串联式压电传感技术用于壳聚糖脱乙酰度测定及其对铜(Ⅱ)离子吸附的研究

基于酸碱滴定过程和金属离子吸附过程中的溶液电导率变化,首次将串联式压电石英晶体传感器(SPQC)用于壳聚糖脱乙酰度测定和壳聚糖对Cu2+的吸附特性考察.实验发现由滴定频率响应曲线测得的脱乙酰度与电位滴定法的测定值相近.用SPQC实时监测壳聚糖对Cu2+的吸附过程,通过比较频移响应曲线,考察了Cu2+初始浓度、吸附剂用量及脱乙酰度对壳聚糖吸附Cu2+性能的影响.结果表明,适当增加Cu2+浓度和吸附剂用量更利于壳聚糖对Cu2+的吸附,随着脱乙酰度的增加,壳聚糖对Cu2+的配位能力增强.     

壳聚糖稀溶液性质的研究

本文在前工作基础上.对不同脱乙酰度壳聚糖在0.2mol/l CH_3COOH+0.1mol/l CH_3COONa的缓冲溶液中进行了分子量、特性粘数、分子尺寸、第二维利系数和扩张因子等稀溶液性质的深入研究.发现Mark-Houwink方程常数K和α有规律地依赖于壳聚糖的脱乙酰度而变化.而且相同分子量时,随着脱乙酰度的增加,壳聚糖在稀溶液中的分子尺寸、特性粘数和扩张因子等增加,而特性比和空间位阻因子随着脱乙酰度的增加而减小.     

壳聚糖超声可控降解及降解动力学研究

通过正交实验法考察了壳聚糖溶液浓度、反应温度、超声强度以及醋酸溶液浓度对超声降解反应的影响,确定了最佳反应条件,制备了一系列不同分子量的壳聚糖.研究了壳聚糖溶液浓度、反应温度以及壳聚糖原料分子参数与降解速率常数的关系.通过红外光谱、X-射线衍射和凝胶渗透色谱对降解产物进行了表征.结果表明,超声降解壳聚糖的最佳条件为10℃,壳聚糖溶液浓度2.5g/L.降解速率常数随壳聚糖溶液浓度和反应温度的降低而增大.高分子量和低脱乙酰度的壳聚糖原料有较高的降解速率和降解速率常数,壳聚糖原料的分子量对降解速率和降解速率常数的影响大于脱乙酰度对其的影响.超声波导致了壳聚糖分子量的降低和产物晶体结构的破坏,但没有改变产物的脱乙酰度和糖残基结构.     

凝胶渗透色谱法研究壳聚糖生物材料酶降解过程的均匀性

壳聚糖是一种重要的生物医用材料,脱乙酰度是影响其生物降解性能的重要因素。运用凝胶渗透色谱研究了脱乙酰 度及相对分子质量分布相似、而聚合单元N-乙酰氨基-D-葡萄糖和D-氨基葡萄糖分布不同的两种壳聚糖材料在溶菌酶作用 下的降解过程,分析检测了壳聚糖材料在降解过程中的重均相对分子质量、相对分子质量多分散性和相对分子质量分布 的变化。发现聚合单元为随机分布的壳聚糖样品,其降解是均匀的;而聚合单元为段状分布的壳聚糖样品,其降解是非 均匀的;表明其聚合单元的分布方式决定壳聚糖材料酶降解过程的均匀性。     

羟丙基三甲基氯化铵壳聚糖制备的可控性研究

用壳聚糖与缩水甘油三甲基氯化铵反应制备羟丙基三甲基氯化铵壳聚糖,所得产物的结构受壳聚糖分子量和脱乙酰度、反应温度、反应时间、壳聚糖与缩水甘油三甲基氯化铵投料比的影响。实验结果表明：随着反应温度升高,羟丙基三甲基氯化铵壳聚糖的取代度增加,在70～80℃达最大;反应时间增加,取代度增加,产物分子量降低。缩水甘油三甲基氯化铵与壳聚糖比例达3：1前取代度随比例升高而增加。脱乙酰度和分子量越大的壳聚糖其季铵盐取代度越高。控制反应温度在30～90℃,反应时间3～10h,投抖比为1：1～4：1,可以得到取代度15％～909／6,分子量1万到100万的羟丙基三甲基氯化铵壳聚糖。     

蘑菇中甲壳素的提取及结构研究

以蘑菇为原料提取甲壳素,并制备壳聚糖。通过滴定法测定由蘑菇制备的壳聚糖的脱乙酰度,用乌氏黏度计测定了比浓黏度,并研究了制备工艺中加热温度和碱处理时间对它们的影响,计算了其产率;对以蘑菇为原料制取的甲壳素、壳聚糖的结构通过红外光谱进行表征。结果表明,在碱处理时间为24h、加热温度为100℃的条件下有较高的脱乙酰度;比浓黏度随着碱处理时间的延长、加热温度的增加都呈下降的趋势;壳聚糖产率为1．69％。制取的甲壳素、壳聚糖的红外光谱图表明,甲壳素在蘑菇中主要是以α-构型存在,α-构型甲壳素在浓碱中经过脱乙酰后生成β-构型的壳聚糖。     

甲壳素类液晶高分子的研究Ⅳ.脱乙酰度对壳聚糖液晶性的影响

通过壳聚糖乙酰化法制备了不同脱乙酰度的壳聚糖 ,并研究了脱乙酰度这一结构因素对壳聚糖溶致液晶性的影响 .观察到脱乙酰度为 5 0 %左右时 ,壳聚糖在水中和二氯乙酸中的溶致液晶临界浓度最高 .壳聚糖在水中的溶致液晶临界浓度远低于在二氯乙酸中的临界浓度 .     

壳聚糖对Zn2+的吸附性能研究

本文用壳聚糖对Ｚｎ＾２＋的吸附条件进行了研究,探讨了脱乙酰度,分子量,粒度大小,溶液的ｐＨ值,温度,Ｚｎ＾２＋起始浓度和不同锌盐等方面对壳聚糖吸附性能的影响。结果表明：壳聚糖对Ｚｎ＾２＋的吸附具有Ｌａｎｇｍｕｉｒ吸附特征,其吸附最佳条件是壳聚糖脱乙酰度为１００％,锌盐为硫酸锌,Ｚｎ＾２＋溶液ｐＨ值为６．０,起始浓度４－５ｍｇ／ｍｌ。     

磁性交联壳聚糖对稀土金属离子的吸附性能

用高胶乙酰度的壳聚糖包埋自制的磁流体，并用戊二醛交联制成磁性壳聚糖（MCG），考察了其对稀土离子La^3 ,Nd^3 ,Eu^3 ,Lu^3 的吸附性能。探讨了溶液的酸度，体系温度，初始离子浓度对MCG吸附性能的影响；发现MCG对稀土离子的吸经纯高脱乙酰度的壳聚糖强，最高吸附率可达到99％以上，并具有良好的重复使用性；其吸附行为满足Langmuir等温式。     

壳聚糖的制备及其抑菌性能的研究

以虾壳为原料,通过化学法从虾壳中制备具有良好抑菌性的壳聚糖,并对制备的壳聚糖的脱乙酰度、分子质量及抑菌性能等进行了研究。研究结果表明,制备出的壳聚糖在脱乙酰度为82.68%,分子质量为9.96×104时,具有良好的抑菌性;其对大肠杆菌的抑菌率为92.58%,对金黄色葡萄球菌的抑菌率为99.94%,对枯草芽孢杆菌的抑菌率为99.61%。     

Chitosan as green kinetic inhibitors for gas hydrate formation

The kinetic inhibiting effect of a number of chitosans on hydrate formation was investigated using methane and methane/ethane gas mixtures.The results indicated that chitosan was a good kinetic inhibitor.The induction time of gas hydrate formation evidently increased with the degree of deacetylation(DD),however,when DD was higher than 80%,the effect of DD on the induction time was negligible.Moreover,it was found that the molecular weight(MW)of chitosan and the addition of polyethylene oxide(PEO)had little effect on the induction time.The optimal concentration of chitosan was found to be 0.6wt%.Finally,the mechanisms of the kinetic inhibitor on the hydrate formation were discussed.     

甲壳胺接枝聚合反应的研究

本文是以过硫酸钾为引发剂，研究甲基丙烯酸甲酯（ＭＭＡ）与甲壳胺的接枝聚合反应．通过对不同脱乙酰度（ｄａ）甲壳胺（ＣＴＳ）的接枝聚合反应条件实验，研究了反应时间，温度，引发剂浓度和单体浓度对接枝聚合反应的影响，从中得到优选的反应条件．在相同条件下，比较不同脱乙酰度甲壳胺及Ｎ－取代甲壳胺的接枝聚合反应结果，表明：甲壳胺中氨基参与了接枝聚合反应的引发过程．     

Studying Flocculation Mechanism of Chitosan with Pyrene-fluores-cence Probe Method

A peak/ratio in pyrene-fluorescence spectrum was employed to measure the polarity of micro-environment of chitosan adsorb-ing py--rene molecules. The authors have in the first time detect-ed the pyrene-fluorescence spectrum of chitosan with different degrees of deacetylation (D. D. ), and found the relationship between the flocculaflon of bentonite colloid by chitosan and the peak/ratio values of different molecular weight (M. W. ) and D .D. of chitosan. We find that M.W. plays a key role in the flocculatlon, but D.D. has limited effect on it. From micro-en-vironmental structure of view, it can be proved that the inter-particle bridging rather than charge neutralization dominates the flocculatlon with chitosan.     

水溶性壳聚糖降血脂作用的化学机理(Ⅰ)──水溶性壳聚糖及其衍生物对胆酸盐的结合能力研究

通过壳聚糖氧化裂解,制备了分子量为8000的水溶性壳聚糖,并通过烷基化反应合成了二乙氨乙基壳聚糖、二甲氨基(1-甲基)乙基壳聚糖及二乙基甲基铵乙基壳聚糖.在体外测定了水溶性壳聚糖及其衍生物对胆酸盐(牛磺胆酸钠和甘氨胆酸钠)的结合能力及其影响因素.结果表明,水溶性壳聚糖结合胆酸盐的能力主要取决于其阳离子化程度.修饰后的壳聚糖结合胆酸盐的能力增强,说明引入更多的胺基或铵基有利于对胆酸盐的结合.     

Characterization of chitosan by pyrolysis—mass spectrometry

Chitosan of different degrees of deacetylation have been prepared from chitin. Pyrolysis-mass spectra of these chitosan samples in the ion source of a mass spectrometer were examined to check for a correlation with the degree of deacetylation, as represented by the amine content. The results indicate that as the degree of deacetylation increases, the peak ratios 80:60, 67:60 and 80:42 increase to a limit, representing the limit of deacetylation of chitin. The 80 and 67 fragments originate from the d-glucosamine moiety of the polymer and the 60 and 42 fragments from the N-ethyl-d-glucosamine moiety. For chitin, the predicted values of these ratios are expected to be low when compared to chitosan, and this is borne out by the experimental data.     

茜素红与壳聚糖的相互作用机理研究

应用光谱法研究在pH=5.0的反应体系中壳聚糖（CTS）与茜素红（AR）的结合 反应，考察了反应体系中AR/CTS摩尔比、NaCl浓度及CTS的脱乙酰度对茜素红与壳 聚糖相互作用的影响，通过实验测得CTS对AR的最大结合数N_E=4.78×10~3，理论 模型预测最大结合数N_c=4.73×10~3，实验值与理论值一致，并对壳聚糖与茜素红 的相互作用机理提出了合理的解释。     

Influence of the Degree of Deacetylation of Chitosan and BMP-2 Concentration on Biocompatibility and Osteogenic Properties of BMP-2/PLA Granule-Loaded Chitosan/β-Glycerophosphate Hydrogels

Compositions based on chitosan/β-glycerophosphate hydrogels with highly porous polylactide granules can be used to obtain moldable bone graft materials that have osteoinductive and osteoconductive properties. To eliminate the influence of such characteristics as chain length, degree of purification, and molecular weight on a designed material, the one-stock chitosan sample was reacetylated to degrees of deacetylation (DD%) of 19.5, 39, 49, 55, and 56. A study of the chitosan/β-glycerophosphate hydrogel with chitosan of a reduced DD% showed that a low degree of deacetylation increased the MSCs (multipotent stromal cells) viability rate in vitro and reduced the leukocyte infiltration in subcutaneous implantation to Wistar rats in vivo. The addition of 12 wt% polylactide granules resulted in optimal composite mechanical and moldable properties, and increased the modulus of elasticity of the hydrogel-based material by approximately 100 times. Excessive filling of the material with PLA (polylactide) granules (more than 20%) led to material destruction at a ~10% strain. Osteoinductive and osteoconductive properties of the chitosan hydrogel-based material with reacetylated chitosan (39 DD%) and highly porous polylactide granules impregnated with BMP-2 (bone morphogenetic protein-2) have been demonstrated in models of orthotopic and ectopic bone formation. When implanted into a critical-size calvarial defect in rats, the optimal concentration of BMP-2 was 10 μg/mL: bone tissue areas filled the entire material’s thickness. Implantation of the material with 50 μg/mL BMP-2 was accompanied with excessive growth of bone tissue and material displacement beyond the defect. Significant osteoinductive and osteoconductive properties of the material with 10 μg/mL of BMP-2 were also shown in subcutaneous implantation.     

Effect of molecular weight and degree of deacetylation on controlled release of isoniazid from chitosan microspheres

Glutaraldehyde cross‐linked chitosan microspheres for controlled release of isoniazid were prepared using chitosan of different molecular weights (MWs) and degrees of deacetylation (DDAs). Chitosan microspheres were characterized for their size, hydrophobocity, degree of swelling and loading of isoniazid. Hydrophobicity of chitosan microspheres increased on increasing the degree of cross‐linking and MW of chitosan. Chitosan microspheres with high degree of deacetylation (DDA) (75 wt%), high MW chitosan (2227 kg mol^?1), and with 12 wt% concentration of glutaraldehyde showed optimum loading and release of isoniazid. The isoniazid from chitosan microspheres was released in two steps, i.e. burst (%R_B) and controlled (%R_C) steps. The microspheres with low MW chitosan (260 kg mol^?1) and low DDA (48 wt%) showed prominent burst release of isoniazid, but microspheres with high MW chitosan (2227 kg mol^?1) and high DDA (75 wt%) have released more isoniazid in a controlled manner (60 wt%) at 37°C in a solution of pH 5.0 ± 0.1. The burst step of drug release (%R_B) has followed first order kinetics, whereas controlled step of drug release (%R_C) followed zero order kinetics. The burst step of drug release was Fickian and controlled step was non‐Fickian in nature. The diffusion constant (D) for isoniazid release was influenced by the properties of chitosan and degree of cross‐linking. Copyright © 2007 John Wiley & Sons, Ltd.     

Characterization of natural chitosan membranes from the carapace of the soldier crab Mictyris brevidactylus and its application to immobilize glucose oxidase in amperometric flow-injection biosensing system

This study investigated characteristics of a chitosan membrane from the carapace of the soldier crab Mictyris brevidactylus intended to construct an amperometric biosensor. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used in this study to characterize these chitosan membranes intended for constructing enzymatic biosensors. Chitosan membranes suffering various durations (>10 min) of deacetylation had small charge-transfer resistances (<7.88 kohms) but large double-layer capacitances (>0.55 microF). They were found in EIS where both the solution resistance and Warburg impedance upon electrode interface were almost independent of the durations and degree of deacetylation. The degree of deacetylation and the thickness of chitosan membranes were also determined. Membrane thickness was slightly dependent with the duration but degree of deacetylation was slightly dependent on the duration. Chitosan membranes with various thicknesses suffered various durations of deacetylation, but this did not influence their electrochemical characteristics. The chitinous membrane was covalently immobilized with glucose oxidase (EC 1.3.4.3) and then attached onto the platinum electrode of a homemade amperometric flow cell. Sensor signal was linearly related to glucose concentration (r=0.999 for glucose up to 1.0 mM). The system was sensitive (S/N>5 for 10 microM glucose) and reproducible (CV<1.3% for 50 microM glucose, n=5).