【作者】 张秀军；

【导师】 郎惠云；

【作者基本信息】 西北大学 ， 分析化学， 2003， 硕士

【摘要】 壳聚糖是从虾、蟹等甲壳纲动物中提取的一种天然碱性高分子多糖，具有良好的生物活性和医学性能，对过渡金属及稀土金属离子具有良好的配位作用。以壳聚糖及改性壳聚糖为基质，络合金属离子所得到的壳聚糖基金属配合物材料具有许多优良的性能，做为一种配合物材料在药物载体、酶固定化剂、分离膜、人工尿素吸附剂、纳米微晶的生长诱导剂、化学催化剂、植物生长调节剂、金属分离及含量检测等领域有着十分广泛的应用前景。 本文合成了壳聚糖及其衍生物的亚铁配合物——壳聚糖亚铁配合物、低分子量的壳聚糖亚铁配合物、壳聚糖-8-羟基喹啉-亚铁配合物和壳聚糖-N-亚水杨基氨基酸希夫碱亚铁配合物等，并采用红外光谱、元素分析、荧光法、紫外-可见吸收光谱法和热分析等分析手段对配体及其高分子配合物进行了表征，研究了壳聚糖对亚铁的吸附动力学及其热分解动力学，推测了它们的结构，并初步探讨了这些配合物在医药、保健品方面的应用。全文主要包括以下几个部分： （一）综述 对近二十年来天然高分子壳聚糖及其衍生物与过渡金属的配位化学及其应用进行了文献综述。 （二）高分子壳聚糖亚铁配合物的合成及吸附动力学 本文研究了壳聚糖对Fe（Ⅱ）离子的吸附行为，并对其吸附动力学行为进行了研究，通过优化条件得到了较为理想的合成产物。运用紫外光谱、红外光谱、元素分析对高分子配合物进行了表征，进而用化学分析、元素分析，并结合热分析的数据，确定了配合物的组成。结果表明：壳聚糖与Fe（Ⅱ）之间发生了配位作用，其吸附行为可用Langmuir单分子层吸附机理解释，并求得吸附表观活化能为20.23kJ/mol和Lagergren一级速率常数为0.25h^-1。 （三）配合物[Fe（CTS）₂]·SO₄·7H₂O的热分解动力学研究 本文研究了壳聚糖对Fe（Ⅱ）离子的吸附行为，通过条件优化，得到了较为理想的合成产物。并应用红外光谱和紫外光谱对高分子配合物进行了表征，进而用化学分析、元素分析确定了配合物的组成，并利用TG一DSC分析，采用常用的22种机理函数，对配合物的非等温动力学数据进行了线性回归拟合处理，求得了配合物主要分解阶段的热分解动力学最可几机理函数和动力学参数（E和A）。 （四）不同聚合度壳聚糖亚铁配合物的合成及其对尿素的吸附作用 本文研究了HZOZ一HAc控制氧化制备壳寡糖的适宜工艺条件，合成了三种不同聚合度（分子量分别为78万、n万和1万）的壳聚糖，并优化了与亚铁配位的条件，得到了三种壳聚糖亚铁配合物。通过优化条件，分别研究了它们对尿素的吸附性能，并与其它不同尿素吸附材料做了比较，结果表明，壳聚糖亚铁配合物对尿素的吸附具有较高的吸附容量和较高的选择性，在 pH值为5.5，尿素的初始浓度为1.smg/mL时，其吸附容量为60.90m岁g，明显高于其它材料，略低于乙烯多胺一Cu（II）配合物的的吸附容量，但鉴于壳聚糖优良的生物活性和医用性能，仍不失为一种高效新型尿素吸附剂材料。 （五）高分子壳聚糖接枝8一经基哇琳亚铁配合物的合成及性能表征 为利用高分子壳聚糖的生物特性，降低药物的毒副作用，寻找理想的高分子药物载体，增加药物的生物特性，本文利用药物设计中的拼合原则，以高分子壳聚糖为载体，用8一经基哇琳进行共价修饰，合成了哇琳类抗疟杀菌药的高分子药物前体。为增加其活性，使之与亚铁配位，合成了壳聚糖一8一轻基哇琳一亚铁配合物，对合成产物进行了元素分析，TG一DTA分析、IR、UV和荧光光谱分析，研究了配合物的有关性质，并优化了配合物的合成条件。 （六）天然高分子壳聚糖固定化亚铁席夫碱配合物的研究 为寻求增强药物的生物相容性，降低其毒副作用，本文利用具有多种生物医用活性的天然高分子壳聚糖的轴向配位作用，合成了壳聚糖一亚水杨基氨基酸希夫碱亚铁配合物，采用IR、元素分析、荧光法、紫外一可见吸收光谱法和热分析等分析手段对配体及高分子配合物进行了表征，推测了它的结构。以核黄素光化学氧化一轻胺-偶氮比色法，研究了该化合物对超氧离子自由基的清除能力。结果表明，壳聚糖固定化的N一亚水杨基氨基酸希夫碱亚铁配合物对超氧离子自由基的清除能力有所缓解，但仍具有较强的抑制作用，这表明壳聚糖可用做氨基酸希夫碱类抗菌药物的缓控释材料。岁岌『北大学闷反d匕毕月七今仑文 （七）反相流动注射化学发光法测定氨基酸 基于在碱性条件下，氨基酸对次氯酸钠一鲁米诺化学发光体系的显著增敏作用，建立了反相流动注射一化学发光法测定氨基酸的新方法，该方法不需对氨基酸进行衍生或转化，可直接进行测定，方法简单、快速，其检出限为0.016林留mL，采样频率为150次爪，对1林岁血L的组氨酸进行连续12次平行测定，其RSD为0.9%。对氨基酸注射液样品中的氨基酸测定的回收率在98.6%一102.1%之间，并和经典的荀三酮比色法进行了对照，获得了满意的结果。更多还原

【Abstract】 Chitosan is a nontoxic natural alkali polysaccharide with excellent biocompatibility and medical function that abstracted from the shell of the crust outline animal such as shrimp or crab etc. It can easily form polymer metal complexes with many transitional metal cations and rare-earth metal ions for its extra electron pair of nitrogen. The metal complexes with chitosan or chitosan derivatives exhibit many splendid function in material application. As a good kind of complex material, it possesses a wonderful application foreground at many domains such as pharmaceutical carriers, fixing agent of enzyme, separative membrane.. man-made urea adsorbent , growth induced agent of nano microcrystal, chemistry catalyzes plant growth adjusted agent as well as metal separation and determination the content of metal etc.This thesis has studied the synthesis of the ferrous complexes of chitosan and its derivatives, for example chitosan-ferrous complex , chitosan-8-oxine-ferrous complex , different molecular weight chitosan-ferrous complex, chitosan-ferrous-N-salicylicdene glycine sciff base complex etc. The structure of the coordinating compounds were confirmed by IR spectra, UV-VIS spectra, element analysis and thermal analysis. Their sorption kinetics and thermal decomposition kinetics have been investigated and conjectured their structure. Their elementary application was studied too. The thesis is divided into seven parts: Part Ⅰ : Review.A review of the coordinate chemistry of natural macromolecule chitosan and its derivatives with transitional metal and their application is given.Part Ⅱ: Study of the adsorption kinetics and mechanism of ferrous ions on chitosanThe sorption isotherm and sorption kinetics of chitosan for ferrous ion have been investigated. Under the optimum sorption conditions of chitosan for ferrous ions, thecoordinating compound between chitosan and ferrous ion was obtained. The structure of the coordinating compound was confirmed by IR specie UV-VIS spectra , element analysis and thermal analysis. The results were satisfied with the Langmuir-single-molecule-layer adsorption mechanism and the Lagergren-one-order equation. The apparent adsorption activation energy is 20.23kJ/mol and the sorption rate constant of the Lagergren-one-order sorption is 0.25h-1 at 293.15K.Part Ⅲ: Thermal decomposition mechanism and non-isothermal kinetics of the complex of ferrous ion with chitosanThe chelating effect of ferrous ion on chitosan have been investigated. By optimizing with the condition to the adsorption of ferrous ion, we have got the comparatively ideal synthetic product outcome. By way of IR spectrum and UV-VIS spectrum corroborated the chelating effect between chitosan and ferrous ion, and using the element analysis and thermal analysis established the component of the chitosan-ferrous complex. The thermal decomposition of the complex and its kinetics were studied by non-isothermal thermogravimety. The stages of the decomposition were identified by TG-DSC curve. The most probable mechanism function and the kinetic parameters(the activation energy,E and pre-exponential constant,A) were obtained from comparing the kinetic parameters by differential and integral methods.Part Ⅳ: Synthesis of complexes of different molecular weight chitosan-Fe( Ⅱ) and their sorption capability of ureaThe optimum preparation craft of the different low-molecular weight chitosan were prepared by H2O2-HAC control oxidation method. It was synthesized three kind of chitosan with different low molecular weight(Mv is 870 thousand , 110 thousand and 10 thousand) and had obtained a series of their ferrous complexes by optimizing the coordinate conditions between low-molecular chitosan and ferrous. The optimal adsorption conditions of urea with different molecular weight chitosan-Fe(Ⅱ) complexes were studied. It was resulted that the complexes exhibit high sorptive capacity and good selectivity for urea. The sorption capacity was influenced by the metal content in the complex, time of sorpti更多还原