Rheological behaviour of polysaccharide aqueous solutions

Several data relative to the viscosity of water-soluble polysaccharide solutions were collected from the literature and processed by different rheological models. Some relationships between the viscosity of these polymer solutions, their molecular weight and their solution concentrations, were established and their validity checked. Thus, an accurate equation correlating the viscosity and both the shear rate and the solution concentration of different water soluble polysaccharides (xanthan, hyaluronan, carboxymethylcellulose) was deduced on the basis of Cross' model which suggests two domains in which the viscosity is constant, i.e. very low and very high shear rate ranges. Then, an expression relating the zero-shear viscosity (A) and the concentration of their solutions was proposed. Finally, an alternative equation to that of Mark–Houwink correlating the molecular weight and the intrinsic viscosity of the water-soluble polysaccharides studied in this paper was found.     

On the thermal stability of xanthan gum

The thermal stability of xanthan gum in dilute aqueous solutions at 90°C is considered. The relative viscosity as a function of ageing time is discussed, and it has been found to depend on the polymer concentration and conformation as well as on the salt content. The effectiveness of a quencher demonstrates the existence of a free-radical process in the degradation. During ageing, the molecular weight first decreases by rapid random hydrolysis of the main chain and loss of the pyruvate and acetate substituents. Later, oligomers are formed corresponding to a breakdown of both the side chain and the main chain. The identification of cellodextrins in the oligomer pool demonstrates the second effect.     

The viscosity dependence on concentration,molecular weight and shear rate of xanthan solutions

Summary This paper concerns the viscosity dependence of Xanthan as a function of polymer concentration, shear rate and molecular weight in the ordered conformation. The different samples with various molecular weights are obtained by ultrasonication. A unique curve is obtained for the reduced specific viscosity ( ) as a function of γ · γ _r ⁻¹ for the different molecular weight samples and polymer concentrations below an overlap concentration C [η]₀⩽ 1.5. The master curve giving the relation as a function of C [η]₀ is drawn and compared with that of polystyrene in good solvent. The largest increase of in semidilute solution may be due to larger interchain interactions and to larger stiffness of the Xanthan molecule.     

Evaluation of DNA isolation procedures for detecting and quantifying environmental Legionella by real-time quantitative PCR

Six methods, QiAamp DNA Mini Kit (Q), Q with Sepharose 4B gel column (Q/G), Q with low melting point agarose (Q/L), freeze-thaw/phenol-chloroform lysis (FT-PC), FT-PC/G, and FT-PC/L, were evaluated for their ability to isolate DNA of sufficient quality to quantify Legionella using qPCR. Samples of mixing Legionella pneumophila (ATCC33152) and humic acid (HA, 0-126.8 mg/l) were treated by the six methods. Q, Q/G, Q/L, FT-PC/G, and FT-PC/L removed HA from 1.9-126.8 to <1 mg/l determined by A260 with a spectrophotometer. Q obtained the highest DNA yield, followed by Q/G. Dilution (10- to 100-fold) of DNA arising from extraction using Q, Q/G, FT-PC, or FT-PC/G prevented qPCR inhibition. The highest recovery of cells was found in DNA extracted by Q and diluted 100-fold, and followed by Q/G. The applicability of Q and Q/G with dilution was further validated with cooling tower waters. Q or Q/G with 10-fold dilution increased L. pneumophila detection, whereas 100-fold dilution obtained the highest cell concentrations. Similar results were found for Legionella spp. except that both 10- and 100-fold dilutions increased cell concentrations. Thus, Q with 10-fold dilution is suggested to detect and quantify Legionella spp. and detect L. pneumophila. For L. pneumophila-positive samples, 100-fold diluted DNA must be re-analyzed to accurately quantify L. pneumophila.     

Dual-layer hollow fibers for gas separation processes produced by quadruple spinning

A novel quadruple spinneret to produce dual-layer hollow fiber membranes by simultaneous spinning of two polymer solutions, using the dual precipitation bath technique is proposed. Hollow fibers aimed at gas separation processes were prepared in extrusion system specifically designed and built for this purpose. A polyurethane polymer was selected as the selective layer (outer-layer), while polyethersulfone was defined as the support (inner-layer). Activated carbon powder was added into the PU solution for further improvement of the transport properties. The hollow fibers showed good adhesion between the polymer layers and a defect-free selective layer. Representative results include a CO₂/N₂ selectivity of 43.     

Gelation of gellan – A review

Gellan is an anionic extracellular bacterial polysaccharide discovered in 1978. Acyl groups present in the native polymer are removed by alkaline hydrolysis in normal commercial production, giving the charged tetrasaccharide repeating sequence: → 3)-β-d-Glcp-(1 → 4)-β-d-GlcpA-(1 → 4)-β-d-Glcp-(1 → 4)-α-l-Rhap-(1 →. Deacylated gellan converts on cooling from disordered coils to 3-fold double helices. The coil–helix transition temperature (T_m) is raised by salt in the way expected from polyelectrolyte theory: equivalent molar concentrations of different monovalent cations (Group I and Me₄N⁺) cause the same increase in T_m; there is also no selectivity between different divalent (Group II) cations, but divalent cations cause greater elevation of T_m than monovalent. Cations present as counterions to the charged groups of the polymer have the same effect as those introduced by addition of salt. Increasing polymer concentration raises T_m because of the consequent increase in concentration of the counterions, but the concentration of polymer chains themselves does not affect T_m. Gelation occurs by aggregation of double helices. Aggregation stabilises the helices to temperatures higher than those at which they form on cooling, giving thermal hysteresis between gelation and melting. Melting of aggregated and non-aggregated helices can be seen as separate thermal and rheological processes. Reduction in pH promotes aggregation and gelation by decreasing the negative charge on the polymer and thus decreasing electrostatic repulsion between the helices. Group I cations decrease repulsion by binding to the helices in specific coordination sites around the carboxylate groups of the polymer. Strength of binding increases with increasing ionic size (Li⁺ < Na⁺ < K⁺ < Rb⁺ < Cs⁺); the extent of aggregation and effectiveness in promoting gel formation increase in the same order. Me₄N⁺ cations, which cannot form coordination complexes, act solely by non-specific screening of electrostatic repulsion, and give gels only at very high concentration (above ∼0.6 M). At low concentrations of monovalent cations, ordered gellan behaves like a normal polymer solution; as salt concentration is increased there is then a region where fluid “weak gels” are formed, before the cation concentration becomes sufficient to give true, self-supporting gels. Aggregation and consequent gelation with Group II cations occurs by direct site-binding of the divalent ions between gellan double helices. High concentrations of salt or acid cause excessive aggregation, with consequent reduction in gel strength. Maximum strength with divalent cations comes at about stoichiometric equivalence to the gellan carboxylate groups. Much higher concentrations of monovalent cations are required to attain maximum gel strength. The content of divalent cations in commercial gellan is normally sufficient to give cohesive gels at polymer concentrations down to ∼0.15 wt %. Gellan gels are very brittle, and have excellent flavour release. The networks are dynamic: gellan gels release polymer chains when immersed in water and show substantial recovery from mechanical disruption or expulsion of water by slow compression. High concentrations of sugar (∼70 wt % and above) inhibit aggregation and give sparingly-crosslinked networks which vitrify on cooling. Gellan forms coupled networks with konjac glucomannan and tamarind xyloglucan, phase-separated networks with kappa carrageenan and calcium alginate, interpenetrating networks with agarose and gelling maltodextrin, and complex coacervates with gelatin under acidic conditions. Native gellan carries acetyl and l-glyceryl groups at, respectively, O(6) and O(2) of the 3-linked glucose residue in the tetrasaccharide repeat unit. The presence of these substituents does not change the overall double helix structure, but has profound effects on gelation. l-Glyceryl groups stabilise the double helix by forming additional hydrogen bonds within and between the two strands, giving higher gelation temperatures, but abolish the binding site for metal ions by changing the orientation of the adjacent glucuronate residue and its carboxyl group. The consequent loss of cation-mediated aggregation reduces gel strength and brittleness, and eliminates thermal hysteresis. Aggregation is further inhibited by acetyl groups located on the periphery of the double helix. Gellan with a high content of residual acyl groups is available commercially as “high acyl gellan”. Mixtures of high acyl and deacylated gellan form interpenetrating networks, with no double helices incorporating strands of both types. Gellan has numerous existing and potential practical applications in food, cosmetics, toiletries, pharmaceuticals and microbiology.     

Cholesteric order in aqueous solutions of the polysaccharide Xanthan

Summary Measurements of birefringence, optical rotation and laser light diffraction show that aqueous solutions of the polyelectrolytic polysaccharide Xanthan at a concentration of 7.5 % (vol/vol) have long range order very similar to cholesteric liquid crystals. The cholesteric screw is left handed implying a rod-like conformation and right handed helicity of individual molecules. The cholesteric phase separates from a less concentrated isotropic solution and spherolites are formed.