酶与有机溶剂

本文阐述了酶在有机溶剂中存在的两种形式:通过表面活性剂聚集体在有机溶剂中的溶解和直接以固态酶的形式悬浮于有机溶剂中.讨论了反胶团(或w/o微乳浊液)系统在酶促反应、选择性提取蛋白质等领域的应用和固态酶悬浮于有机溶剂中的性质和特点,并展望了这些系统的发展前景.     

外消旋苯丙氨酸的配位萃取拆分

以苯丙氨酸为研究对象，应用手性溶剂萃取拆分技术，考察了在含有配位金属离子和N－n－烷基化氨基酸的两相系统系统中被折拆分后苯丙氨丙氨酸对映体的分配行为。着重研究了在有机溶剂及水相中萃丙氨酸的初始浓度、萃取温度、配位金属离子等对萃取拆分效果的影响，结果显示，温度和浓度对萃取拆分的影响不大，而有机溶剂和配位离子对萃取拆分效果的影响较大。     

DNNSA反胶团萃取净化含镍电镀废水研究

研究了油水比、萃取剂浓度、萃取时间等对DNNSA反胶团萃取净化含镍电镀废水性能的影响,并采用图解法对逆流萃取理论级数进行了研究.结果表明:有机相煤油负载DNNSA反胶团萃取净化含镍电镀废水是可行的;提高油水比可以提高萃取效率;萃取时间为20 min达到萃取平衡;萃取剂浓度由0.005 7 M升高到0.446 M时,萃取效率提高了66.81%,即提高有机相中反胶团的数量有利于萃取反应的进行;DNNSA浓度为0.1 M时,其萃取容量约为3.57 g.L-1,多级逆流萃取理论级数为4级.     

A homochiral metal-organic porous material for enantioselective separation and catalysis

Inorganic zeolites are used for many practical applications that exploit the microporosity intrinsic to their crystal structures. Organic analogues, which are assembled from modular organic building blocks linked through non-covalent interactions, are of interest for similar applications. These range from catalysis, separation and sensor technology to optoelectronics, with enantioselective separation and catalysis being especially important for the chemical and pharmaceutical industries. The modular construction of these analogues allows flexible and rational design, as both the architecture and chemical functionality of the micropores can, in principle, be precisely controlled. Porous organic solids with large voids and high framework stability have been produced, and investigations into the range of accessible pore functionalities have been initiated. For example, catalytically active organic zeolite analogues are known, as are chiral metal-organic open-framework materials. However, the latter are only available as racemic mixtures, or lack the degree of framework stability or void space that is required for practical applications. Here we report the synthesis of a homochiral metal-organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantioselective manner. Our synthesis strategy, which uses enantiopure metal-organic clusters as secondary building blocks, should be readily applicable to chemically modified cluster components and thus provide access to a wide range of porous organic materials suitable for enantioselective separation and catalysis.     

反胶团法提取溶菌酶的研究

本文对AOT/异辛烷反胶团用于从鸡蛋清中萃取溶菌酶进行了研究.对商品AOT、精制AOT和重复使用的AOT加以比较后发现未经提纯处理的商品AOT对萃取虽有影响,但仍具实用性.AOT/异辛烷反胶团系统能有效地保护溶菌酶的活性.此外,对AOT浓度、水相pH值、离子强度等对萃取过程的影响也作了讨论.     

脂肪酶促Ketoprofen对映体选择性酯化反应--有机溶剂、助溶剂及添加剂的影响

系统研究了有机介质、助溶剂及添加剂对脂肪酶Novozym 435(Candida antarctica lipase B)催化的Ketoprofen的对映体选择性酯化反应的影响.以环己烷为反应介质,Novozym 435表现出较高的活性和对映体选择性;助溶剂及添加剂对Ketoprofen的立体选择性酯化反应有较大影响: 极性助溶剂苯和甲苯能提高酶反应的对映体选择性;添加少量的18-Crown-6能提高酯化反应速率和对映体选择性;在研究的范围内,N,N-二甲基甲酰胺(DMF)不能提高酶反应对映体选择性.     

反胶束系统稳定性的热力学分析

反胶束是表面活性剂在非极性的有机介质中形成的纳米级尺度的球状聚集体，属热力学稳定体系。文章从低界面张力效应、稀释效应、分散熵效应、弯矩效应四个方面对反胶束体系的稳定性作了唯象的分析，通过对反胶束形成过程体系自由能变化△F求极值。得到一个反胶束水池半径与体系物性参数的关联式。对关联式所作的分析表明。随着表面活性剂浓度的提高，反胶束水池半径有增大的趋势。与文献报道的实验规律一致。     

Reverse micelles extraction of nattokinase： From model system to real system

Nattokinase (also named subtilisin NAT) was pri- marily isolated from a traditional fermented food in Japan, ‘‘Natto’’, by Sumi et al.[1]. Since then more and more reports of pharmacological researches on natto- kinase demonstrated that nattokinase showed many advantages, such as longer half life, greater fibrinolytic activity than plasmin, availability for both oral admini- stration and intravenous instillation, both preventive and therapeutic measure against thrombosis, less risk of he…     

复合反应的胶束催化研究Ⅱ—— CTAB胶束对结晶紫褪色反应的影响

研究了在５．００×１０－３ｍｏｌＬ－１ＮａＯＨ溶液中,表面活性剂ＣＴＡＢ胶束对结晶紫褪色反应的影响,建立了平行一级和二级反应胶束催化的数学模型,得出了胶束相中的一级和二级反应速率常数．实验结果表明,ＣＴＡＢ胶束对结晶紫的一级反应表现出催化作用,ＣＴＡＢ胶束相中的一级速率常数为本体相中一级速率常数的１６２５倍,而ＣＴＡＢ胶束对结晶紫的二级反应表现出禁阻作用,ＣＴＡＢ胶束相中的二级速率常数为本体相中二级速率常数的０．００７１１倍     

Iscom, a novel structure for antigenic presentation of membrane proteins from enveloped viruses

We describe here a novel type of immunostimulating complex, called 'iscom', in which virus membrane proteins are presented in a multimeric form. The matrix of the iscom is the glycoside Quil A (Spikoside; Iscotec AB), extracted from the bark of Quillaja saponaria Molina, which forms micelles at the critical micellar concentration of 0.03%. In micelle form, Quil A probably has regions accessible for hydrophobic interaction with the membrane proteins so that it can form complexes with them. Iscoms have been prepared with membrane proteins of para-influenza-3 (PI-3), measles and rabies viruses, and their immunizing potency tested in animals. In these experiments, iscoms prove to be at least 10 times more potent than micelles formed by aggregation of the membrane proteins alone. Iscoms of PI-3 and measles viruses also stimulate the formation of antibody to the fusion (F) protein, which is considered to be poorly immunogenic. No side effects of iscoms or of protein micelles have been observed.     

Mechanism of silk processing in insects and spiders

Silk spinning by insects and spiders leads to the formation of fibres that exhibit high strength and toughness. The lack of understanding of the protein processing in silk glands has prevented the recapitulation of these properties in vitro from reconstituted or genetically engineered silks. Here we report the identification of emulsion formation and micellar structures from aqueous solutions of reconstituted silkworm silk fibroin as a first step in the process to control water and protein-protein interactions. The sizes (100-200 nm diameter) of these structures could be predicted from hydrophobicity plots of silk protein primary sequence. These micelles subsequently aggregated into larger 'globules' and gel-like states as the concentration of silk fibroin increased, while maintaining solubility owing to the hydrophilic regions of the protein interspersed among the larger hydrophobic regions. Upon physical shearing or stretching structural transitions, increased birefringence and morphological alignment were demonstrated, indicating that this process mimics the behaviour of similar native silk proteins in vivo. Final morphological features of these silk materials are similar to those observed in native silkworm fibres.     

反胶束萃取纤维素酶

研究了十六烷基三甲基溴化铵－异辛烷－正辛醇反束溶液萃取纤维素酶的性能,考察了水相ＰＨ、离子度和种类,酶浓度以及有机相中表面活性浓度,助溶剂浓度,溶剂比等因素对萃取行为的影响,并从反胶束微观结构给予解释,同时选择出了萃取纤维素酶的可行条件。     

脲引起反相胶束酵母醇脱氢酶的紫外与荧光变化

比较了ＡＯＴ－异辛烷及水相两种体系中脲引起的酵母醇脱氢酶（ＹＡＤＨ）紫外和荧光变化。在水相反应系统中随着脲浓度增加（至３．０ｍｏｌ／Ｌ），酶活性迅速下降并全部失活，构象发生重大改变，２２０ｎｍ处的紫外吸收增加，荧光强度减小，３３６ｎｍ处的荧光峰红移１２ｎｍ至３４８ｎｍ，在Ｒ＝１５的反相胶束体系中，酶浓度相同时ＹＡＤＨ活力相当于水相ＹＡＤＨ的６３％左右，但脲浓度增至３．０ｍｏｌ／Ｌ时ＹＡＤＨ的活力基本无变化，２４０ｎｍ和２７０ｎｍ处的紫外吸收峰、３５７ｎｍ处的荧光发射峰均随着脲浓度的增加有所升高。上述结果表明脲对两种体系中ＹＡＤＨ的分子构象和活力的影响是不同的     

Enantiospecific electrodeposition of a chiral catalyst

Many biomolecules are chiral--they can exist in one of two enantiomeric forms that only differ in that their structures are mirror images of each other. Because only one enantiomer tends to be physiologically active while the other is inactive or even toxic, drug compounds are increasingly produced in an enantiomerically pure form using solution-phase homogeneous catalysts and enzymes. Chiral surfaces offer the possibility of developing heterogeneous enantioselective catalysts that can more readily be separated from the products and reused. In addition, such surfaces might serve as electrochemical sensors for chiral molecules. To date, chiral surfaces have been obtained by adsorbing chiral molecules or slicing single crystals so that they exhibit high-index faces, and some of these surfaces act as enantioselective heterogeneous catalysts. Here we show that chiral surfaces can also be produced through electrodeposition, a relatively simple solution-based process that resembles biomineralization in that organic molecules adsorbed on surfaces have profound effects on the morphology of the inorganic deposits. When electrodepositing a copper oxide film on an achiral gold surface in the presence of tartrate ion in the deposition solution, the chirality of the ion determines the chirality of the deposited film, which in turn determines the film's enantiospecificity during subsequent electrochemical oxidation reactions.     

胶束纸色谱法分离酚类物质

应用不同电荷的水溶性表面活性剂(正相胶束)纸色谱法分离酚类,研究胶束溶液在其临界胶束浓度前后及有机添加剂对分离的影响。     

Review on aggregation of acid extractants in solvent extraction of metal ions: remark on the general model

The aggregation behavior of various acid extractants in the solvent extraction systems of metal ions is re-examined and explained according to knowledge obtained in recent work. The conclusions are as follows. (1) Complexes formed by the extractants and metal ions can form reversed micelles in organic diluents, depending on the microstructures of the complexes. The dimers of the acid extractant cannot percolate to the metal-extractant aggregates, and the acid-salt complexes are always formed in the aggregates. The reversed micelles or the W/O microemulsions formed by different species cannot be associated with each other to form a unified aggregate. (2) In solvent extraction systems, hydration of the extractants and metal ions can be considered as the driving force of forming reversed micelles. (3) Information of the first approach to the insight of the bicontinuous microemulsion of NaDEHP shows that various components in the aqueous phase behave confined and very similar to the typical AOT/n-heptane W/O microemulsions. (4) In the extraction of lanthanide ions by the W/O microemulsion of sodium naphthenate, the saponification is a process of forming reversed micelle or W/O microemulsion, while the extraction step is a process of destroying reversed micelles or W/O microemulsion droplets.     

Synthesis and characterization of chiral mesoporous silica

Chirality is widely expressed in organic materials, perhaps most notably in biological molecules such as DNA, and in proteins, owing to the homochirality of their components (d-sugars and l-amino acids). But the occurrence of large-scale chiral pores in inorganic materials is rare. Although some progress has been made in strategies to synthesize helical and chiral zeolite-like materials, the synthesis of enantiomerically pure mesoporous materials is a challenge that remains unsolved. Here we report the surfactant-templated synthesis of ordered chiral mesoporous silica, together with a general approach for the structural analysis of chiral mesoporous crystals by electron microscopy. The material that we have synthesized has a twisted hexagonal rod-like morphology, with diameter 130-180 nm and length 1-6 micro m. Transmission electron microscopy combined with computer simulations confirm the presence of hexagonally ordered chiral channels of 2.2 nm diameter winding around the central axis of the rods. Our findings could lead to new uses for mesoporous silica and other chiral pore materials in, for example, catalysis and separation media, where both shape selectivity and enantioselectivity can be applied to the manufacturing of enantiomerically pure chemicals and pharmaceuticals.     

姜黄素PLGA-PEG-PLGA胶束的制备及理化性质研究

本文以膜透析法制备载药胶束,研究了载体材料用量、药物投入量、透析时间、溶剂等对胶束的载药量、包封率及粒径的影响。对所制得胶束的理化性质如粒径分布、微观形态及体外释放进行了研究。采用UV法研究姜黄素溶液对照和姜黄素载药胶束的体外释放,对其释放曲线进行拟合。结果显示采用膜透析法制备的PLGA PEG PLGA载药胶束,平均粒径26.29 nm,包封率(70.03±0.34)%,载药量(6.4±0.02)%。姜黄素对照溶液和姜黄素胶束体外释放分别符合双指数双相动力学模型。     

不对称催化氢化反应研究

不对称催化氢化反应具有完美的原子经济性和清洁高效等特点,是最受青睐的不对称合成方法之一。虽然人们已经发展了很多用于不对称催化氢化的催化剂,但是这些催化剂往往存在稳定性差、活性低、底物适用范围窄、反应条件苛刻等问题,真正高效的手性催化剂很少。通过系统深入的研究,发展了30多个用于不对称氢化反应的原创性手性螺环催化剂,实现了潜手性酮、α-取代羰基化合物、不饱和羧酸、非保护烯胺等4大类20多种不对称氢化反应,反应的活性和对映选择性处于目前的最好水平,其中部分反应已经被用于手性药物及其中间体的生产,在国内外产生了重要影响。     

Inverse Thermal-Responsive Glyco-Polypeptide Polymer for One-Pot Glyco-Affinity Proteomic

1 Introduction Proteins are ultimately responsible for the biological processes in cells, body fluids, and tissue specimens. This presents enormous challenges to the field of proteomics, which aims to identify, characterize and assign biological functions of all proteins. Determining individual protein in complex biological samples often requires some type of separation as a prerequisite for its measurement. The complexities of chemical structure and in the physiological function of every prot…