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用于清除亲脂性毒物的载体膜的制备及传质机理研究
Preparation of Carrier Membranes and Study on Mechanisms of Lipophilic Toxins Removal
【作者】 石巍;
【导师】 张凤宝;
【作者基本信息】 天津大学 , 化学工程, 2003, 博士
【摘要】 以氯甲基聚砜为基材,通过相转化法制备出具有底部贯通孔的非对称膜,通过胺化和羟基化反应,分别制得胺化聚砜膜和羟基化聚砜膜,再采用羰基二咪唑和双环氧烷两种活化试剂对其进行活化,将牛血清白蛋白固载在膜内,获得固定白蛋白促进传递膜。通过将固定载体膜内的质量传递与电阻电容回路中的电子传递相类比,提出适用于非对称膜固定载体促进传递的数学模型。该模型可较好地描述膜中的促进传递行为,并能有效预测膜内载体的适宜浓度。将所制备的促进传递膜应用于体外脱毒的模拟实验,该膜对亲脂性毒物-胆红素具有较高的清除性能。以20小时计,促进传递膜对结合胆红素的清除率为43.6%,而相应空白膜仅为3.4%。以尼龙膜为基膜,分别将亲水性物质-羟乙基纤维素和壳聚糖共价键合在膜上,制得尼龙-羟乙基纤维素复合膜和尼龙-壳聚糖复合膜。其中尼龙-壳聚糖复合膜具有胺基和羟基两种活性基团、良好的亲水性能、较佳的血液和生物相容性,可广泛应用于亲和微滤。再采用多种活化试剂将聚赖氨酸固载在膜内,制备了用于吸附胆红素的亲和微滤膜。以高浓度的茚三酮显色液与固体壳聚糖反应,再采用乙醇水溶液稀释反应液的方法,解决了固载在基材上壳聚糖含量的测定问题。本法所获得的标准曲线的线性相关性。建立了适用于真实吸附条件下的亲和膜分离机理的数学模型。该模型可有效准确地预测穿透时间和饱和时间,以及出口浓度随溶质浓度、轴向扩散程度、膜厚、流速等变化的影响。实验证明,本法所制备的亲和膜对胆红素具有较高的吸附容量和清除性能,并能通过简单的洗脱方式使其再生。
【Abstract】 An asymmetric membrane with finger-like and interlocking pores was made by the phase inversion process using chloromethyl polysulfone as matrix. Aminated and hydroxylated polysulfone membranes were prepared by amination and hydroxylation reaction, respectively. Then bovine albumin (BSA)-fixed membranes were obtained by crossed-linking albumin into porous membrane with 1,1’-carbonyldiimidazole and bisoxirane reagents, respectively.A mathematical model for facilitated transport in asymmetric membranes with fixed site carriers was derived by assuming an instantaneous, microscopic concentraion fluctuation in the membrane. An analogy was employed between the mass transfer for the faciliated transport with fixed carrier membrane and the electron transfer in a resistor-capacitor (RC) circuit. The utility of the model was demonstrated by experimental data, and the sensitivity analysis was carried out to show the effects of the parameters in the model on the facilitating factor. In addition, the optimized carrier concentration in the membrane was determined.The BSA-fixed membranes were used to remove lipophilic toxins, bilirubin, from the simulation plasma. The experimental results showed that the transfer rate of bilirubin was obviously enhanced after fixing albumin into the high-flux asymmetric membrane. The clearance of bilirubin was 43.6%, while blank membrane was only 3.4%.Activated membranes for covalent immobilization of hydroxyethyl cellulose (HEC) and chitosan were obtained by the reaction of microfilitration nylon membrane with activation reagents such as bisxirane, 1,1’-carbonyldiimidazole, epibromohydrin and formaldehyde. Chitosan-nylon composite membrane with two active group (-NH2 and -OH) had a hydrophilic surface and good blood compatibility, so it can be widely used in affinity separation. Immobilization of polylysine (PLL) onto HEC and chitosan-coated membranes via activation reagents provided PLL affinity membrane, respectively.A simple method for quantitative analysis of solid chitosan based on the ninhydrin reaction was achieved by diluting the reaction solution with 50% (v/v)<WP=4>alcohol aqueous solution. The reaction of chitosan with ninhydrin was sensitive and reproducible. Reliability of regressions: .A mathematical model including convection, diffusion and Freundlich adsorption was proposed and solved by finite difference method. It can be well used to explore the effects of axial diffusion, flow velocity, association kinetic and nonuniformities in membrane thickness, porosity and pore size on membrane performance. The results can be used to develop a basis for proper design, operation and application of affinity membrane based separation processes.Such PLL-HEC and PLL-chitosan affinity membranes were tested to adsorb bilirubin from the phosphate buffer solution and simulation plasma. The experimental results showed that they had a high affinity capacity for bilirubin. These membrane can be renewed by washing the membrane with NaOH solution, phosphate buffer solution and albumin solution.
【Key words】 fixed carrier; facilitated transport; affinity membrane; chitosan; bilirubin; mathematical model;
- 【网络出版投稿人】 天津大学 【网络出版年期】2003年 03期
- 【分类号】TB43
- 【下载频次】297