浅谈黄原胶及其在农药制剂加工中的应用

黄原胶是极具发展潜力的生物多糖,独特的分子结构使其具有良好的增稠、乳化和稳定作用,已被广泛应用于日用化工、石油开采、纺织印染、食品、医药、涂料、农药等众多工业领域,拥有广阔的市场前景。本文对黄原胶的结构、特性、生产工艺以及主要应用领域等进行了简单综述,总结了黄原胶在农药制剂加工中的应用现状,指出黄原胶优越的流变特性对悬浮剂、水乳剂、悬乳剂等农药制剂悬浮稳定性的提高具有重大意义,最后展望了黄原胶未来的发展前景。     

钙离子诱导的海藻酸钠/黄原胶凝胶化临界行为研究

研究了海藻酸钠/黄原胶混合体系的相行为及其对海藻酸钠-钙离子凝胶化临界行为的影响.当海藻酸钠浓度为0.5 wt%时,随着黄原胶的添加,混合体系出现相容、相分离及液晶3种不同的相行为.与纯黄原胶溶液相比,海藻酸钠/黄原胶混合溶液在更低的黄原胶浓度下开始形成液晶,这是由于混合体系中相分离的发生导致了黄原胶有效浓度升高.利用葡萄糖酸内酯(GDL)在线酸化Ca-EDTA,释放钙离子,研究了不同钙离子引入量时(f=[Ca2+]/[COO-])混合体系的黏弹性.Winter-Chambon分析发现临界凝胶点(f gel)随黄原胶浓度的增加而降低.当相分离发生时,临界凝胶点急剧降低,当液晶结构形成后,临界凝胶点呈现上升趋势.通过对比Winter-Chambon方法和临界凝胶点模量松弛法所测得的松弛临界指数(nw和nr),发现黄原胶的添加使海藻酸钠临界凝胶失去结构自相似性.相分离的发生导致临界凝胶结构排列更加致密,而液晶的出现使临界凝胶结构排列相对疏松.     

生物高分子黄原胶的性能、应用与功能化

讨论了黄原胶生物大分子的结构与性能关系，从有关黄原胶的性能、开发应用以及在抗菌素药物负载与控择、分散稳定与防腐作用，及其与有机硅化合物配伍制备消泡表面活性材料等，进行功能化改性方面，综述了近20年来国内外研究状况，并探讨了开展生物高分子黄原胶应用与开发研究的思路。     

黄原胶分子形貌的电镜研究

本文用扫描电镜研究了温度、超声波处理及浓度对黄原胶分子形貌的影响,并用透射电镜研究了黄原胶单分子的形貌及分子量。认为黄原胶分子在一般情况下具有较规则的二、三、四级结构,论述了其初、高级结构之间的关系,得出了黄原胶分子是由40余个亚基组成的右手双螺旋这一结论,计算出其分子量为6×10~6至25×10~6。     

黄原胶物化性质研究进展

黄原胶(Xanthan Gum)是一种阴性菌(Xanthomonas Campestris)胞外异聚多糖,属于生物高分子。它具有增粘性、悬浮性、耐酸碱、抗盐钙等许多优异性能,广泛应用于探矿、钻井、食品等几十个工业部门。因此,自1961年黄原胶问世以来,便引起人们的关注。它的化学结构已被测定,对它的性能研究逐渐展开。由于它是聚电解质、粘度又高、分子量又大,因此,对它的溶液性质的研究十分困难。然而,正是对它的溶液性质研究较多。本文主要综述黄原胶溶液行为研究的进展。     

黄原胶在水溶液中构象的研究

本文用GPC法研究了水溶液中黄原胶的构象及构象的变化。指出在低离子强度下,黄原胶主要是以多分子缔合状态而存在,少量以单分子状态而存在。缔合状态下的黄原胶分子呈分段的双股螺旋构象。     

黄原胶分子量的研究

Dintzis曾用经典光散射法测得经90℃、4 mool/L尿素处理3h的黄原胶分子量为2×10~6,不加热的分子量为13×10~6和50×10~6,但未知确切数据.Rinaudo和Milas以相同的方法在l×10~(-3)～l mool/L的氯化钠溶液中测得黄原胶的分子量为2×10~6.Southwick用动态光散射法在4 mol/L尿素中测出其分子量为2.16×10~6.G Holzwarth用透射电镜测出分子量为4×10~6～20×10~6之后,他又通过测定沉降系数和特性粘数,由MFS等式算出黄原胶原始分子量为15×10~6.可见,虽然实验方法和样品不同,但仍可确定其分子量在2×10~650×10~6之间。     

黄原胶的数均分子量研究

用改良型Bruss膜渗透计测定了黄原胶超声波碎片的6个分级试样的数均分子量M_n及第二维利系数A_2,黄原胶在0.1mol/L NaCl水溶液中的M_n值大约是镉乙二胺饱和水溶液(cadoxen)中M_n的2倍,表明它在0.1 mol/L NaCl水溶液中为双螺旋链同时共存少量单链分子的双或多股缔合体,而在cadoxen中则变为单无规线团,在cadoxen/水混合液中当cadoxen重量分数W_(cad)为0.6左右时,黄原胶双螺旋链及缔合分子解开成单股链的过程基本完成。     

黄原胶的分子量

黄原胶是一种具有超高分子量的细菌胞外多糖,只溶于水中,作为增粘剂而得到广泛的应用。由于其侧链上含有可电离的三糖基团,表现出很强的聚电解质行为,因而给分子量及分子量分布的测定带来许多困难。 许多学者对黄原胶的分子量进行了研究。但由于测试方法和实验条件以及样品的差异,     

魔芋精粉与黄原胶协同相互作用及其凝胶化的研究

魔芋精粉与黄原胶均为非凝胶多糖,但二者共混可以得到凝胶．当魔芋精粉与黄原胶的共混比例为３０／７０、多糖总浓度为１％,可达到协同相互作用的最大值．同时也讨论了制备温度（Ｔｐ）和体系盐离子浓度对凝胶化的影响,并从其ＦＴＩＲ谱图上分析了这两种多糖分子间相互作用的机理．     

Comparative study of thermal degradation behavior of graft copolymers of polysaccharides and vinyl monomers

The thermal degradation of graft copolymers of both polysaccharides (guar gum and xanthan gum) showed gradual decrease in mass loss. Pure guar gum degraded about 95% but pure xanthan gum degraded about 76% up to 1173.15 K, while graft copolymers of guar gum and xanthan gum degraded only 65–76% up to 1173.15 K. Acrylic acid grafted guar gum and xanthan gum showing two-step degradation with formation of anhydride and ketonic linkage during heating, same pattern of degradation was found for xanthan gum-g-methacrylic acid. Guar gum-g-acrylamide degraded in single step and xanthan gum-g-acrylamide started to degrade above 448.15 K and it is a two-stage process and imparts thermal stability due to the formation of imide linkage with evolution NH₃. Guar gum-g-methacrylamide degraded in three steps due to the loss of NH₃ and CO₂ successively. 4-vinyl pyridine grafted both polysaccharides show single step degradation due to loss of pyridine pendent. N-vinyl formamide grafted guar gum and xanthan gum started to degrade at about 427.15 K, showed two-stage degradation process with the evolution of CO and NH₃ molecules while guar gum-g-(N-vinyl-2-pyrrolidone) degraded into two steps by the loss of pyrrolidone nucleus. Gum-g-2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS) showed two-step degradation processes in two successive degradation steps, while xanthan gum-g-AMPS has started degradation at about 427.15 K and completed in five degradation steps. Overall, it was found that the grafted polysaccharides are thermally more stable than pure polysaccharides.     

The displacement efficiency and rheology of welan gum for enhanced heavy oil recovery

The displacement efficiency of welan gum on enhanced heavy oil recovery has been investigated by comparing that of xanthan gum which is commonly used for polymer flooding, and it is found that the displacement efficiency of biopolymer welan gum is higher (>7.0 % at the normal permeability) than that of xanthan gum. In‐depth rheological investigations show that both storage modulus and loss modulus of welan gum solution are higher than those of xanthan gum solutions at the same concentration, temperature and salinity. The higher displacement efficiency for enhanced heavy oil recovery by welan gum is mainly caused by its stronger ability to form aggregates. Although the molecular weight of welan gum is lower than that of xanthan gum, the aggregates of welan gum molecules help to improve the sweep efficiency. It is proposed that welan gum improves oil recovery by drawing and dragging on the residual oils which is derived from the interlinked network structures formed by the adjacent double helices in the arrangement of the zipper model. The intermolecular structures formed by zipper model are stable in high temperature and high salinity condition. Copyright © 2014 John Wiley & Sons, Ltd.     

RHEOLOGICAL BEHAVIOR OF ERWINIA GUM IN AQUEOUS SOLUTION*

Erwinia (E) gum, an extracellular polysaccharide, is composed of fucose, galatose, glucose andglucuronic acid. Its viscosity behavior was investigated by a low-shear-rate multiball viscometer and arotational viscometer. Its weight-average molecular weight M_w and intrinsic viscosity [η] in 0.2 mol/L NaClaqueous solution were measured by light scattering method at 35℃and viscometry at 25℃and found to be1.06×10~6 g/mol and 1050 mL/g, respectively, and its aggregates in aqueous solution were proved by gelpermeation chromatography (GPC). These results indicated that E gum in water has exceedingly highviscosity and exhibits Binham fluid behavior, owing to its aggregation. The viscosity of E gum decreasedwith increasing temperature, and the turning point appeared at 38℃for dilute solution and 80℃forconcentrated solution suggesting that the aggregates of E gum in water started to disaggregate under thesetemperatures. In addition, the aggregates can be disrupted by adding either acid or base. The experimentalresults indicated that the E gum is a good thickening agent, and its fluid behavior is similar to xanthan.     

A Study of the Effects of Aeration and Agitation on the Properties and Production of Xanthan Gum from Crude Glycerin Derived from Biodiesel Using the Response Surface Methodology

The effects of aeration and agitation on the properties and production of xanthan gum from crude glycerin biodiesel (CGB) by Xanthomonas campestris mangiferaeindicae 2103 were investigated and optimized using a response surface methodology. The xanthan gum was produced from CGB in a bioreactor at 28 °C for 120 h. Optimization procedures indicated that 0.97 vvm at 497.76 rpm resulted in a xanthan gum production of 5.59 g L^?1 and 1.05 vvm at 484.75 rpm maximized the biomass to 3.26 g L^?1. Moreover, the combination of 1.05 vvm at 499.40 rpm maximized the viscosity of xanthan at 0.5 % (m/v), 25 °C, and 25 s^?1 (255.40 mPa s). The other responses did not generate predictive models. Low agitation contributed to the increase of xanthan gum production, biomass, viscosity, molecular mass, and the pyruvic acid concentration. Increases in the agitation contributed to the formation of xanthan gum with high mannose concentration. Decreases in the aeration contributed to the xanthan gum production and the formation of biopolymer with high mannose and glucose concentrations. Increases in aeration contributed to increased biomass, viscosity, and formation of xanthan gum with greater resistance to thermal degradation. Overall, aeration and agitation of CGB fermentation significantly influenced the production of xanthan gum and its properties.     

Effect of Xanthan Gum on the Performance of Aqueous Film-Forming Foam

Solution properties of aqueous film-forming foam (AFFF) formulations containing different xanthan gum contents were investigated first by varying the mass fraction of xanthan gum in the range of 0.1–0.5%. Foam properties and fire-extinguishing performance of the AFFF formulations were then evaluated. Results indicated that xanthan gum content slightly affected surface tension of foam solutions. However, xanthan gum significantly affected viscosity of AFFF concentrates. Foaming of the AFFF formulations was hardly affected by xanthan gum, but foam stability of the compounds was obviously enhanced with the addition of xanthan gum. Optimal xanthan gum content was determined as 0.3%, which resulted in the shortest 90% control time and fire extinguishment time. Burnback time of foams increased with the addition of xanthan gum because of the enhanced foam stability.     

Xanthan gum production from cassava bagasse hydrolysate with Xanthomonas campestris using alternative sources of nitrogen

Cassava bagasse was hydrolyzed using HCl and the hydrolysate was used for the production of xanthan gum using a bacterial culture of Xanthomonas campestris. Cassava bagasse hydrolysate with an initial concentration of approx 20 g of glucose/L proved to be the best substrate concentration for xanthan gum production. Among the organic and inorganic nitrogen sources tested to supplement the medium—urea, yeast extract, peptone, potassium nitrate, and ammonium sulfate—potassium nitrate was most suitable. Ammonium sulfate was the least effective for xanthan gum production, and it affected sugar utilization by the bacterial culture. In media with an initial sugar concentration of 48.6 and 40.4 g/L, at the end of fermentation about 30 g/L of sugars was unused. Maximum xanthan gum (about 14 g/L) was produced when fermentation was carried out with a medium containing 19.8 g/L of initial reducing sugars supplemented with potassium nitrate and fermented for 72 h, and it remained almost the same until the end of fermentation (i.e., 96 h).     

Feasibility of Polyvinyl Alcohol as a Transdermal Drug Delivery System for Terbutaline Sulphate

A series of terbutaline sulphate drug incorporated polyvinyl alcohol (PVA) matrix films were produced by the solvent evaporation method. The effect of xanthan gum and plasticizers (propylene glycol and dibutyl phthalate) on the rate and amount of drug diffusion from PVA membrane across the hydrated cellophane membrane has been evaluated, using an open glass diffusion‐tube. The obtained films were clear, smooth and flexible having sufficient mechanical strength. The mechanical performance of the dry PVA films with xanthan gum and plasticizers were also ascertained. Polyvinyl alcohol‐xanthan gum blends showed a high rate of drug release compared to that of polyvinyl alcohol film alone. Among the two plasticizers employed, propylene glycol showed better permeability. Among different formulations studied, the formulation PVA/xanthan gum/propylene glycol (F7) was found to be an optimized composition for efficient transdermal delivery of the model drug, terbutaline sulphate. The mechanism of drug diffusion has been evaluated using the Peppas model. Stability studies carried out on polymer‐drug formulations revealed that the drug is stable at 40°C and 75% RH for a period of 6 weeks.     

Investigation of Adsorption of Xanthan Gum on Enamel by Tapping Mode Atomic Force Microscopy

By using tapping mode atomic force microscopy (TMAFM), a polymer layer was found on the enamel surface after the exposure to xanthan gum solutions. The layer thickness is closely related to the exposure time and the concentration of xanthan gum solution. The thickness data were evaluated by a Kruskal-Wallis test and Box-Whisker Plot at a 95% confidence level (p＜0. 05), and a statistically significant difference among the thickness data groups was demonstrated. After the exposure to 1000, 400, 100 mg/L xanthan gum solutions, the mean of layer thickness at the adsorption equilibrium is in the ranges of 103.5--122.06,82.4--88.94 and 45. 27--55.55 nm, respectively. This phenomenon suggests that the viscosity modifying a-gents in the beverage might be adsorbed on the enamel surface during consumption, which may form a barrier that can protect the enamel from being attacked by acid and therefore reduce dental erosion.     

黄原胶水凝胶的分子网络模型

本文结合二次采油中作为压裂液的黄原胶水凝胶,从其成胶机理着手分析,以Carreau-Bird模型为基点,在分子网络模型中引进了吸附反应动力学项以及计及流体触变性质的函数f(t),并把自由链、迷向链及破碎网络对应力的贡献模拟成牛顿性,从而导出本构方程。方程中的参数值由凝胶的粘弹性性质及非线性物质函数决定,用有约束的优化方法进行优化后得到,模型计算的结果与实验数据大致相符。