反胶团法在蛋白质萃取及超细微粒制备方面的研究进展

反胶团法作为新的萃取分离技术可以有效地分离生物活性物质。综述了反胶团有关的概念、理论，反胶团萃取蛋白质的基本原理、影响因素、理论模型、应用开发，以及反胶团制备超细微粒的基本原理和研究现状，提出了目前这些研究领域存在的问题与展望。     

二(2-乙基己基)磷酸铵反胶束萃取碱性氨基酸的研究

研究以二（２－乙基己基）磷酸铵表面活性剂在磺化煤油中形成的反胶束对碱性氨基酸的萃取。分别测定了该反胶束萃取氯化铵浓度为１．５，２．５，３．５和４．５ｍｏｌ／Ｌ的水溶液中的碱性氨基酸的分配系数，结果表明，该反胶束具有优良的萃取性能，可从无机盐浓度更高的氨基酸水溶液中萃取出氨基酸。     

络合萃取法提取L—苯丙氨酸转化液中的丙酮酸

选用三辛胺（TOA）萃取L－苯丙氨酸转化液中的丙酮酸,研究了萃取时间、稀释剂、萃取剂浓度、水相pH值对平衡常数的影响以及反萃条件。结果表明：萃取15min即可达平衡;pH值低对萃取有利,极性稀释剂有利于萃取,TOA浓度以0.4-0.6mol/L为好,2mol/L的NaOH可有效反萃丙酮酸。     

反胶团萃取中性蛋白酶的研究

本文以中性蛋白酶为对象，研究了水相ｐＨ值，离子强度、油水相体积比和酶液浓度等因素对反胶团萃取酶的影响。结果萃取率可达４０％。此外，本文对酶液的多级萃取过程也作了初步探索，结果表明，采用ＤＭＢＡＣ／正庚烷／正辛醇反胶团体系，选择最佳的萃取条件下，单级表明，一定浓度的酶液经三次萃取后，总的活性单位收率接近５０％，因而，反胶团萃取可望成为一种分离和提纯生物产品的新方法。     

反胶团萃取α－淀粉酶的优化实验

采用新型ＤＭＢＡＣ／正庚烷反胶团体系，进行萃取分离提纯α－淀粉酶．考察了表面活性剂浓度、ｐＨ、离子强度、温度等参数对萃取的影响，确定了优化工艺条件，单级萃取α－淀粉酶的总收率可达７８．０％．     

头孢唑啉钠在吐温80-硫酸钠液-固萃取体系中的分配行为

对头孢菌素类抗生素——头孢唑啉钠在吐温80-硫酸钠液-固萃取体系中的分配行为做了初步研究，试验了成相聚合物吐温80的体积分数、成相盐硫酸钠的浓度和体系pH值对头孢唑啉钠在吐温80固相中正萃取的影响；硫酸钠浓度对头孢唑啉钠在硫酸钠盐水相中反萃取的影响，结果表明：吐温80在体系中体积分数为12％，硫酸钠浓度为1．48mol／L，pH5．0时，吐温80固相对头孢唑啉钠的正萃取率为72．0％；正萃取后，收集并溶解吐温80固相，调节二次成相硫酸钠浓度为0．53mol／L，pH9．0，硫酸钠盐水相对头孢唑啉钠的反萃取率为70％，结果表明，头孢唑林钠在该体系中有较高的萃取率和较好的稳定性。     

反胶团法萃取菜籽蛋白质工艺研究

研究了CTAB/异辛烷/正辛醇反胶团体系萃取分离菜籽蛋白质的前萃工艺.考察了水相pH、离子强度、原料加料量、萃取时间对菜籽蛋白质萃取率的影响,最后采用了四因素四水平正交实验,得出反胶团法分离菜籽蛋白质的前萃最优工艺条件为:菜籽粉加入量为0.6 g,KCl浓度0.09 mol/L,pH值7.0,萃取时间80 min.在最佳工艺条件下,前萃率可达70.19%.     

吐温80-硫酸钠液-固萃取分离头孢拉定

对头孢菌素类抗生素——头孢拉定在吐温80-硫酸钠液—固萃取体系中的分配行为做了初步研究。试验了成相聚合物吐温80浓度，成相盐硫酸钠浓度和体系pH对头孢拉定在吐温80固相中正萃取的影响，硫酸钠浓度对其在硫酸钠盐水相中反萃取的影响。结果表明：在吐温80在体系中的浓度为12％，硫酸钠浓度为1．48mol／L，pH7．5时，吐温80固相对头孢拉定正萃取率为58．2％；调整二次成相硫酸钠浓度0．63mol／L，pH3．5时，硫酸钠盐水相对头孢拉定反萃取率近95％。结果表明，头孢拉定在该体系中有较高的萃取率和较好的稳定性，显示吐温80-盐液—固萃取体系应用于分离抗生素等生物小分子有较大开发价值。     

膦氧化物萃取Au（CN）2^—

膦氧化物萃取剂Ｃｙａｎｅｘ９２１和Ｃｙａｎｅｘ９２３用于从金的氰化物溶液中萃取Ａｕ（ＣＮ）＾－２,反应可在常温下进行;煤油作稀释剂,锂盐作盐析剂,能明显提高萃取率;萃取反应在３ｍｉｎ即可达到平衡;Ｃｙａｎｅｘ９２１和Ｃｙａｎｅｘ９２３的萃取效果相近。在６０℃时,ＫＣＮ水溶液能将萃入有机相的Ａｕ（ＣＮ）＾－２完全反萃取出来。     

DMBAC反胶团体系萃取α—淀粉酶的研究

本文研究了表面活性剂DMBAC(十二烷基二甲基苄基氯化铵)在正庚烷有机溶剂中形成的反胶团体系对α—淀粉酶的萃取性能。考察了pH值、离子强度等因素对反胶团萃取α—淀粉酶的影响。研究结果表明,控制适当的条件,酶提取的总活性收率可达60％,用DMBAC反胶团体系,直接由工业生产发酵液中提取α—淀粉酶的实验研究,也取得了较好结果。     

Formation of Copolymer-Ag Nanoparticles Composite Micelles in Three-dimensional Co-flow Focusing Microfluidic Device

A novel method was presented to create composite micelles of amphiphilic copolymers and Ag nanoparticles(NPs) in a three-dimensional co-flow focusing microfluidic device(3D CFMD). Self-assembly of the copolymers was initiated by the fast mixing of water and a blend dispersion of hydrophobic Ag NPs and amphiphilic copolymers. At the same time, the hydrophobic Ag NPs enter the core of copolymer micelles, based on the hydrophobic interaction. The copolymer-Ag NPs composite micelles have a core-shell structure with copolymer shell and Ag NPs core. COMSOL Multiphysics is used to simulate the concentration distribution of copolymers and Ag NPs under different flow rates. Co-assembly microfluidic conditions are determined based on simulation results. Under suitable microfluidic conditions, both block copolymers and gradient copolymers can co-assemble with hydrophobic Ag NPs to form composite micelles, respectively. This microfluidic coassembly method will have a good prospect in the preparation of composite micelles of amphiphilic copolymers and metal nanoparticles.     

The effect of umbrella-type branching on the blood circulation and tumor targeting of star-branched PLA-PMPC copolymer micelles

The effect of branching on the blood circulation and tumor targeting of polymer nanovehicles in vivo was investigated in this study. For the purpose, star-branched poly(lactic acid) and poly(2-methacryloyloxyethyl phosphorylcholine)(PLA-PMPC)copolymers with umbrella-type AB_3,(AB_3)_2, and(AB_3)_3 architecture were synthesized by branching at the PLA core. Micelles self-assembled from these copolymers were used to evaluate the effect of core branching on blood circulation and tumor targeting. The results showed that branching changed the behavior of polymeric self-assembly in solution, thereby changing the size and surface anti-fouling performance of the polymeric micelles. Moreover, star-branched copolymer micelles with a higher branching degree allowed their payload to persist better in blood(half-time prolonged from 7.1, 8.6 to 13.8 h) and for a 1.72-fold higher content at the tumor site. These studies suggest that raising the branching degree of amphiphilic copolymer potentially offers a promising strategy for the design of carriers capable of enhanced circulation and targeting in vivo.     

几种降解性脂肪族聚酸酐的合成及性能表征

通过高真空熔体缩聚法合成了下列几种基于脂肪癸二酸的共聚物：癸二酸－间苯二酸共聚物（ＰＳＡ－ＰＩＰＨ）、癸二酸－聚乙二醇共聚物（ＰＳＡ－ＰＥＧ）、癸二酸－酒石酸共聚物（ＰＳＡ－ＰＴＴＡ）、癸二酸与四氢呋喃－环氧乙烷共聚醚（Ｍｒ＝１５００）的共聚物（ＰＳＡ－ＰＥＧ／ＴＨＦ）．采用１Ｈ或１３Ｃ核磁共振分析、红外光谱分析、差示扫描量热法（ＤＳＣ）对获得的聚合物进行了分析和表证．测定了聚合物的熔点及特性粘数．ＤＳＣ测定结果表明ＰＳＡ－ＰＥＧ和ＰＳＡ－ＰＥＧ／ＴＨＦ具有较低的结晶度．实验表明ＰＳＡ－ＰＩＰＨ、ＰＳＡ－ＰＴＴＡ比ＰＳＡ具有更好的成膜性质．     

磷酸二异辛酯对SDSS反胶束提取蛋白质的影响及其量子化学研究

考察了磷酸二异辛酯（D2EHPA）的用量对用琥珀酸二油酯磺酸钠（SDSS）形成的反胶束体系提取细胞色素C（cyt—C）的影响。用量子化学DFT—B3LYP／6—31G＊方法全优化计算了SDSS阴离子的几何和电子结构，确证其反反式异构体较为稳定，较合理地解释了以相关反胶束提取蛋白质的实验事实。     

星状pH响应聚合物及其自组装胶束研究

研究了一种星状聚合物——金刚烷基聚己内酯-b-聚甲基丙烯酸二乙氨基乙酯-b-聚甲基丙烯酸单甲氧基聚乙二醇酯（Ad-（PCL-b-PDEAEMA-b-PPEGMA）₄）及其自组装胶束以用于阿霉素（DOX）递送.采用ROP和ARGET ATRP方法合成该聚合物，其自组装胶束具有良好的稳定性（CMC=3.4 mg/L）；DOX负载胶束在pH=5.0下的释放速率明显快于pH=7.4和pH=6.8.结果表明，pH响应Ad-（PCL-b-PDEAEMA-b-PPEGMA）₄胶束可作为抗癌药物靶向递送的潜在载体.     

CMC型高分子表面活性剂在稀溶液中分子聚集形态

采用激光光散射、荧光光谱对羧甲基纤维素型高分子表面活性剂在稀溶液中的分子形态进行了研究，发现高分子表面活性剂的表面张力等温线出现多折点现象。在低于临界胶柬浓度的稀溶液中，单个高分子表面活性剂分子趋向卷曲，疏水嵌段形成非极性微区，形成疏水嵌段为核亲水嵌段为壳的单分子胶柬，其形态不规则，粒径在100nm以下，尺寸分布较宽。     

稀土络合催化环氧丙烷聚合——Ⅱ聚环氧丙烷的结构分析

用(13)~C-NMR波谱研究了稀土聚环氧丙烷的微结构。通过分析不同水铝比的催化体系所得产物的(13)~C-NMR谱图,初步探讨了聚合机理。以Lorentz线型模拟不同级分聚合物的(13)~C-NMR谱,用计算机进行分峰处理。定量估算它们的等规度。用X-射线衍射方法测得不同微观结构聚环氧丙烷的结晶性。     

内交联型水性聚氨酯皮革光亮剂的合成

以PPG（聚环氧丙烷二醇）、BDO（1，4－丁二醇）、DMPA（二羟甲基丙酸）、三官能度高光泽性单体及TDI（甲苯二异氰酸酯）为原料合成了内交联型水性聚氨酯皮革光亮剂，讨论了合成工艺对产品性能的影响。     

Self-assembly of Gradient Copolymer Synthesized by Spontaneous Batch RAFT Emulsion Polymerization and Its Application on Encapsulating Ag Nanoparticles

The gradient copolymers of acrylic acid and trifluoroethyl methacrylate(coded as P(TFEMAgrad-AA)) were synthesized via reversible addition-fragmentation transfer(RAFT) emulsifier-free emulsion polymerization. The spontaneous batch feeding approach was used to control the gradient chain sequence. Transmission electron microscopy(TEM) analysis revealed that the P(TFEMA-grad-AA) can self-assemble to form spherical micelles, rodlike micelles or vesicles in selective solvents. Morphological transition of the P(TFEMA-grad-AA) micelles was sensitive to the water content of the dioxane/water mixed solvent. More interestingly, Ag nanoparticles(NPs) were encapsulated by the P(TFEMA-grad-AA) micelles during the selfassembly process. The gradient chain sequence made the Ag NPs easily enter the core of the micelles, even when P(TFEMA-grad-AA) had less hydrophobic fluoro-units and more hydrophilic units. TEM images with energy dispersive spectrometer indicated that the nanocomposite micelles consisted of a Ag NPs core and a gradient copolymer shell.     

Synthesis and Immobilization of Polystyrene-b-Polyvinyltriethoxysilane Micelles

Diblock copolymers polystyrene-block-polyvinyltriethoxysilane(PS-b-PVTES) were synthesized via atom transfer radical polymerization(ATRP), which self-assembled into spherical micelles in solvent of THF-methanol mixtures. The self-assembled micelles were immobilized by cross-linking reaction of VTES in a shell layer of micelles. The chemical structures of block copolymers and morphology of micelles were characterized in detail. It was found that the size of immobilized micelles was strongly affected by the copolymer concentration, composition of mixture solvent, and block ratios.