不同分子量壳聚糖和壳聚糖硫酸酯的抗氧化活性

不同分子量壳聚糖和壳聚糖硫酸酯的抗氧化活性;壳聚糖;壳聚糖硫酸酯;超氧阴离子自由基（ ）;羟自由基（·OH）;抗氧化活性     

低分子量壳聚糖的Sm3+配合物的合成和表征

壳聚糖经双氧水降解制得低分子量壳聚糖,低分子量壳聚糖与Sm3 反应制得配合物。分别用红外、紫外、荧光等测试手段对低分子量壳聚糖及其与Sm3 形成的配合物的结构和性能进行了表征。结果表明,低分子量壳聚糖与Sm3 发生了螯合作用,形成了较稳定的配合物。     

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.     

N,O-羧甲基壳聚糖的合成和性质研究

采用多段升温法将壳聚糖改性,合成了取代度为1.84、平均分子量为3.08×105、等电点为7.28的N,O-羧甲基壳聚糖(CMC),分别用紫外光谱、红外光谱、荧光光谱对其结构进行了表征,并对其水溶液的Zeta电位、电导率、表面张力以及水分散体系中羧甲基壳聚糖微粒的粒径分布进行了研究.结果表明, N,O-羧甲基壳聚糖具有表面活性;介质的pH值和浓度对羧甲基壳聚糖溶液的稳定性有很大的影响.     

壳聚糖季铵盐的合成及结构表征

用异相法合成了水溶性壳聚糖季铵盐衍生物，并用红外光谱及核磁共振谱进行结构表征。结果表明：在中性反应条件下，壳聚糖分子的季铵盐衍生化反应主要发生于亲该中心Ｃ２位的氨基上，所合成的壳聚糖季铵盐衍生物可直接溶解于水。其水溶液可以任意比例与乙醇、丙二醇、甘油等混溶。     

聚醚型非离子表面活性剂分子量测定方法的研究(Ⅰ)

关于聚醚型非离子表面活性剂分子量的测定方法主要有用对甲苯磺酸及4-N,N二甲氨基吡啶或N-甲基咪唑为乙酰化催化剂测定聚醚多元醇的羟基数(即羟值法),用蒸气压渗透(VPO)法测定数均分子量,以及用凝胶渗透色谱(GPC)法进行分子量分级测定等。70年代以来,已开始将红外光谱、核磁共振谱、高效液相色谱及质谱等方法用于非离子表面活性剂的平均分子量测定。由于羟值法简便、快速和仪器简单,在工业生产中一直沿用为聚醚分子量测定的常规分析方法。但由于羟值法与VPO法的理论基础不同,两法所测分子量往往有一定差别。为此我们用羟值法对不同分子量的聚乙二醇(PEG)标样及本实验室合成的各种聚环氧乙烷无规聚醚进行分子量测定,并与VPO法对照,考察两方法的差别及羟值法的适用范围。     

荧光技术在两亲性聚合物研究中的应用

本文综述了应用荧光技术研究不同结构的两亲性聚合物性质的研究进展,涉及的不同结构两亲性聚合物主要有两亲性嵌段共聚物、两亲性接枝共聚物、两亲性树状聚合物以及其他结构的两亲性聚合物;说明了荧光技术可以用于研究聚合物疏水(或亲水)基团的结构参数(如骨架、长度、取代度和分子量)的变化,对两亲性聚合物的微环境性质(如微极性、微黏度、局部黏结力)、聚集行为(如临界聚集浓度)以及其他性质(如临界胶束浓度)的影响规律,以便对功能性更强的两亲性聚合物的合成提供理论指导。     

不同分子量壳聚糖对蒙脱土插层复合物的影响

于醋酸溶液中通过溶液插层技术将不同分子量的壳聚糖与钠基蒙脱土进行插层复合,制备了系列壳聚糖/蒙脱土插层复合物. 通过XRD、TEM、FTIR测试技术对插层复合物的结构进行了表征. 结果表明,仅通过醋酸溶液处理,残留的HAc就可使MMT层间距由原来的1.3 nm增加至1.55 nm,并使结构规整性提高;降低壳聚糖分子量有利于MMT层间距增大,并出现更多剥离形态的蒙脱土;当壳聚糖分子量为4.1×104时,最大层间距可达2.48 nm,但进一步降低壳聚糖分子量层间距反而略微减小;红外光谱分析表明,插层复合物中壳聚糖与蒙脱土间存在明显的静电作用. TGA分析结果表明,插层复合物中壳聚糖的含量随分子量的降低而增加,残留的醋酸使插层复合物中壳聚糖的热稳定性能下降.     

羟乙基壳聚糖的合成及其与聚乳酸的相容性

本文以异丙醇为溶剂,碱化壳聚糖与2-氯乙醇反应制备了羟乙基壳聚糖,对产物的结构与性能进行了分析表征;然后以二甲基亚砜为溶剂,采用溶液共混法制备了一系列不同组成的壳聚糖/聚乳酸和羟乙基壳聚糖/聚乳酸复合膜,对两组分间的相容性进行了研究。结果表明,羟乙基化反应在-OH和-NH2上均有发生,壳聚糖单元糖环上的羟乙基取代度为2.46;改性后,壳聚糖结晶性能和起始热分解温度下降,溶解性能得到改善。复合膜的电镜结果显示,在壳聚糖/聚乳酸复合膜中,相分离现象显著存在,壳聚糖在聚乳酸基体中的分散不均匀,有团聚现象,随着壳聚糖含量增加,两组分间的相分离程度增大,团聚现象更为严重,当壳聚糖含量达到50%时,已难以制备完整的复合膜;与之相反,羟乙基壳聚糖/聚乳酸复合膜中两种组分之间的相容性有所改善,相分离现象不明显,并且,当羟乙基壳聚糖含量从10%增加到50%,复合膜中两种组分之间的相容性变化不大。     

两亲性多肽自组装及其应用

两亲性多肽分子具有类似天然磷脂分子的两亲特性、丰富的分子结构、独特新颖的组装体结构以及特殊的生物学功能,是多肽自组装研究的热点领域.本文总结了近年来关于两亲性多肽自组装研究及应用的进展,介绍了几种常见的两亲性多肽,并进一步阐述其分子结构特征、组装行为和机理、组装体结构和功能以及在纳米技术和生物医学领域中的应用.     

New approach to the quaternization of chitosan and its amphiphilic derivatives

Regioselective quaternization of chitosan and its amphiphilic derivatives has been carried out by means of reaction with betaine in the presence of the coupling reagent 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ) in aqueous media at pH 5.5 ± 0.5. This reaction results in preparation of N-/(trimethylammonio)acetyl/chitosan chloride and its amphiphilic derivatives. The degree of quaternization increases with increasing EEDQ/chitosan ratio and is partly accompanied by N-ethoxycarbonylation. That side-product formation can be minimized by increasing betaine/EEDQ ratio.     

Graft Copolymerization of (Dimethylamino)Ethyl Methacrylate onto Chitosan Initiated by Ceric Ammonium Nitrate

Abstract

(Dimethylamino)ethyl methacrylate (DMAEMA) was grafted onto chitosan using ceric ammonium nitrate as initiator in acetic acid solution. The effects of reaction variables on the grafting percentage and efficiency percentage were investigated, including the amounts of monomer and initiator, reaction time and reaction temperature. The grafted copolymers were confirmed by FTIR, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results of TGA and DSC indicated the improvement of thermal stability for chitosan‐g‐poly(PDMAEMA). Solubility test revealed the improved hydrophilicity of grafted chitosan in aqueous acetic acid solution, and its swelled behavior in mixtures of glacial acetic acid and anhydrous ethanol (the ratios of 1:1 and 1:2, v/v). The grafted copolymer possessed amphiphilic structure and exhibited properties of polymeric surfactant.     

两亲性羧甲基壳聚糖衍生物的表面活性研究

将羧甲基壳聚糖与烷基缩水甘油醚在碱性条件下反应,合成了一系列新型的两亲性化合物(2-羟基-3-烷氧基)丙基-羧甲基壳聚糖,对其表面性质的研究结果表明,对同一衍生物,在所研究范围内,取代度越高,降低表面张力的能力及效率越高;对同一取代度的不同衍生物,疏水链越长,降低表面张力的能力越强;对链较短和取代度较大的衍生物,如(2-羟基-3-丁氧基)丙基羧甲基壳聚糖(HBP-CMCHS),在外加电解质存在时溶液的表面张力曲线出现2个转折点,表明可能有分子内胶束形成;而对链较长的衍生物,如(2-羟基-3-十二烷氧基)丙基羧甲基壳聚糖(HDP-CMCHS),则无明显的临界胶束浓度,有外加电解质时表面张力曲线也未出现2个转折点.     

制备壳聚糖衍生物接枝聚乙二醇侧链的简单方法

壳聚糖及其衍生物由于其可再生性、生物相容性以及结构中的多种活性基团,具有多种优良的性质,已经广泛应用于化妆品、食品、医药、农业、环保等多个行业中.     

Solid-state synthesis of amphiphilic chitosan-polyethylene systems by the maleinization of both components

N-acylated chitosan modified by maleic anhydride was prepared by the method of the solid-state synthesis (Bridgman anvils, semipilot extruder). In contrast to the synthesis under homogeneous conditions, solid-state acylation is accompanied by the reaction of imidization of the formed amic acid as well as by reaction through double bonds, thus leading to the formation of derivatives of succinic anhydride. By simultaneous or subsequent interaction of chitosan modified with maleic anhydride with a PE matrix, either modified or not modified with maleic anhydride, new chitosan-polyethylene composite materials are prepared, and these composites are characterized by the combined valuable medicinal and biochemical properties of chitosan and high mechanical characteristics of the polyolefin component. The above composites are of obvious interest as amphiphilic sorbents, which are highly resistant to the action of aggressive media, as well as antimicrobial and biodegradable PE-based materials.     

异相法制备磺酸基取代壳聚糖衍生物

用3-氯-2-羟基丙磺酸钠与壳聚糖在较低温度下进行非均相反应制备了一系列取代度,结构新颖的改性壳聚糖.实验表明化学改性能极大的提高壳聚糖在水溶液中的溶解性能.研究了不同的反应条件对壳聚糖取代度的影响并用核磁共振表征了它们的结构.反应可在中性、较为温和的条件下进行,通过改变反应时间和反应物比例能有效的控制改性壳聚糖的取代度.改性后的壳聚糖能溶解于中性的水溶液中,浊度实验表明产物具有明显的两性聚电解质特征,其等电点约在pH=5.7.该方法为制备化学改性壳聚糖的一种有效的方法.     

Polymeric micelle systems of hydroxycamptothecin based on amphiphilic N-alkyl-N-trimethyl chitosan derivatives

This research investigated the possible utilization of amphiphilic N-octyl-N-trimethyl chitosan (OTMCS) derivatives in solublization and controlled release of 10-hydroxycamptothecin (10-HCPT), a hydrophobic anticancer drug. The release behavior of the 10-HCPT-OTMCS micelles was measured and compared to that of a commercial 10-HCPT lyophilized powder in vitro and in vivo. This research also examined the effects of chemical structure of the chitosan derivatives and the micellar preparation conditions on the encapsulation efficiency, drug loading content, and particle size of the polymeric micelles. The results showed that these chitosan derivatives were able to self-assemble and form spherical shape polymeric micelles with an average particle size range of 24–280 nm and a drug loading content of 4.1–32.5%, depending on the modified structures and loading procedures. The solubility of 10-HCPT in aqueous fluid was increased about 80,000-fold from 2 ng/ml in water to 1.9 mg/ml in OTMCS micellar (degree of octyl and trimethyl substitution is 8% and 54%, respectively) solution. In addition, OTMCS was able to modulate the in vitro release of 10-HCPT and improve its pharmacokinetic properties and lactone ring stability in vivo. These data suggested the possible utilization of the amphiphilic micellar chitosan derivatives as carriers for hydrophobic drugs for improving their delivery and release properties.     

Influence of ultraviolet-irradiated oxygen on depolymerization of chitosan

In the present paper, the depolymerization of chitosan was carried out by the ultraviolet-irradiated oxygen treatment. Influence of reaction conditions on depolymerization of chitosan was investigated. The chemical structure of the depolymerized chitosan was characterized by FT-IR and ¹³C NMR spectra. The FT-IR and ¹³C NMR spectra suggested that there was no obvious modification of chemical structure of the depolymerized chitosan. The X-ray diffraction analysis showed that crystalline structure of chitosan can be destroyed by ultraviolet-irradiated oxygen. The use of depolymerization of chitosan by ultraviolet-irradiated oxygen treatment can be a convenient, timesaving, and cost-efficient method for replacing the expensive and time-consuming enzymatic or chemical methods that are currently used to depolymerize chitosan.     

Grafting of 18β-Glycyrrhetinic Acid and Sialic Acid onto Chitosan to Produce a New Amphipathic Chitosan Derivative: Synthesis,Characterization, and Cytotoxicity

Chitosan is the only cationic polysaccharide found in nature. It has broad application prospects in biomaterials, but its application is limited due to its poor solubility in water. A novel chitosan derivative was synthesized by amidation of chitosan with 18β-glycyrrhetinic acid and sialic acid. The chitosan derivatives were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and measurement of the zeta potential. We also investigated the solubility, cytotoxicity, and blood compatibility of chitosan derivatives. 18β-glycyrrhetinic acid and sialic acid could be grafted onto chitosan molecular chains. The thermal stability of the synthesized chitosan derivatives was decreased and the surface was positively charged in water and phosphate-buffered saline. After chitosan had been modified by 18 β-glycyrrhetinic acid and sialic acid, the solubility of chitosan was improved greatly in water and phosphate-buffered saline, and percent hemolysis was <5%. Novel amphiphilic chitosan derivatives could be suitable polymers for biomedical purposes.     

臭氧降解法制备壳低聚糖及其结构表征

以85％脱乙酰度、相对分子质量为25×10^4的壳聚糖为原料,在20℃、pH为3、氧气流量0．7m^3／h的条件下降解6h,降解液用氨水调至pH为9,无沉淀,分别用截留相对分子质量为2k、3k、5k、10k的中空纤维膜超滤,获得所需聚合度的壳低聚糖。降解产物的结构用红外光谱、核磁共振碳谱表征,结果说明降解前后的结构基本没有变化。降解产物的聚合度用飞行时间质谱表征,其中经过2k中空纤维膜超滤后的壳低聚糖聚合度主要为4～10。