The effect of phase viscosity ratio on the rheology of liquid two phase gelatin-locust bean gum systems

The rheological behaviour of liquid two phase gelatin–locust bean gum (LBG) systems, comprising of (a) liquid LBG enriched continuous phase, and (b) flow-deformable gelatin-enriched dispersed particles seems to be determined, at the same phase composition, by phase viscosity ratio (μ). In the μ range from 0.03 to 0.21, viscosity dropped to values noticeably lower (13–40 times) than those of the corresponding LBG solution. Decrease in the viscosity of the mixtures was not observed at μ=0.5–0.6, corresponding that to the maximum energy scatter inside the droplets, in agreement with Mason’s conception of droplet deformation and disruption of liquid Newtonian emulsions.     

The influence of locust bean gum and dextran on the gelation of κ-carrageenan

The interaction of κ-carrageenan with locust bean gum and dextran has been studied by rheology, differential scanning calorimetry (DSC), and electron spin resonance spectroscopy (ESR). Rheological measurements show that the carrageenan gel characteristics are greatly enhanced in the presence of locust bean gum but not in the presence of dextran. Carrageenan/locust bean gum mixtures show two peaks in the dsc cooling curves. The higher temperature peak corresponds to the temperature of gelation and its intensity increases at the expense of the lower temperature peak as the proportion of locust bean gum in the mixture increases. Furthermore, the DSC heating curves show enhanced broadening when locust bean gum is present, indicating increased aggregation. These results are taken as evidence of carrageenan/locust bean gum association. The gelation process has also been followed by ESR using spin-labeled carrageenan. On cooling carrageenan solutions, an immobile component appears in the ESR spectra signifying a loss of segmental mobility consistent with chain stiffening due to the coil → helix conformational transition and helix aggregation. For carrageenan/locust bean gum mixtures, carrageenan ordering occurs at temperatures corresponding to the higher temperature DSC setting peak and the temperature of gelation. Similar studies using spin-labeled locust bean gum show that its mobility remains virtually unaffected during the gelation process. It is evident, therefore, that carrageenan and locust bean gum interact only weakly. It is proposed that at low carrageenan concentrations the gel network consists of carrageenan helices cross-linked by locust bean gum chains. At high carrageenan concentrations the network is enhanced by the additional self-aggregation of the “excess” carrageenan molecules. For carrageenan/dextran mixtures, only one peak is observed in the dsc cooling curves. The onset of gelation shifts to higher temperatures only at very high (20%) dextran concentrations and this is attributed to volume exclusion effects. Furthermore, there is no enhanced broadening of the peaks in the DSC heating curves as for the carrageenan/locust bean gum systems. It is therefore concluded that carrageenan/dextran association does not occur. The difference in behavior between locust bean gum and dextran is attributed to the greater flexibility of the dextran chains. © 1996 John Wiley & Sons, Inc.     

Impact of incorporations of various polysaccharides on rheological and microstructural characteristics of heat-induced quinoa protein isolate gels

This study aimed to investigate the properties of heat-induced gels (85 °C for 30 min) of quinoa protein isolate (QPI) in the presence and absence of various polysaccharides including guar gum (GG), locust bean gum (LBG), and xanthan gum (XG) at pH 7. For this purpose, samples with three gum concentrations (0.05, 0.1, and 0.2 wt%) at a fixed QPI concentration (10 wt%) and a fixed ionic strength (50 mM NaCl) were studied in terms of their gelation behaviour, small and large deformation rheological properties, water holding capabilities, and microstructural characteristics. Rheological measurements revealed that all polysaccharides incorporation could improve gel strength (complex modulus, G*) and breaking stress, accelerate gel formations, and more stiffer gels were obtained at greater polysaccharide concentrations. The XG exhibited the most gel strengthening effect followed by LBG and GG. Incorporation of 0.2 wt% XG led to a 15 folds increase in G* compared to the control. Confocal laser scanning microscopy observation revealed that the polysaccharides also altered gel microstructures, with the gels containing XG showing the most compact gel structures. The findings of this study may provide useful information for the fabrication of novel QPI based food gel products with improved texture.

     

Associative phenomena in galactomannan-deacetylated xanthan systems

The interaction between mesquite seed galactomannan (MSG; D-mannose to D-galactose ratio (M/G) approximately 1.1) and deacetylated xanthan (DX) in 5 mM NaCl leading to synergistic gel formation at 25 degrees C was investigated and compared with the far more studied system made of xanthan and locust bean gum (LBG; M/G approximately 3.5). Rheology and differential scanning calorimetry were used to measure temperatures of gel formation and transition enthalpy as a function of polymer composition, while circular dichroism was used to probe the conformation of DX in the LBG-DX system. MSG and DX associate at 25 degrees C with a well defined stoichiometry of 0.6:1.0 (w/w) at low ionic strength favouring the disordered coil state of DX. When LBG was used in place of MSG in water or 5 mM NaCl, two types of mechanisms of interpolymeric association are envisaged.     

Microscopy of xanthan/galactomannan mixtures

Polarization microscopy has been used to investigate the structure of 50/50 xanthan/galactomannan (guar gum or locust bean gum) mixtures in aqueous solution, the total concentration ranging from 0.5 to 4%. By the use of polarized light microscopy birefringent areas resulting from the formation of cholesteric mesophases in xanthan gum was clearly seen as has previously been reported by several authors. In xanthan/galactomannan mixtures, we also observed birefringent areas. Moreover, these zones in the blend appeared more anisotropic than with xanthan gum alone. This suggests that xanthan molecules organize themselves as liquid crystalline mesophases in definite enriched xanthan areas resulting from a concentration of xanthan inside these birefringent zones. Upon heating, this anisotropy disappears at a temperature well below the helix-coil transition temperature of xanthan molecules. In fact, this loss of order of the mixed system occurs at the same temperature as the melting temperature of the gel, as assessed by the use of rheological measurements. Since the ordered helical structure of the xanthan molecules still exists beyond the melting temperature while anisotropy disappears, this suggests that the xanthan molecules are no longer concentrated in specific areas but more evenly distributed in the medium. Gel melting would, therefore, be the result of the disappearance of these xanthan enriched areas.     

The effect of degradation on κ-carrageenan/locust bean gum/konjac glucomannan gels at acidic pH

The feasibility of textural and rheological modification of gels containing κ-carrageenan (KC) and locust bean gum (LBG) by addition of konjac glucomannan (KGM) was investigated. Special attention was paid to the effect of polysaccharide degradation during heating at acidic pH. The general effect of polysaccharide degradation was to decrease the Young's modulus, while the fracture strain in extension was scarcely affected unless the degradation was very severe.     

Studies on κ-carrageenan/locust bean gum mixtures in the presence of sodium chloride and sodium iodide

The solution properties of κ-carrageenan and κ-carrageenan/locust bean gum mixtures have been studied by small deformation oscillation measurements and differential scanning calorimetry (DSC) in the presence of sodium chloride and sodium iodide. Both salts induced the κ-carrageenan to undergo a coil-helix conformational change as noted by an increase in the storage and loss moduli (G′, G′) and by an exothermic peak in the DSC cooling curves. The enthalpy ΔH_c-h and temperature of the conformational transition T_c-h were higher in Nal compared to NaCl and T_c-h increased with increasing the concentration of both electrolytes. Gelation was not observed for carrageenan or carrageenan/locust bean gum mixtures in the presence of up to 200 mM Nal. Although carrageenan alone did not gel in the presence of 100 mM NaCl, a weak gel was obtained for a mixture containing 0.9%/0.1% carrageenan/locust bean gum. Furthermore, the mixture showed hysteresis in both the rheological and DSC cooling and heating curves. A strong gel was produced for carrageenan alone in the presence of 200 mM NaCl and the gel strength increased on adding a small proportion of locust bean gum (0.9%/0.1%). © 1997 John Wiley & Sons, Inc. Biopoly 41: 657–671, 1997     

Phase equilibria and mechanical properties of gel-like water-gelatin-locust bean gum systems

The establishment of phase equilibrium in aqueous gelatin-locust bean gum (LBG) systems in the process of cooling from 313 to 291 K in specific conditions, passes ahead of the gelation process(.) This allows the suggestion that macrostructure and mechanical properties of the system can be predicted on the basis of knowledge of its phase diagram, obtained for the liquid gelatin-LBG systems comprising gelatin molecular aggregates. Textural and rheological analysis of gel-like gelatin-LBG systems demonstrate the effect of two factors determining their mechanical properties and acting opposite each other when the concentration of LBG in the system increases: concentration of gelatin by LBG in the process of phase separation, and decrease in the density of the gel network.     

A celluloytic complex from <Emphasis Type="Italic">Clostridium cellulovorans</Emphasis> consisting of mannanase B and endoglucanase E has synergistic effects on galactomannan degradation

In our previous study using a fluorescently labeled cohesin biomarker, we detected and identified a putative cellulosomal mannanase belonging to the glycosyl hydrolase family 26 from Clostridium cellulovorans in xylan-containing cultures. In this study, a mannanase gene, manB from C. cellulovorans, was expressed in Escherichia coli. The optimal pH of a purified enzyme was around pH 7.0 and the optimal temperature was 40°C. The purified mannanase B (ManB) showed high hydrolytic activity toward galactomannan. An assembly of ManB with mini-CbpA, which contains a carbohydrate-binding module that provides proximity to insoluble substrates, increased the activity toward galactomannan [locust bean gum (LBG) and guar gum] 1.7- and 2.0-fold over those without mini-CbpA. We tested the synergistic effects on galactomannan (LBG and guar gum) degradation using cellulosomal mannanase ManB with cellulosomal endoglucanase E, which was predicted to have mannanase activity in C. cellulovorans as a cellulolytic complex. When assembled with the mini-CbpA, the mixture of endoglucanase E (EngE) and ManB at a molar ratio of 1:2 showed the highest synergistic effect (2.4-fold) on LBG. The mixture at a ratio of 1:3 showed the highest synergistic effect (2.8-fold) on guar gum. These synergistic actions indicated that ManB assembled with mini-CbpA hydrolyzed insoluble galactomannan, which in turn promoted soluble galactomannan degradation by EngE.     

Improved Hypolipidemic Effects of Xanthan Gum-Galactomannan Mixtures in Rats

This study describes the effects of mixtures of xanthan gum and galactomannan, guar gum, or locust bean gum, on the lipids in plasma and liver in non-diabetic and diabetic rats. Non-diabetic rats were fed cholesterol-free diets with 3% guar gum, locust bean gum, or xanthan gum (3G, 3L, and 3X), or a mixture of xanthan gum and guar gum or locust bean gum (1:2, w/w) (2G1X, 2L1X) for 2 weeks. Rats fed diets not containing these polysaccharides were used as controls. The total cholesterol in plasma and the triacylglycerol in liver were significantly lowered in rats fed the 2G1X diet. The 3G, 3X, 3L, and 2L1X diets showed no significant effect on the total cholesterol and triacylglycerol in plasma and liver. In the streptozotocin-induced (STZ) diabetic rats, the total cholesterol in plasma was lowered in rats fed the 3G, 3X or 2G1X diet for 4 weeks, and the 2G1X diet was more effective than the 3G and 3X diets. The triacylglycerol in plasma in STZ diabetic rats was also significantly lowered by the 2G1X diet. These results showed that a mixture of xanthan gum and guar gum has an improved hypolipidemic effect on non-diabetic and STZ diabetic rats. The effects of the 2G1X diet on the diabetic symptoms in STZ diabetic rats, suppression of food and water intakes, decrease in glucose in urine, and lowering of plasma glucose, were also observed.     

Characterization of the Bacillus subtilis WL-3 mannanase from a recombinant Escherichia coli

A mannanase was purified from a cell-free extract of the recombinant Escherichia coli carrying a Bacillus subtilis WL-3 mannanase gene. The molecular mass of the purified mannanase was 38 kDa as estimated by SDS-PAGE. Optimal conditions for the purified enzyme occurred at pH 6.0 and 60 degrees C. The specific activity of the purified mannanase was 5,900 U/mg on locust bean gum (LBG) galactomannan at pH 6.0 and 50 degrees C. The activity of the enzyme was slightly inhibited by Mg(2+), Ca(2+), EDTA and SDS, and noticeably enhanced by Fe(2+). When the enzyme was incubated at 4 degrees C for one day in the presence of 3 mM Fe(2+), no residual activity of the mannanase was observed. The enzyme showed higher activity on LBG and konjac glucomannan than on guar gum galactomannan. Furthermore, it could hydrolyze xylans such as arabinoxylan, birchwood xylan and oat spelt xylan, while it did not exhibit any activities towards carboxymethylcellulose and para-nitrophenyl-beta-mannopyranoside. The predominant products resulting from the mannanase hydrolysis were mannose, mannobiose and mannotriose for LBG or mannooligosaccharides including mannotriose, mannotetraose, mannopentaose and mannohexaose. The enzyme could hydrolyze mannooligosaccharides larger than mannobiose.     

Improved hypolipidemic effects of xanthan gum-galactomannan mixtures in rats

This study describes the effects of mixtures of xanthan gum and galactomannan, guar gum, or locust bean gum, on the lipids in plasma and liver in non-diabetic and diabetic rats. Non-diabetic rats were fed cholesterol-free diets with 3% guar gum, locust bean gum, or xanthan gum (3G, 3L, and 3X), or a mixture of xanthan gum and guar gum or locust bean gum (1:2, w/w) (2G1X, 2L1X) for 2 weeks. Rats fed diets not containing these polysaccharides were used as controls. The total cholesterol in plasma and the triacylglycerol in liver were significantly lowered in rats fed the 2G1X diet. The 3G, 3X, 3L, and 2L1X diets showed no significant effect on the total cholesterol and triacylglycerol in plasma and liver. In the streptozotocin-induced (STZ) diabetic rats, the total cholesterol in plasma was lowered in rats fed the 3G, 3X or 2G1X diet for 4 weeks, and the 2G1X diet was more effective than the 3G and 3X diets. The triacylglycerol in plasma in STZ diabetic rats was also significantly lowered by the 2G1X diet. These results showed that a mixture of xanthan gum and guar gum has an improved hypolipidemic effect on non-diabetic and STZ diabetic rats. The effects of the 2G1X diet on the diabetic symptoms in STZ diabetic rats, suppression of food and water intakes, decrease in glucose in urine, and lowering of plasma glucose, were also observed.     

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.     

Conditions of formation, purification, and characterization of an alpha-galactosidase of Trichoderma reesei RUT C-30.

Trichoderma reesei RUT C-30 formed an extracellular alpha-galactosidase when it was grown in a batch culture containing lactose or locust bean gum as a carbon source. Short-chain alpha-galactosides (melibiose, raffinose, stachyose), as well as the monosaccharides galactose, dulcitol, arabinose, and arabitol, also induced alpha-galactosidase activity both when they were used as carbon sources (at a concentration of 1%) in batch cultures and in resting mycelia (at concentrations in the millimolar range). The addition of 50 mM glucose did not affect the induction of alpha-galactosidase formation by galactose. alpha-Galactosidase from T. reesei RUT C-30 was purified to homogeneity from culture fluids of galactose-induced mycelia. The active enzyme was a 50 +/- 3-kDa, nonglycosylated monomer which had an isoelectric point of 5.2. It was active against several alpha-galactosides (p-nitrophenyl-alpha-D-galactoside, melibiose, raffinose, and stachyose) and galactomannan (locust bean gum) and was inhibited by the product galactose. It released galactose from locust bean gum and exhibited synergism with T. reesei beta-mannanase. Its activity was optimal at pH 4, and it displayed broad pH stability (pH 4 to 8). Its temperature stability was moderate (60 min at 50 degrees C resulted in recovery of 70% of activity), and its highest level of activity occurred at 60 degrees C. Its action on galactomannan was increased by the presence of beta-mannanase.     

Gelling interactions of phycocolloids extracted from red algae with a galactomannan from locust bean and a glucomannan from konjac tuber

The synergistic interaction between three red algae extracts and the galactomannan from locust bean (Ceratonia siliqua L.) and the glucomannan from the konjac tuber (Amorphophallus konjac C. Koch (syn.A. rivieri Durien var. konjac (C. Kock) Engler)) has been characterized in terms of gel properties. The extract obtained fromEucheuma alvarezii Doty (E. cottonii of commerce) was highly synergistic with bothkonjac flour and locust bean gum.Furcellaria fastigiata (Huds.) Lamour andEucheuma gelatinae (Esper) extracts were only slightly synergistic with locust bean gum, but were found to be highly synergistic with konjac flour.     

Thermal, Mechanical, and Molecular Relaxation Properties of Frozen Sucrose and Fructose Solutions Containing Hydrocolloids

Model frozen systems formulated with 20wt% sucrose or fructose and with the addition of 0.3 or 0.5wt% of xanthan gum (XG), guar gum (GG), locust bean gum (LBG), or a 50wt% mixture of XG and LBG were studied by differential scanning calorimetry, dynamic mechanical analysis, and ¹H-pulsed nuclear magnetic resonance. Melting onset of either the sucrose or fructose model systems was not affected by the addition of hydrocolloids. As expected, ice content was lower in fructose than in sucrose systems. Addition of hydrocolloids had no effect on ice content, except when the blend of XG and LBG was added to the fructose system, where ice content was significantly diminished. Hydrocolloids decreased molecular mobility for both frozen sucrose or fructose solutions, especially for the addition of XG/LBG blend. Relaxation times and storage modulus of the frozen systems with added hydrocolloids were significantly lower than the control frozen sugar solutions.     

Steady-state and pulsed NMR studies of gelation in aqueous agarose

Steady-state and pulsed NMR techniques have been used to investigate molecular motion in sols and gels of agarose. In passing through the sol–gel transition, the molecular mobility of water molecules is reduced only by a small amount, whereas motion of the polymer chains is greatly attenuated. The results are discused in terms of the network theory of gelation, with references to the role of water in the process and the nature of the “junction zones” between polymer chains. T₂ and line-width measurements are dominated by exchange broadening. The effects of exchange rate and differences in relaxation time between the exchanging sites are discussed. The temperature hysteresis behavior of agarose gels has been investigated and the effects of “ageing” correlated with changes in nuclear relaxation times. The synergistic increase in gel strength obtained on adding locust bean gum (LBG) to agarose has been investigated. The results indicate that LBG does not form double-helix junctions and may decrease rates of gelation by steric effects. At high agarose concentration, the LBG remains mainly in solution in interstitial water, but at low agarose concentration, it is suggested that the LBG can link gel aggregates together into a self-supporting structure, producing a synergistic increase in gel strength. Comparisons have been made between the nature of the agarose–LBG interaction and agarose–cellulose interactions in biological systems.     

Influence of galactomannans with different molecular weights on the gelation of whey proteins at neutral pH

The effect of locust bean gum, a galactomannan, with different molecular weights on the microstructure and viscoelastic properties of heat-induced whey protein gels has been studied using confocal laser scanning microscopy and small-deformation rheology. The results obtained clearly showed that differences in the molecular weight of the polysaccharide have a significant influence on the gel microstructure. Homogeneous mixtures and phase-separated systems, with dispersed droplet and bicontinuous morphologies, were observed by changing the polysaccharide/protein ratio and/or the molecular weight. At 11% whey protein, below the gelation threshold of the protein alone, the presence of the nongelling polysaccharide induces gelation to occur. At higher protein concentration, the main effect of the polysaccharide was a re-enforcement of the gel. However, at the higher molecular weight and concentration of the nongelling polymer, the protein network starts to lose elastic perfection, probably due to the formation of bicontinuous structures with lower connectivity.     

Role of galactomannan composition on the binary gel formation with xanthan

The influence of the galactomannan characteristic ratios (M/G) on the temperature of gelation (Tg) and the gel strength of mixtures of galactomannan with xanthan is reported. Two galactomannans were investigated: one highly substituted from the seeds of Mimosa scabrella (M/G = 11), and the other, less substituted, from the endosperm of Schizolobium parahybae, with (M/G = 30) [Ganter JLMS, Zawadzki-Baggio SF, Leitner SC, Sierakowski MR, Reicher F. J Carbohydr Chem 1993;12:753]. The xanthan:galactomannan systems (4:2 g l(-1), in 5 mM NaCl) showed a temperature of gel formation (Tg) of 24 degrees C for that of S. parahybae [Bresolin TMB, Milas M, Rinaudo M and Ganter JLMS. Int J Biol Macromol 1998;23:263] and 20 degrees C for the galactomannan of M. scabrella, determined by viscoelastic measurements and microcalorimetry. A Tg of 40-50 degrees C was found by Shatwell et al. [Shatwell KP, Sutherland IW, Ross-Murphy SB, Dea ICM. Carbohydr Polym 1991;14:29] for locust bean gum-LBG (M/G = 43). Lundin and Hermansson [Lundin L, Hermansson AM. Carbohydr Polym 1995;26:129] reported a difference of 13 degrees C for Tg of two LBG samples with M/G = 3 (40 degrees C) and 5 (53 degrees C), in mixtures with xanthan. It appears that the more substituted galactomannans have lower temperatures of gelation in the presence of xanthan. The mechanism of gelation depends also on the M/G ratio. For the lower values it involves only disordered xanthan chains in contrast to M/G ratios higher than 3. In addition, the presence of the galactomannan from M. scabrella increased slightly the temperature of the conformational change (Tm) of xanthan probably due to the ionic strength contribution of proteins (3.9%) present in the galactomannan. On the other hand, the galactomannans from S. parahybae, with 1.5% of proteins and M. scabrella, with 2.4% of protein, did not show this effect, the Tm of xanthan alone or in a mixture being practically unchanged.     

Synthesis and Fungicidal Activity of Diaryl 1,1 -Dichloroethyl-phosphonates

Non-Newtonian behavior and dynamic viscoelasticity of a series of aqueous mixed solutions of xanthan and locust bean gum were measured using a rheogoniometer, and the rheological properties were analysed. A gelation occurred in the mixture at the concentration of 0.2% total gums at room temperature. The flow curves of the mixture solutions showed a yield value and approximated to plastic behavior at 50°C. The maximum dynamic modulus was obtained when the mixing ratio of xanthan to locust bean gum was 1:2, while comparable high moduli were also obtained in the mixing ratio of 1: 3 or 1:4. A mixture of deacetylated xanthan and locust bean gum showed the highest dynamic modulus, about two times that of the mixture of native or Na-form xanthan. The dynamic modulus of the mixtures decreased rapidly with increasing temperature. In contrast, the dynamic viscosity was scarcely changed during increasing temperature in the mixing ratio of 2: 1. The dynamic modulus was decreased by addition of urea (4.0 M), NaCl (0.1%) and MgCl₂. We concluded that the intermolecular interaction between xanthan and locust bean gum might occur between the side chains of the former and backbone of the latter, as in a lock-and-key effect.