Solvent stabilizing effects on the order-disorder transition of schizophyllan in aqueous mixtures of carboxylic acids.

Schizophyllan is a triple helical β-1,3--glucan, and shows the cooperative order-disorder transition in the aqueous solution at the triple helix state. In this paper, the solvent stabilizing effects of two carboxylic acids, acetic acid and citric acid, on the cooperative order-disorder transition of aqueous schizophyllan solution were investigated from DSC and SEC-MALS measurements. The transition temperature (T) was shifted to higher temperature with increasing the molar fraction of carboxylic acid in the mixture (x).

Association with Imidazole in the Cooperative Order-Disorder Transition in Aqueous Solution of Schizophyllan.

Schizophyllan, a triple helical polysaccharide, exhibits cooperative order-disorder transition (CODT) in aqueous solutions. The transition transforms the ordered structure (triple helix I) formed between the branched side chains and solvent molecules into the disordered structure (triple helix II) without dissociation of the triple helix. The CODT behaviors in HO-imidazole mixtures containing HCl with different molar ratios of imidazole/HCl were investigated by adiabatic calorimetry and differential scanning calorimetry on two schizophyllan solutions with different molar masses.

Crossover of Rate-Limiting Process in Plasma Gel Growth by Contact with Source of Gelator.

Plasma is regarded as a solution of precursor polymers specifically transformed to gel-forming polymers by a reaction with initiators. We developed a theory for the gel growth dynamics of plasma induced by contact with a source of gelators that are yielded by the initiation. In developing the theory, we combined the Ginzburg-Landau type dynamics with the gelator diffusion dynamics expressed by the moving boundary picture.

Gel growth of aqueous konjac glucomannan solution containing sodium trimetaphosphate dialyzed with dilute sodium hydroxide.

The growth rate of the hydrogel of the aqueous konjac glucomannan (KGM) solution containing sodium trimetaphosphate (STMP) dialyzed with aqueous NaOH was investigated in a rectangular cell. The growth rate of the KGM-STMP gel depended on both the KGM and STMP concentrations in addition to the NaOH concentration. The initial growth rate of the KGM-STMP gel was closely related to the diffusion of NaOH into the KGM-STMP solution, leading to the ring-opening reaction of STMP and the deacetylation of KGM at the interface.

Conformation and cooperative order-disorder transition in aqueous solutions of β-1,3-d-glucan with different degree of branching varied by the Smith degradation.

β-1,3-d-glucan with different degrees of branching were obtained by selectively and gradually removing side chains from schizophyllan, a water-soluble triple helical polysaccharide, using the Smith degradation. Size exclusion chromatography combined with a multi-angle light scattering detection was performed in aqueous 0.1 M NaCl.

Cooperative Order-Disorder Transition of Carboxylated Schizophyllan in Water-Dimethylsulfoxide Mixtures.

Carboxylated schizophyllan ("sclerox") is a chemically modified polysaccharide obtained by partial periodate oxidation and subsequent chlorite oxidation of schizophyllan, a water-soluble neutral polysaccharide having a β-1,3-linked glucan backbone and a β-1,6-linked d-glucose residue side chain at every third residue of the main chain. The triple helix of schizophyllan in water has a cooperative order-disorder transition associated with the side chains. The transition is strongly affected by the presence (mole fraction) of dimethylsulfoxide (DMSO).

Effects of carboxylation of the side chains on the order-disorder transition in aqueous solution of schizophyllan, a triple helical polysaccharide.

Schizophyllan and scleroglucan are water-soluble polysaccharides having repeating units consisting of three β-1,3-linked glucose residues in the main chain and a single β-1,6-linked glucose residue as the side chain. This polysaccharide dissolves as a triple helix in an aqueous solution and shows a cooperative order-disorder transition between the side chain and solvent molecules while retaining the triple helical conformation. Periodate and subsequent chlorite oxidations selectively modify the side chain glucose to provide the corresponding dicarboxylate units.

Conformation of carboxylated schizophyllan in aqueous solution.

Carboxylated schizophyllan (sclerox) samples of different degrees of oxidation were molecularly characterized by size exclusion chromatography equipped with a multi-angle light scattering detector (SEC-MALS) in 0.10 M aqueous NaCl solution. The molar mass distribution obtained by SEC-MALS shows that sclerox of low degree of oxidation is dissolved mainly as the trimer, whereas the trimer and single chain coexist in solution of sclerox of high degree of oxidation.

Water structures of differing order and mobility in aqueous solutions of schizophyllan, a triple-helical polysaccharide as revealed by dielectric dispersion measurements.

Dielectric dispersion measurements were made on aqueous solutions of a triple-helical polysaccharide schizophyllan over a wide concentration range 10-50 wt % at -45 to +30 degrees C. In the solution state, three different water structures with the different relaxation times tau were found, namely, bound water (taul), structured water (taus), and loosely structured water (tauls) in addition to free water (tauP). Structured water is less mobile and loosely structured water is nearly as mobile as free water, but bound water with taul is much less mobile, thus taul >> taus >> tauls greater, similar tauP.

Static water structure detected by heat capacity measurements on aqueous solutions of a triple-helical polysaccharide schizophyllan.

Heat capacity measurements were made on aqueous solutions of a triple-helical polysaccharide schizophyllan by precision adiabatic calorimetry over a wide range of concentrations 30.45-90.93 wt % at temperatures between 5 and 315 K.

Ordering in aqueous polysaccharide solutions. II. Optical rotation and heat capacity of aqueous solutions of a triple-helical polysaccharide schizophyllan.

Deuterium oxide solutions of schizophyllan, a triple-helical polysaccharide, undergoing an order-disorder transition centered at 17 degrees C, were studied by optical rotation (OR) and heat capacity (C(p)) to elucidate the molecular mechanism of the transition and water structure in the solution and frozen states. The ordered structure at low temperature consisted of the side chains and water in the vicinity forming an ordered hydrogen-bonded network surrounding the helix core and was disordered at higher temperature. In the solution state appeared clearly defined transition curves in both the OR and C(p) data.

Ordering in aqueous polysaccharide solutions. I. Dielectric relaxation in aqueous solutions of a triple-helical polysaccharide schizophyllan.

Deuterium oxide solutions of a triple-helical polysaccharide schizophyllan, undergoing an order-disorder transition centered around 17 degrees C, were studied by the time-domain reflectometry (TDR) to obtain dielectric dispersions in the solution and frozen states. In the solution state, the dispersion below the transition temperature is resolved in three dispersions (relaxation times at 0 degrees C) ascribed to side chain glucose residue (1; 102 ns), structured water (s; 2.0 ns) and bulk water (h), respectively, from low to high frequencies.