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磷酸盐/聚合物基分子印迹材料的制备与特性
Preparation and Characterization of Phosphate/Polymer-based Molecular Imprinting Materials
【作者】 高宁;
【导师】 成国祥;
【作者基本信息】 天津大学 , 材料学, 2007, 博士
【摘要】 本论文分别采用共沉淀法、煅烧法及模板法制备了多种磷酸盐;采用混熔法制备了银基磷酸盐/聚氯乙烯基材料;采用反相悬浮法制备了磷酸钙/海藻酸钙复合微球;采用溶出法制备了磷酸盐/聚氯乙烯基离子印迹材料;采用硅烷交联法制备了磷酸钙/海藻酸钙分子印迹复合微球。并对上述磷酸盐/聚合物基材料的制备、结构和特性分别进行了研究。从微生物与银系抑菌剂材料表面相互作用的角度出发,归纳了Ag+抑菌性能的更合理的评价方法,实验通过具体实验比较研究了TTC活性显色测定与平板培养活菌计数法、抑菌圈法等评价效果。通过银离子印迹磷酸盐/聚氯乙烯基材料制备即银基磷酸盐/聚氯乙烯基材料的溶出实验研究,探讨和提出了银离子的溶出及其在磷酸盐/聚合物基复合材料中的迁移模式。以磷酸钙/海藻酸钙复合微球为载体,以乙烯基三(β-甲氧基乙氧基)硅烷(A-172)和γ-氨基丙基三乙氧基硅烷(KH-550)硅烷为功能单体和交联剂,以甲基橙为模板,采用表面印迹技术,制备了磷酸钙/海藻酸钙分子印迹复合微球(CP/CA MICMs)。采用紫外分光光度计测试了MICMs的吸附和识别性能。研究表明,所得的印迹物对模板的吸附满足Langmiur吸附模型,其吸附速度和吸附容量与功能单体种类、载体类型、模板与功能单体的比率等因素有关。水相中模板和功能单体主要以静电作用和疏水作用相结合。MICMs对其模板分子表现出较好的分子识别性能,而在相同情况下未印迹的空白聚合物则无此识别特性。印迹复合微球的识别性能与功能单体种类、载体类型、模板与功能单体的比率和微球比表面积等因素有关。
【Abstract】 Calcium phosphate was fabricated via templates method and silver-based phosphate was prepared by co-deposition means. Silver-based phosphate/PVC was prepared by mixing and melting the silver-based phosphate and PVC powder. Calcium alginate/calcium phosphate composite microspheres were fabricated via inverse suspension (W/O) with chloroform and hexane as dispersed phase, ethyl cellulose as disperser, mixture of calcium phosphate and sodium alginate solution as dispersing phase and calcium chloride solution as the cross-linker. Ion imprinted phosphate/polyvinyl chloride was prepared by stripping means. The phosphate/polymer-based materials were characterized as far as their structure is concerned.From the viewpoint of the interaction of microorganism and the silver-based antibacterial, the more reasonable estimate methods were proposed. The test results indicated that the TTC active coloration determination and flat cultivation bacteria account methods were suitable for the estimation of contact antibacterial.The Ag+ dissolve behavior of the silver-based phosphate/PVC was determined in the dissolve tests. The transplant disciplinarian of Ag+ in the silver-based phosphate/PVC was discussed and proposed.Surface molecular imprinted calcium phosphate/calcium alginate composite microspheres (CP/CA MICMs) were synthesized by using CP/CA CMs as the supporting matrix, ethylenetri(β-methoxy)ethyoxysilane (A-172) andγ-amidopropyltriethyoxysilane (KH-550) as the functional monomers and crosslinking agents,and methyl orange as template in aqueous solution. The capability of CP/CA MICMs was tested by ultraviolet spectrophotometer. The result showed that CP/CA MICMs adsorbed their templates in the way of Langmiur, and their adsorption properties were influenced by the functional monomer, the carriers and the ratio of the template to the functional monomer. The functional monomers were showed to combine the templates mainly through electrostatic and hydrophobic interactions in the water system. The CP/CA MICMs exhibited a specific recognition to their templates. These abilities of CP/CA MICMs were influenced by the functional monomers, the carriers, the ratio of the template to functional monomers and the specific areas of the MICMs.
【Key words】 Calcium phosphate; Silver-based phosphate; PVC; Calcium alginate; silane; Antibacterial estimate; Dissolve; Ion imprinting; Calcium phosphate/calcium alginate; Composite microspheres; Silane crosslinking; Surface imprinting; Selective adsorption;