diagram of agar organogels.

A comprehensive study of hydration of polyanionic agar molecules in its solution and gel phase in glycerol-water binary solvent is reported. Raman spectroscopy results predict differential water structure arrangement for glycerol-water binary solvent, 0.02% (w/v) agar in glycerol solution and 0.3% (w/v) agar organogel. The 3200 cm(-1) Raman band pertaining to ice-like structure of water was found to increase in gel phase alike in glycerol-water solvent while it decreased in agar solutions with increase in glycerol concentration. In contrast, the partially structured water corresponding to the component 3310 cm(-1) of Raman spectra increased in agar solution, and decreased in gel phase similar to glycerol-water solvent case. We have explained these observations based on a simple model where the available oxygen to hydrogen atom ratio in a given solvent-polymer system uniquely defines hydration in solution and gel phases. The gelation concentration was found to increase from 0.18 (for water) to 0.22% (w/v) (50% v/v glycerol solution) as the glycerol concentration was raised. Correspondingly, the gelation temperature, T(g), showed a decline from 40 to 20 °C, and the gel melting temperature, T(m), revealed a reduction from 81 to 65 °C in the same glycerol concentration regime. Two distinctive features are evident here: (i) presence of glycerol as a cosolvent does not favor the gelation of agar as compared to water and (ii) agar organogels are softer than their hydrogels. A unique 3D phase diagram for the agar organogel is proposed. Circular dichroism data confirmed that the agar molecules retained their biological activity in these solvents. Thus, it is shown that thermo-mechanical properties of these organogels could be systematically tuned and adapted as per application requirement.

Effect of ionic strength on surface-selective patch binding-induced phase separation and coacervation in similarly charged gelatin-agar molecular systems.

Coacervate is defined as a polymer-rich dense phase, which remains in thermodynamic equilibrium with its low concentrated phase called the supernatant. The effect of ionic strength (I = 0-0.1 M NaCl) on the mechanism of surface patch binding-induced protein-polysaccharide interaction leading to complex coacervation, between agar (a polyanionic polysaccharide) and gelatin B (a polyampholyte protein), both having similar net charge, at a particular mixing ratio, [gelatin]/[agar] = 1, was studied at various temperatures (20-40 °C). The coacervation transition was probed by turbidity and zeta-potential measurements. The intermolecular association had the signature of surface-selective binding, and a model calculation could explain the potential energy of interactions operative in such processes. The thermo-mechanical features of the coacervates were found to be strongly dependent on ionic strength, which has been interpreted as originating from formation of salt-bridges between the biopolymers. The microstructure of the coacervate materials was analyzed using rheology and small angle neutron scattering (SANS) techniques, which probed the heterogeneity prevailing in the system that had characteristic length in the range 1.3-2.0 nm, and the same data yielded the correlation length of concentration fluctuations, which was estimated to lay in the range 2.4-4 nm. It is concluded that the coacervation transition driven by surface-selective binding is not influenced by the ionic strength of the solution, but the mobile ions participate in the structural organization of the interacting polyions in the coacervate.

Interaction of gelatin with room temperature ionic liquids: a detailed physicochemical study.

Interaction of gelatin (G) with room temperature ionic liquids (ILs), 3-methyl-1-octylimidazolium chloride [C(8)mim][Cl] and 1-butyl-3-methylimidazolium octylsulfate [C(4)mim][C(8)OSO(3)], have been investigated through tensiometry, conductivity, steady-state fluorescence, turbidity, and dynamic light scattering (DLS). We have observed that the nature of interactions in G-[C(8)mim][Cl] system are remarkably different as compared to G-[C(4)mim][C(8)OSO(3)] system. At low concentrations, much below the critical micelle concentration (cmc) of IL, the IL monomers are adsorbed at the native G at the interface forming G-IL (monomer) complex, whereas both the monomers and lower IL aggregates are interacted with G in bulk leading to G-IL (aggregate) complex. The increased hydrophobic character of the G-IL complexes is evidenced from pyrene fluorescence. Turbidity measurements showed interestingly distinguished coacervation characteristics in the investigated systems. In case of G-[C(4)mim][C(8)OSO(3)] system, the coacervates dissolve in the free micellar solution whereas G-[C(8)mim][Cl] coacervates remain stable up to very high concentration. DLS provided useful information about the changes in size of gelatin and the nature of interactions between gelatin and ILs. Thermodynamic parameters of micellization with and without gelatin have been derived and compared.

Syneresis in agar hydrogels.

Agar hydrogels exhibit syneresis which creates internal osmotic stress on the physical network. It was observed that such a stress gives rise to characteristic pulsating modes (breathing modes). Experiments carried over a period of 60-day revealed that the network deformations grew monotonously when the solvent released by syneresis was removed periodically from gel surface. However, when the solvent was not withdrawn, the gel exhibited very slowly relaxing breathing modes. The swelling-deswelling dynamics has been discussed in the generalized framework of a dissipative damped oscillator.

Universal growth of microdomains and gelation transition in agar hydrogels.

Investigations were carried out on aqueous sols and gels of agar (extracted from red seaweed Gelidiella acerosa) to explore the growth of microdomains en route to gelation. Isothermal frequency sweep studies on gel samples revealed master plots showing power-law dependence of gel elastic modulus, |G*|, on oscillation frequency, omega as |G*| approximately omegan, independent of temperature, with 0.5Tg). The S(q,t) behavior close to the gel transition point (Tg approximately (38+/-3 degrees C determined from rheology) followed a stretched exponential function: S(t)=A exp(-t/ts)beta. The beta factor increased from 0.25 to 1 as the gel temperature approached 25 degrees C from Tg, and relaxation time, ts, showed a peak at T approximately 30 degrees C. The SLS data (in the sol state) suggested the scaling of scattered intensity, Is(q) approximately epsilon(-gamma) (epsilon=(T/Tg-1), T>Tg) with gamma=0.13+/-0.03, and the presence of two distinct domains characterized by a Guinier regime (low q) and a power-law regime (high q). Close to and above Tg (+2 degrees C), IS(q) scaled with q as Is(q) approximately q(-alpha) with alpha=2.2+/-0.2, which decreased to 1.4+/-1 just below Tg (-2 degrees C), implying a coil-helix transition for 0.2% (w/v) and 0.3% (w/v) samples. For a 0.01% sample, alpha=3.5+/-0.5 which indicated the presence of spherical microgels.

Swelling and de-swelling kinetics of gelatin hydrogels in ethanol-water marginal solvent.

Controlled osmotic swelling and de-swelling measurements have been performed on gelatin, a polyampholyte, hydrogels suspended in water-ethanol marginal solvent at room temperature (20 degrees C) where the alcohol concentration was changed from 0 to 100% (v/v). The change in gel mass was monitored as function of time until osmotic equilibrium was established with the surrounding solvent. It was observed that osmotic pressure of polymer-solvent mixing, pi(m)<