Rheological properties of mixtures of κ-carrageenan from Hypnea musciformis and galactomannan from Cassia javanica

Mixed gels of κ-carrageenan (κ-car) from Hypnea musciformis and galactomannans (Gal) from Cassia javanica (CJ) and locust bean gum (LBG) were compared using dynamic viscoelastic measurements and compression tests. Mixed gels at 5 g/l of total polymer concentration in 0.1 M KCl showed a synergistic maximum in viscoelastic measurements for κ-car/CJ and κ-car/LBG at 2:1 and 4:1 ratios, respectively. The synergistic maximum obtained from compression tests carried out for mixed gels at 10 g/l of total polymer concentration in 0.25 M KCl was the same for both κ-car/CJ and κ-car/LBG gels. An enhancement in the storage modulus (G′) and the loss modulus (G″) was observed in the mechanical spectra for the mixtures in relation to κ-car. The proportionally higher increase in G″ compared with G′, as indicated by the values of the loss tangent (tan δ), suggests that the Gal adhere non-specifically to the κ-car network.     

Conformation and association of κ-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 κ-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 δ 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.     

Rheological and calorimetric study of the sol–gel transition of κ-carrageenan

Rheological and DSC techniques were used to study the effect of κ-carrageenan and KCl concentrations, 0–300 mM, on the sol–gel transition as well as on the linear viscoelasticity, at 25 °C, of the resulting gels. In heating and cooling DSC tests, the peak temperature was taken as the sol–gel transition point. In rheological tests, sol–gel transitions were determined from the variation of dynamic moduli with frequency and temperature, the independence of the phase angle on frequency and the evolution with temperature of dynamic moduli on cooling and heating at constant frequency and strain. Transition temperatures from DSC and rheology were in good agreement among them and with those previously reported. The three procedures yielded similar results, but the transition temperatures were more easily determined through the independence of the phase angle on frequency. Frequency sweeps showed gel behavior with stiffness increasing with polysaccharide and salt concentration. Below 100 mM KCl, G′ increased notably, whereas higher concentrations produced only marginal increases.     

Mixtures of pregelatinised maize starch and κ-carrageenan: Compatibility, rheology and gelation

Compatibility, flow and visco-elastic properties of a pregelatinised maize starch mixed with κ-carrageenan were investigated. After cooking of the pregelatinised starch, some undissolved granules remained in solution. Aqueous mixtures of κ-carrageenan and starch were studied at 60 °C and 20 °C by combining rheological measurements and microscopic observations under conditions allowing gelation of carrageenan and non-gelation of starch. The viscometric study of mixed dilute solutions of amylose from pregelatinised starch and carrageenan showed that the components are slightly incompatible. Mixture viscosity and elastic modulus were studied at 60 °C in details as a function of mixture composition for a total polymer concentration of 3%; both were found to be significantly higher than the corresponding theoretical additive values. This finding was interpreted by starch granules excluded volume effect. At 20 °C, no noticeable increase of mixture elastic modulus was found as compared with the additive value. The absence of the synergistic effect is supposed to be due to the formation of highly inhomogeneous gels with agglomerates of undissolved granules.     

Rheological properties of barley β-glucan

Health benefits of cereal β-glucan are linked to its high viscosity. Although viscosity of β-glucan gum solutions has been reported previously, there are conflicting reports about its behavior at elevated temperatures. Therefore, the viscosity behavior of barley β-glucan gum obtained in a pilot plant (PP) or in a laboratory (LAB) was determined at different shear rates (1.29–129 s⁻¹) and temperatures (0.1–75 °C) in this study. Viscosity decrease with temperature was demonstrated for both gums and activation energy E_a was calculated from the Arrhenius equation. None of the fresh gum solutions exhibited thixotropic behavior at ≤1% (w/w) concentration, but the measurement demonstrated that increased shear rate is not applicable to polymer solutions of low viscosity. Information about rheological properties of β-glucan will lead to better understanding of its behavior under physiological and processing conditions.     

Rheological properties of guar galactomannan solutions during hydrolysis with galactomannanase and alpha-galactosidase enzyme mixtures

Guar galactomannan, a naturally occurring polysaccharide, is susceptible to hydrolysis by three enzymes: beta-mannosidase, beta-mannanase, and alpha-galactosidase. The beta-mannosidase cleaves a single mannose unit from the nonreducing end of the guar molecule, the beta-mannanase cleaves interior glycosidic bonds between adjacent mannose units, and the alpha-galactosidase cleaves the galactose side branches off the guar. In this study, hydrolysis of guar solutions using hyperthermopilic versions of these enzymes together in different proportions and combinations are examined. The enzymatic reactions are carried out in situ in a rheometer, and the progress of the reaction is monitored through measuring the variation in zero shear viscosity. We find the presence of alpha-galactosidase to affect the action of both beta-mannanase and beta-mannosidase with respect to solution rheology. However, this effect is more pronounced when the alpha-galactosidase and beta-mannanase or beta-mannosidase enzymes were added sequentially rather than simultaneously. This likely is the result of debranching of the guar, which facilitates attack on beta-1,4-linkages by both the beta-mannanase and the beta-mannosidase enzymes and increases hydrolytic rates by the individual enzymes. A rheology-based kinetic model is developed to estimate the reaction rate constants and interpret synergistic effects of multiple enzyme contributions. The model fits the experimental data well and reveals that both the native and the debranched guar have the same activation energy for beta-mannanase action, although debranching considerably increases the frequency of enzyme-guar interactions.     

Synthesis and NMR structural analysis of O-succinyl derivative of low-molecular-weight κ-carrageenan

Low-molecular-weight (LMW) κ-carrageenan was achieved through mild hydrochloric acid hydrolysis of κ-carrageenan. The acylation of LMW κ-carrageenan was performed by use of tetrabutylammonium (TBA) salt of the anionic polysaccharide fragments, succinic anhydride, 4-dimethylaminopyridine and tributylamine under homogeneous conditions in N,N-dimethylformamide at 80 °C. Investigation of FT-IR spectrum of the succinylated LMW κ-carrageenan showed that a monoester derivative with succinyl group was formed when LMW κ-carrageenan reacted with succinic anhydride. The ¹H and ¹³C NMR spectroscopy has been used to characterize the fine structure of O-succinyl derivative of the LMW κ-carrageenan. The ¹³C and ¹H NMR chemical shifts of disaccharide unit of O-succinyl LMW κ-carrageenan have been fully assigned using 2D NMR spectroscopic techniques.     

Rheological properties of mixtures of protein-polysaccharide-dynamic viscoelasticity of blend gels of acylated gelatin, kappa-carrageenan, and agarose

Complex Young's modulus of blend gels of gelatin and kappa-carrageenan or agarose has been measured in order to clarify the protein-polysaccharide interaction in biological systems. The mixture of gelatin and kappa-carrageenan showed phase separation in the intermediate volume fraction of gelatin, and it formed a homogeneous gel when the volume fraction of gelatin is very large or very small. Since the dynamic Young's modulus for blend gels of kappa-carrageenan and gelatin was larger than the calculated one from a theory for dispersed systems, some structural reinforcing must occur. The mixture of agarose and gelatin showed the inverse tendency. It was concluded that the role of electrolytic groups was dominant in dilute gels, while molecular entanglement became more important in concentrated gels.     

Structure elucidation and properties of a non-ionic galactomannan derived from the Cassia pleurocarpa seeds

A non-ionic water soluble galactomannan made up of d-galactose and d-mannose was isolated from the seed endosperm of Cassia pleurocarpa. Acid catalyzed fragmentation, periodate oxidation, methylation and selective enzymatic hydrolysis revealed that the repeating unit of the heteropolysaccharide had a backbone of beta(1-->4) linked d-mannopyranosyl units to which D-galactopyranosyl units are linked as side chains through alpha(1-->6) linkages. The properties such as viscosity, water/saline retention, gelling behavior, and shelf life of the galactomannan indicated that the material may be exploited in biomedical applications for example drug delivery and tissue engineering fields.     

Solution properties of the galactomannans extracted from the seeds of Caesalpinia pulcherrima and Cassia javanica: comparison with locust bean gum.

The galactomannans from the seeds of Caesalpinia pulcherrima and Cassia javanica were extracted from the milled seeds in water at room temperature. Both products, as well as a commercial sample of locust bean gum (LBG), were purified by precipitation in isopropyl alcohol. The intrinsic viscosity determined for LBG, [eta] = 15.2 dl/g, was slightly higher than those for the other two galactomannans. The dependence of the specific viscosity at zero shear rate on the coil overlap parameter, C[eta], revealed a similar behaviour for the three galactomannans. A master curve was obtained with a critical concentration, C*, at C*[eta] = 3.3. The slope of the curve in the concentrated regime is higher than the values in the range of 3.9-6.6, obtained for the generalized behaviour of several random coil polysaccharides. Dynamic experiments showed that, at the concentrations studied, the behaviour of the galactomannans was typical of systems with predominant entanglement networks in the region between the terminal and plateau zones of frequency response. The correlation between dynamic and steady shear properties (Cox Merz rule) was satisfactory for the three galactomannans.     

Anti-inflammatory properties of intestinal Bifidobacterium strains isolated from healthy infants

Certain Bifidobacterium strains have been shown to inhibit inflammatory responses in intestinal epithelial cells. However, the precise mechanisms of these effects, including the chemical nature of the active compounds, remain to be elucidated. Here partial characterization of the anti-inflammatory properties of Bifidobacterium strains isolated from feces of healthy infants is reported. It was found that conditioned media (CM) of all strains studied are capable of attenuating tumor necrosis factor-α (TNF-α) and lipopolysaccharide- (LPS) induced inflammatory responses in the HT-29 cell line. In contrast, neither killed bifidobacterial cells, nor cell-free extracts showed such activities. Further investigations resulted in attribution of this activity to heat-stable, non-lipophilic compound(s) resistant to protease and nuclease treatments and of molecular weight less than 3 kDa. The anti-inflammatory effects were dose- and time-dependent and associated with inhibition of IκB phosphorylation and nuclear factor-κ light chain enhancer of activated B cells (NF-κB)-dependent promoter activation. The combined treatments of cells with CMs and either LPS or TNF-α, but not with CMs alone, resulted in upregulation of transforming growth factor-β1, IκBζ, and p21(CIP) mRNAs. Our data suggest certain species-specificities of the anti-inflammatory properties of bifidobacteria. This observation should prompt additional validation studies using larger set of strains and employing the tools of comparative genomics.     

Physical characteristics of calcium induced κ- carrageenan networks

The presence of an optimum counter-ion concentration in calcium-induced κ-carrageenan gels at low polymer concentrations of 5 and 10 g/l is observed. At approximately the stoicheometric molar ratio of 1 calcium per carrageenan sulphate, a gel with high elastic modulus, high optical clarity and fine network structure is observed. On further increase of counter-ion concentration beyond this optimum, elastic modulus decreases significantly associated with sharp increase in the gels turbidity together with a network characterised with coarse and large-pore mesh.

The quite complete characterisation of the various gel networks both mechanically by ways of oscillatory and static rheology and optically by turbidimetry and cryo-SEM shows that the extensive structural charge neutralisation of the polysaccharide by divalent calcium ions is responsible for a marked aggregation of the polymer strands reminiscent of precipitation. At lower counter-ion to polymer ratios, onset of gelation might prevent such phase separation.     

Responsiveness of κ-carrageenan microgels to cationic surfactants and neutral salts

The objective of this study was to examine the responsiveness of chemically cross-linked κ-carrageenan microspheres to different types of neutral salt electrolytes as well as to surfactants of varying chain lengths. In the presence of increasing salt concentration microsphere size changed radically from D[4,3] values of 320 μm to approximately 160 μm. The level of salt concentration needed to bring about this change varied depending on electrolyte type. This common behaviour was attributed to the difference in free cationic counter-ions concentration between the inside and outside of the microsphere and can be explained due to the effect of the Donnan equilibrium. The rheological properties of these microgels in their swollen and collapsed states were also explored with results showing that the collapsed microspheres had a greater impact on the viscosity of the system probably as a result of some aggregation of the collapsed microgels at rest due to surface charge screening at these high salt concentrations. The effect of surfactant on microsphere size showed a dramatic drop in D[4,3] values from 320 μm to approximately 120 μm for BAC, DoTAB, MTAB and CTAB at specific critical concentrations. This critical aggregation concentration was found to increase linearly on a log–log scale with the critical micelle concentration of these surfactants in water, indicating that the alkyl chain length of the surfactants had an effect on the critical aggregation concentration.