AFM studies on gelation mechanism of xanthan gum hydrogels

The effect of annealing on xanthan gum molecules was investigated using atomic force microscopy (AFM). The values of height and width of xanthan gum molecules in AFM images are ca. 1 nm, which strongly indicates that xanthan gum molecules extended on the mica surface are in mono- or double layers. When xanthan gum aqueous solution was annealed, a network structure was observed. In contrast, a network structure was not observed for non-annealed solution. AFM images provide direct information concerning oscillational change of the network structure. It is concluded that xanthan gum molecular chains in aqueous solution aggregate and dissociate in an oscillational manner with increasing annealing time and that a homogeneous network structure was formed by annealing at 40 °C for 24 h.     

Valorisation of chicken feathers for xanthan gum production using Xanthomonas campestris MO-03

Xanthan gum is an important commercial polysaccharide produced by Xanthomonas species. In this study, xanthan production was investigated using a local isolate of Xanthomonas campestris MO-03 in medium containing various concentrations of chicken feather peptone (CFP) as an enhancer substrate. CFP was produced with a chemical process and its chemical composition was determined. The addition of CFP (1–8?g/l) increased the conversion of sugar to xanthan gum in comparison with the control medium, which did not contain additional supplements. The highest xanthan production (24.45?g/l) was found at the 6?g/l CFP containing control medium in 54?h. This value was 1.73 fold higher than that of control medium (14.12?g/l). Moreover, addition of CFP improved the composition of xanthan gum; the pyruvate content of xanthan was 3.86% (w/w), higher than that of the control (2.2%, w/w). The xanthan gum yield was also influenced by the type of organic nitrogen sources. As a conclusion, CFP was found to be a suitable substrate for xanthan gum production.     

Revisiting the conformation of xanthan and the effect of industrially relevant treatments

The structure and conformation of xanthan in aqueous solution following various processing treatments typically encountered in its application were investigated in this study. Treatments such as heating, autoclaving, high pressure homogenisation and irradiation were subjected to the same sample. Parameters such as weight average molecular weight (M(w)), polydispersity index, root mean square radius of gyration, intrinsic viscosity and Huggins constant were used to monitor the effect of these treatments. Additionally, we have quantified the mass recovery of samples examined by gel permeation chromatography and light scattering to properly account for all fractions present in xanthan solutions. Atomic force microscopy (AFM) images together with height measurements confirmed that xanthan conformation is double helical ordered renatured state (pre-heat treated by the manufacturer) in dilute solution conditions and random coil conformation in very dilute solution. The ordered (renatured) conformation is shown to have partially molten double helix, with more flexibility than the perfectly ordered native double helix. Heat treatment for 2h at 85°C reduces the M(w) of xanthan to half its initial value, and mass recovery measurements indicate that it completely overcomes its associative nature. Thermally treated xanthan solution in the dilute region leads to an order-disorder transition, as determined by contour length per unit mass. Similarly, irradiation of xanthan solution results in an order-disorder transition together with the production of single strand low molecular weight molecules. Autoclaving and high pressure homogenisation treatments cause degradation of xanthan. The results from treated xanthan solutions following high pressure homogenisation and irradiation confirm that xanthan does not reassociate. A revised summary of xanthan conformation in solution together with schematic models following the various treatments are proposed.     

E.s.r. study of the conformational transition of spin-labelled xanthan gum in aqueous solution

The order to disorder transition of xanthan molecules in aqueous solutions has been studied using e.s.r. spectroscopy. Nitroxide spin-label was covalently attached to carboxyl groups on the xanthan side chains. The e.s.r. spectra obtained for aqueous spin-labelled xanthan solutions at varying ionic strengths contained both isotropic and anisotropic components at room temperature. The anisotropic component was attributed to the association of the side chains with the xanthan cellulosic backbone and was found to be present in greater proportions at increasing ionic strength. The spectra gradually changed with rising temperature and the proportion of anisotropic component decreased. This spectral change reflected the disruption of the side chain association with the backbone during the conformational change. Hysteresis effects were observed following sequential heating and cooling cycles suggesting that chain aggregation occurred.     

Yield stress components of waxy corn starch–xanthan mixtures: Effect of xanthan concentration and different starches

Yield stress of 6% (w/w) waxy maize (WXM), cross-linked waxy maize (CLWM), and cold water swelling (CWS) starches in xanthan gum dispersions: 0%, 0.35%, 0.50%, 0.70%, and 1.0% was measured with the vane method at an apparent shear rate of 0.05 s⁻¹. The intrinsic viscosity of the xanthan gum was determined to be: 112.3 dL/g in distilled water at 25 °C. Values of the static (σ_0s) and dynamic (σ_0d) yield stress of each dispersion were measured before and after breaking down its structure under continuous shear, respectively. The WXM and CWS starches exhibited synergistic behavior, whereas the CLWM starch showed antagonistic effect with xanthan gum. The difference (σ_0s − σ_0d) was the stress required to break the inter-particle bonding (σ_b). The contributions of the viscous (σ_v) and network (σ_n) components were estimated from an energy balance model. In general, values of σ_b of the starch–xanthan gum dispersions decreased and those of σ_n increased with increase in xanthan gum concentration.     

微生物胞外多糖研究进展

微生物胞外多糖主要是指微生物产生的一些水溶性胶,近几年来由于糖化学的迅速发展,微生物胞外多糖理论和应用的研究逐渐受到了人们的关注。对黄原胶、结冷胶多糖的结构与性能、研究现状和应用状况进行了综述。     

The influence of thermal treatment and operational conditions on xanthan produced by X. arboricola pv pruni strain 106

The influence of thermal treatment and operational conditions (pH and stirrer speed) used in the process of xanthan production by Xanthomonas arboricola pv pruni strain 106 were evaluated through yield of xanthan, aqueous solution and fermentation broth viscosity, sodium content, pyruvate and acetyl content and molar mass. Different conditions used during the fermentation affected the xanthan characteristics. Thermal treatment decreased the final yield and pyruvate and acetyl content, and increased the xanthan aqueous solution and fermentation broth viscosities, as well as molar mass. In this study the best combination of yield and viscosity was obtained with the use of pH 7 and 400 rpm during fermentation and post-fermentation thermal treatment. Aggregation of xanthan molecules promoted by heating and detected through an increase of molar mass was apparently affected by the sodium content. As a result, a correlation between molar mass and xanthan solution viscosity could be observed.     

Chemoenzymatic synthesis and hydrogelation of amylose-grafted xanthan gums

This paper reports the chemoenzymatic synthesis of an amylose-grafted xanthan gum. An amine-functionalized maltooligosaccharide was chemically introduced to xanthan gum by condensation with its carboxylates using a condensing agent to produce a maltooligosaccharide-grafted xanthan gum. Then, a phosphorylase-catalyzed enzymatic polymerization of glucose 1-phosphate from the graft chain ends on the xanthan gum derivative was performed, giving an amylose-grafted xanthan gum. Furthermore, the product formed a gel with an ionic liquid, which was converted into a hydrogel with high water content by replacement of the ionic liquid with water. The ionically cross-linked hydrogel was also provided by soaking the primary formed hydrogel in FeCl₃ aqueous solution. The mechanical properties of the resulting hydrogels were evaluated by compressive testing.     

pH-Dependent interaction between sodium caseinate and xanthan gum

Xanthan gum and sodium caseinate are used to improve stability and texture of food. To investigate interactions between them, the effects of pH on structure of sodium caseinate–xanthan gum complex were analyzed. HCl titration showed that the absorbance of the mixture was different from that of sodium caseinate alone throughout the acidification, and that syneresis in the mixture was delayed in acidic pH. Rennet digestion clarified that xanthan gum retarded degradation of κ-casein at pH 2.7. Atomic force microscopy revealed that xanthan gum interaction with sodium caseinate was pH-dependent. Sodium caseinate particles were individually bound with xanthan gum at pH 6.6, and a side-by-side aggregation of sodium caseinate along xanthan gum was observed at pH 4.2. The mixture formed a network composed of rod-like fibers at pH 2.7. These results indicate that hydrophobic and electrostatic interactions play a role in the complex formation at neutral and acidic pH, respectively.     

黄原胶降解的研究进展

综述了黄原胶的理化特性、降解意义及降解方法,重点介绍了生物法降解黄原胶的国内外研究进展,并对降解黄原胶的研究方向提出了寻求更多降解途径、开发寡糖产品等建议.     

培养基的组成对黄原胶发酵产量与质量的影响研究

本文着重研究了培养基各组分对胶产量与质量的影响。结果表明:氮源是极显著因素,碳源是显著因素,无机盐与柠檬酸对质量与产量的影响各有主次;以蔗糖代替葡萄糖可使产量与质量有较大提高。此外还分析了培养基中CaCO_3的加入、消泡剂的选择、H_2O_2水的添加等各因素对产胶的影响。     

Thermal stability and chain conformational studies of xanthan at different ionic strengths

The aim of the present study was to determine the influence of the ionic strength on the thermal stability of xanthan, i.e. xanthan resistance to chain breaking at high temperatures. Xanthan solutions of various ionic strengths were kept at 80, 90 and 95°C for periods up to 95 h. The thermal stability was determined by measuring the intrinsic viscosity after the heating periods. The experiments showed a critical ionic strength for the thermal stability of xanthan between 10 and 100 mm NaCl or KCl in this temperature range. Below the critical ionic strength the intrinsic viscosity was rapidly reduced, whereas above the critical ionic strength the intrinsic viscosity was virtually unaffected by heating.We then looked for a possible correlation between thermal stability and secondary structure of xanthan. The transition ionic strength (I_m) of xanthan solutions, i.e. where xanthan is midway between an ordered and a disordered structure, was determined by NMR at constant temperatures. I_m was found to be in the range of 24 mm at 80°C to 60 mm NaCl at 95°C, thus lying in the range of the critical ionic strength of the thermal stability. This suggests a close relationship between thermal stability and secondary structure of xanthan, indicated by the enhanced thermal stability in the ordered state. We believe this enhanced thermostability arises from a double-stranded conformation in the ordered state, as in DNA. The presence of double-stranded xanthan is also indicated by electron micrographs taken at both high and low ionic strengths.The transition temperature (T_m) of xanthan was determined by NMR and optical rotation measurements. At the ionic strength of 7·5 mm the two methods resulted in T_m values of 67 and 52°C respectively. This difference in T_m can possibly be due to the fact that the observed NMR and optical rotation (OR) effects are caused by different molecular phenomena.     

Formulation variables affecting drug release from xanthan gum matrices at laboratory scale and pilot scale

The purpose of this research was to study processing variables at the laboratory and pilot scales that can affect hydration rates of xanthan gum matrices containing diclofenac sodium and the rate of drug release. Tablets from the laboratory scale and pilot scale proceedings were made by wet granulation. Swelling indices of xanthan gum formulations prepared with different amounts of water were measured in water under a magnifying lens. Granules were thermally treated in an oven at 60°C, 70°C, and 80°C to studythe effects of elevated temperatures on drug release from xanthan gum matrices. Granules from the pilot scale formulations were bulkier compared to their laboratory scale counterparts, resulting in more porous, softer tablets. Drug release was linear from xanthan gum matrices prepared at the laboratory scale and pilot scales, however, release was faster from the pilot scales. Thermal treatment of the granules did not affect the swelling index and rate of drug release from tablets in both the pilot and laboratory scale proceedings. On the other hand, the release from both proceedings was affected by the amount of water used for granulation and the speed of the impeller during granulation. The data suggest that processing variables that affect the degree of wetness during granulation, such as increase in impeller speed and increase in amount of water used for granulation, also may affect the swelling index of xanthan gum matrices and therefore the rate of drug release.     

“Melt-in-the-mouth” gels from mixtures of xanthan and konjac glucomannan under acidic conditions: A rheological and calorimetric study of the mechanism of synergistic gelation

The effect of acidification on a typical commercial xanthan and on pyruvate-free xanthan (PFX), alone and in gelling mixtures with konjac glucomannan (KGM), has been studied by differential scanning calorimetry (DSC) and small-deformation oscillatory measurements of storage modulus (G′) and loss modulus (G″). For both xanthan samples, progressive reduction in pH caused a progressive increase in temperature of the disorder–order transition in DSC, and a progressive reduction in gelation temperature with KGM. This inverse correlation is interpreted as showing that synergistic gelation involves disruption of the xanthan 5-fold helix, probably by attachment of KGM to the cellulosic backbone of the xanthan molecule (as proposed previously by a research group in the Institute of Food Research, Norwich, UK). Higher transition temperature accompanied by lower gelation temperature for PFX in comparison with commercial xanthan at neutral pH is explained in the same way. However, an additional postulate from the Norwich group, that attachment of KGM (or galactomannans) can occur only when the xanthan molecule is disordered, is inconsistent with the observation that gelation of acidified mixtures of KGM with PFX can occur at temperatures more than 60 °C below completion of conformational ordering of the PFX component (as characterised by DSC). Increase in G′ on cooling for mixtures of commercial xanthan with KGM at pH values of 4.5 and 4.25 occurred in two discrete steps, the first following the temperature-course observed for the same mixtures at neutral pH and the second occurring over the lower temperatures observed for mixtures of KGM with PFX at the same values of pH. These two “waves” of gel formation are attributed to interaction of KGM with, respectively, xanthan sequences that had retained a high content of pyruvate substituents, and sequences depleted in pyruvate by acid hydrolysis. At pH values of 4.0 and lower, gelation of mixtures of KGM with commercial xanthan followed essentially the same temperature-course as for mixtures with PFX, indicating extensive loss of pyruvate under these more strongly acidic conditions. Mixtures prepared at pH values in the range 4.0–3.5 gave comparable moduli at room temperature (20 °C) to those obtained at neutral pH, but showed substantial softening on heating to body temperature, suggesting possible applications in replacement of gelatin in products where “melt-in-the-mouth” characteristics are important for acceptability to the consumer.     

改性黄原胶酯化条件的优化及结构的表征

为了提高黄原胶的速溶性和粘度,将黄原胶进行改性处理。将黄原胶与马来酸酐进行酯化反应,探讨了黄原胶与马来酸酐摩尔比、反应时间和反应温度等因素的影响,以取代度为指标,利用响应面方法确定,该酯化反应的最优条件为:黄原胶与马来酸酐摩尔比1∶11.5、反应时间24.4 h、反应温度66℃。对改性黄原胶进行红外光谱、光散射和X-射线衍射等结构表征,表明酯化改性成功,且进一步解释了速溶性和粘度提高的原因。改性黄原胶细胞毒性实验,显示无毒性。结果表明,改性黄原胶的速溶性和粘度有很大提高,0.2%改性黄原胶的速溶性和粘度较对照提高了近3倍,在食品、药品等领域具有潜在的应用价值。     

黄原胶(Xanthan Gum)的特性、生产及应用

黄原胶是野油菜黄单孢菌分泌于胞外的中性水溶性多糖。由于其独特的流变性质而有着极其广泛的工业应用。介绍了黄原胶的生产、特性、降解以及应用,并对其应用潜力作了预测。     

Application of conductivity studies and polyelectrolyte theory to the conformation and order-disorder transition of xanthan polysaccharide

The conductivity of xanthan (extracellular polysaccharide from Xanthomonas campestris) in the potassium salt form has been studied over the temperature range 5–80°C spanning the order-disorder conformational transition. In salt-free solution data analysis using Manning's polyelectrolyte-conductivity theory gives a charge spacing, b, of 0.58±0.04 nm for the low temperature ordered form, consistent with a single rather than a double helix (b=0.58 and 0.29 nm respectively). In solutions with 0.01 M added KBr the increase in counterion condensation on conformational ordering is found from conductivity studies to be — ^–1= 0.20 ± 0.02, in good agreement with the value 0.20±0.02 using polyelectrolyte-equilibrium theory for the variation of transition-midpoint temperature with added salt determined from opticalrotation data.     

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.     

Viscoelastic properties of dispersed chitosan/xanthan hydrogels

In this work a gel was formed by complexation of two natural polyelectrolytes, chitosan and xanthan. Changes in the hydrogels rheological properties have been studied in terms of hydrogel concentration (7–10% w/w), chemical media used for the hydrogel dispersion, and ‘test lag time’; i.e., the time between hydrogel dispersion in the chemical media and the start of the rheological test (up to 390 min). The viscoelastic properties of this polysaccharide system were characterized by oscillatory shear measurements under small-deformation conditions and the results show that chitosan/xanthan hydrogels behave like weak gels. The shear modulus increased almost linearly with frequency in the range studied (0.1–65 s⁻¹). The effects of hydrogel concentration and dispersion medium have been related to electrostatic equilibrium and by the presence of counter-ions modifying the internal structure of the hydrogel.     

Nutritional study of Xanthomonas campestris in xanthan gum production by factorial design of experiments

A nutritional study of Xanthomonas campestris in the production of xanthan gum was carried out by factorial design and analysis of experiments. The concentrations of nutrients such as nitrogen, phosphorus, magnesium, and sulfur were studied by means of a factorial design at two levels, reduced to a half with four central points for error estimation. Three responses were considered, corresponding to biomass, sucrose, and xanthan concentrations, at four different times: 12, 16, 20, and 24 h. The influence of nitrogen, phosphorus, and magnesium on the biomass, and the influence of nitrogen, phosphorus, and sulfur on xanthan production, were significant, although any variable influenced sucrose consumption. An optimized medium was proposed for xanthan production.