离子液体中均相合成N-乙酰化壳聚糖及其性能研究

合成了对壳聚糖溶解效果好、可重复使用的离子液体氯化2-氨基乙酸[Gly]Cl,用1H NMR和FT-IR对其结构进行了确定。在制得的离子液体水溶液中,制备了水溶性N-乙酰化壳聚糖。用XRD和FT-IR对产物进行了结构表征。通过单因素实验得到了较佳反应条件:n(乙酸酐)∶n(壳聚糖)=2.75∶1,反应温度60℃,反应时间5 h。并对产物的吸湿保湿性能进行初步研究,结果表明,产物具有良好的吸湿保温性能。还考察了离子液体的重复使用性能,重复使用3次后,N-乙酰化壳聚糖的取代度仍大于89%。     

超声波合成羧甲基壳聚糖及表征

采用超声波辐射,以壳聚糖为原料、乙醇为分散介质、一氯乙酸为羧甲基化试剂合成了羧甲基壳聚糖,通过四因素三水平正交实验得出最优合成条件为：mNaOH/m壳聚糖为1．5;mclCH2COOH/m壳聚糖为1．5;反应时间2h;反应温度60℃;采用红外光谱仪、紫外-可见分光光度计、热重／差热分析仪、X射线衍射仪、扫描电镜对产物结构进行了表征．     

Study on volume ratio and plasticizer screening of free coating membranes composed of ethyl cellulose and chitosan

The aim of this study was to optimize the formula of free blended coating membrane of ethyl cellulose (EC) and chitosan (CS), including their suitable ratio range and the best plasticizer used. The dry films were produced by a casting/solvent evaporation method, with different volume ratio of EC and CS solution plasticized by various plasticizers, respectively. The wet films were prepared by immersing dry films in pH 6.8 phosphate buffer saline (PBS) for 24 h. The promising ratio range of EC/CS was below 20/5 or 20/6 with various plasticizer, which was determined by comparing the viscosity of the blended solutions and the morphology of the blended films. The efficiency of plasticization was evaluated by measuring glass transition temperature (T_g). All the testing plasticizers have good compatibility with EC or CS and dibutyl phthalate (DBP) have the strongest efficiency inducing the lowest T_g (39.9°C) of the film. Mechanical properties were evaluated by the ratio of tensile strength (T) to elastic modulus (E). In the wet state, the films with DBP had the highest T/E value (1.2). The results of leaching of plasticizers also verified that DBP was the most stable plasticizer in the films. The release rates of tetramethylpyrazine phosphate (TMPP) through the pellets coated with the blended films of EC/CS (20 : 6 v/v) plasticized by various plasticizers showed that the more water‐soluble the plasticizer was, the more quickly TMPP dissolved from the coated pellets, which further indicated that the water‐insoluble plasticizers (such as DBP) could be more applicable to keep the sustained or controlled release property of the blended films in wet state. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1932–1939, 2006     

棉织物的抗菌免烫整理研究

通过正交试验探讨了用H2 O2 氧化降解法制备适用于与聚羧酸MAA - 1配合进行抗菌免烫整理的低聚水溶性壳聚糖的最佳工艺 ,研究了降解壳聚糖与聚羧酸MAA - 1配合对棉织物进行抗菌免烫整理的工艺以及降解壳聚糖的质量浓度和相对分子质量对整理效果的影响。结果表明 :用 80g/L的聚羧酸MAA - 1和 4 0 g/L相对分子质量为 90 0 0的降解壳聚糖分两浴整理的棉织物的褶皱回复角为 2 71°,DP等级为 4 .0 ,断裂强力保留率为 6 4 % ,对大肠杆菌和金黄色葡萄球菌的抗菌率分别为 94%和 83%。经过 2 0次洗涤 ,其WRA为 2 5 7° ,DP等级为 3.7,而抗菌率则均保持在洗涤前的 80 %以上。阴离子染料 (直接冻黄G)染色的K/S值较用聚羧酸MAA - 1整理的棉织物提高了 1 .85。     

Synthesis and properties of chitosan-modified poly(vinyl butyrate)

Modification of chitosan by grafting of vinyl butyrate was carried out in homogeneous phase using potassium persulfate as redox initator and 1.5% acetic acid as solvent. The percent grafting and grafting efficiency were analysed and the high grafting efficiency up to 94% was observed. The effects of reaction variables such as monomer concentration, initiator concentration, temperature and reaction time were investigated. It was observed that the solubility of chitosan was markedly reduced after grafting with vinyl butyrate. The grafted product is insoluble in common organic solvents as well in dilute organic and inorganic acids. Characterization of the graft copolymers were carried out by using Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM) technics. Characteristic signal of carbonyl group was observed at 1,731 cm⁻¹ which belongs to the poly vinyl butyrate segments in the graft copolymer. The melting transition of the chitosan main chain in the copolymer shifted to 124°C from its original value 101°C. In addition to these, we have also studied topology of the graft copolymer and the SEM micrograph showed continuous homogenous matrix which means there is no phase separation.     

天然高分子壳聚糖在环保领域中的研究及应用

综述了壳聚糖在水处理、大气污染治理、减轻水果蔬菜农药污染以及在制备生物降解材料上的应用及研究进展。     

Periodontal ligament cells cultured on the tricalcium phosphate/chitosan scaffolds in vivo and in vitro

To search suitable scaffolds for periodontal tissue regeneration, different ratios of tricalcium phosphate/chitosan(TCP/chitosan) scaffolds were prepared through a freeze-drying process. Human periodontal ligament cells(HPLCs) were incubated on the scaffolds in vitro. Cells were cultured on the scaffolds, detected by scanning electron microscopy (SEM). HPLCs were analyzed by MTT assay and alkaline phosphatase(ALP) activity detection. HPLCs were seeded onto the scaffolds. Then these scaffolds with HPLCs were implanted subcutaneously into athymic mice. The state of periodontal tissue regeneration was detected after 4 weeks. As the ratio of TCP increased, TCP/chitosan scaffolds accelerated HPLCs proliferation significantly higher than the pure chitosan scaffold. HPLCs produced the cementoid tissue in vivo. The periodontal tissue regeneration engineering is able to be applied with TCP/chitosan scaffolds.     

Evaluation of apatite-coated chitosan microspheres for bone regeneration

The apatite-coated chitosan microspheres were fabricated by incubating chitosan in five times simulated body fluid. The apatite deposited on the microspheres was similar to natural bone mineral, as demonstrated by scanning electron microscopy, X-ray diffraction spectra and Fourier transformed-infrared spectroscopy analyses. Rat bone marrow-derived mesenchymal stem cells （BMSCs） were seeded on apatite- coated microspheres to investigate the effect of this scaffold on cell proliferation and differentiation. BMSCs seeded on uncoated microspheres were served as a control. In vivo experiment was evaluated by transplanting the microspheres loaded with or without BMSCs in 5-mm cranial defects of Wistar rats. Bone regeneration was investigated via micro-CT and histological analysis. It was found that apatite-coated chitosan microspheres could significantly promote the proliferation and alkaline phosphatase activity of BMSCs compared with uncoated microspheres. Histological slices and Micro-CT images at 8 weeks revealed much better regeneration of bone in the apatite-coated microspheres loaded with BMSCs than the control. In addition, the defect filled with pure microspheres induced little new bone formation. Our findings suggest that the apatite-coated chitosan microspheres scaffold is a promising carrier of stem cells for cranial bone tissue engineering.     

Adsorption behavior of cross-linked chitosan modified by graphene oxide for Cu（Ⅱ） removal

Cross-linked chitosan（CS）,cross-linked chitosan/graphene（CS/RGO10） and cross-linked chitosan/graphene oxide（CS/GO10） were prepared as adsorbents for Cu（Ⅱ）.The effects of pH,contact time,adsorbent dosage and initial concentration of Cu（Ⅱ） on the adsorbing abilities of CS,CS/RGO10 and CS/GO10 to Cu（Ⅱ） were investigated.The results demonstrate that the adsorption capacities of CS/GO10 and CS/RGO10 are greater than that of CS,especially at pH 5.0 and the adsorption capacities are 202.5,150 and 137.5 mg/g,respectively.Their behaviors obey the Freundlich isotherm model very well.Additionally,CS/GO10 has the shortest time to achieve adsorption equilibrium among them and can be used as a perspective adsorbent for Cu（Ⅱ）.     

β-环糊精改性壳聚糖微球的制备及其性能研究

采用反相悬浮法,通过环氧氯丙烷交联制备β-环糊精改性交联壳聚糖微球(CDS),用FTIR和SEM进行表征,研究其对甲基橙(MO)的吸附和缓释性能。考察吸附时间、溶液p H值、MO浓度、温度等因素对CDS微球吸附的影响,并与交联壳聚糖(CTS)微球进行比较。结果表明,在p H 4.0、交联CTS微球1h可达吸附平衡,而CDS 2 h达到平衡;吸附数据均符合Freundlich等温方程和二级动力学方程。