咪唑类离子液体的研究进展

咪唑类离子液体以其独特的物理化学性质和在众多领域的巨大应用潜能而引起广泛的关注.本文结合我们的研究工作,对近期国际上关于咪唑类离子液体的气-液和液-液平衡、咪唑类离子液体的表面活性剂行为、传统表面活性剂在咪唑类离子液体中聚集体的形成、表面活性剂/水(油)/咪唑类离子液体三元体系超分子自组装体形成等方面的一些主要研究成果进行了综合评述.在此基础上,提出了进一步开展非传统表面活性剂/离子液体体系超分子自组装体及离子液体结构对聚集体形成、结构、性质影响等研究的设想.     

胆酸盐参与的自组装及微纳米材料制备

胆酸盐类物质可看作是一类阴离子型甾族生物表面活性剂,鉴于其特殊的两亲性骨架结构、独特的物理化学性质及其良好的生物相容性和环境友好性,其在溶液中能够参与超分子自组装形成有序聚集结构,且可以作为模板在微纳材料制备领域有着重要应用。本文结合我们课题组的研究工作,综述了近期国内外相关研究,详细介绍了生物小分子氨基酸对胆酸盐聚集行为的影响、胆酸盐参与形成的超分子凝胶及胆酸盐参与构筑的微纳米材料制备等方面的研究进展,以期对胆酸盐参与的自组装及微纳米材料制备领域的研究有更全面更深入的了解,为后续的应用研究提供坚实的基础。     

PEO-PPO嵌段聚醚的聚集行为及其在药物载体领域的应用

聚氧乙烯-聚氧丙烯(PEO-PPO)嵌段聚醚是一类非离子型高分子表面活性剂,其结构具有很多独特之处:分子结构具有丰富的可设计性,强烈的温度依赖的胶束化行为以及溶剂选择的多样性,这些都极大丰富了其在溶液中自组装形成聚集体的研究内容。本文结合本课题组的工作着重综述了近期国内外有关线型和支状PEO-PPO嵌段聚醚在水溶液中聚集特性的研究进展,以及酸/碱、无机盐、醇类、小分子表面活性剂和聚合物等添加剂对其聚集行为的影响。PEO-PPO嵌段聚醚具有良好的生物相容性,在水溶液中能形成以PPO链段为疏水内核, PEO链段为亲水外壳的胶束结构,该结构非常适于作为疏水药物的载体。因此本文还综述了此类嵌段聚醚作为药物载体方面的研究成果,期望为药物剂型的开发研究提供理论支持。     

表面活性离子液体参与构筑的胶束体系

离子液体(ILs)的可设计性,使得新型表面活性离子液体(SAILs)不断涌现,从而将具有不同功能基团的ILs引入到了传统的有序分子聚集体中,这也将有助于实现有序分子聚集体的可控性和功能化。本文综述了SAILs在水溶液及离子液体中的胶束化行为,重点总结了烷基碳链长度、阴离子类型和阳离子结构对SAILs聚集行为的影响,分类归纳了SAILs与传统表面活性剂复配体系的协同增效作用,并探讨了SAILs构建的胶束体系的发展方向。     

新型表面活性剂研究进展--Bola型表面活性剂与Gemini型表面活性剂

对两类新型表面活性剂--Bola型表面活性剂和Gemini型表面活性剂,从结构特点、研究历史、水中的溶解性与Krafft点、表面活性与表面吸附、临界胶团浓度、水中的聚集体类型与转化、研究前景等方面进行综述.     

Gemini表面活性剂分子结构对其水溶液中聚集行为的影响

Gemini表面活性剂是通过联接基团将两个具有亲水亲油性质的两亲结构单元在其亲水头基上或靠近亲水头基处以共价键方式连接而成的一类表面活性剂。这类表面活性剂由于联接基团的引入具有比传统单链表面活性剂更高的表面活性,同时分子结构中更多的可调控因素使其在水溶液中表现出更为丰富的自聚集行为,而且分子不同部位结构的改变对分子内或分子间相互作用产生不同的影响,可实现通过分子结构的设计有效调控其自聚集能力和聚集体结构。本综述将从联接基团、烷基链、亲水头基、反离子和其它功能性基团这五个方面概述近些年Gemini表面活性剂水溶液中聚集行为方面的研究进展,总结人们对Gemini表面活性剂分子间相互作用规律的认识,期望对于进一步发展这类高效的表面活性剂体系提供有益的帮助。     

聚合物与表面活性剂相互作用的分子模拟研究进展

聚合物与表面活性剂复配体系已广泛应用于医药、生物、石油石化等领域。从微观上认识其相互作用机理对指导其生产实际有着重要作用,因而此方面的研究倍受关注。随着分子模拟技术的发展,聚合物与表面活性剂在分子水平上的相互作用机理研究已经被广泛开展,并获得了大量有用的信息。本文综述了耗散粒子动力学(DPD)和粗粒度分子动力学(CG-MD)在聚合物与表面活性剂相互作用方面的应用,分别对中性聚合物与离子型表面活性剂,以及带相反电荷的聚电解质和表面活性剂在溶液相和界面相的相互作用进行了阐述,并揭示了聚合物/表面活性剂聚集体结构形态的变化规律。     

大分子自组装特性计算机模拟的研究

包括表面活性剂在内的大分子在溶液中可以形成聚集体的特性,使其在工业和生活领域得到广泛的应用.研究其自组装特性对生命体内两亲大分子的聚集行为以及生物矿化和仿生合成的研究均具有重要意义.本文分别从分子热力学和分子动力学的角度,对以表面活性剂为主的大分子自组装特性计算机模拟的研究进展进行了综述,分析并展望了对大分子溶液体系理论模拟研究的发展前景。     

介观模拟方法研究高分子表面活性剂在水介质中的聚集行为

高分子表面活性剂已广泛应用于许多领域, 其构型复杂、分子量大等特点使其聚集行为不同于小分子表面活性剂. 从微观上认识其聚集行为可为应用提供指导, 因而此方面的研究倍受关注. 计算机模拟技术的发展使我们能成功地在微观或介观水平上获得高分子表面活性剂聚集行为的信息. 本文综述了耗散粒子动力学(DPD)和介观动力学(MesoDyn)在高分子表面活性剂聚集行为研究中的应用. 着重介绍了这两种介观模拟方法研究单一高分子表面活性剂溶液的相行为及其与低分子表面活性剂之间的相互作用, 揭示了实验中难以观测的微观相分离及聚集体结构形态的变化规律. 这些信息可以为实验研究提供指导和补充.     

酯基Gemini双季铵盐表面活性剂的研究进展

Gemini双季铵盐表面活性剂性能优异但生物和化学降解性差,在Gemini双季铵盐表面活性剂结构中引入酯基官能团可以提升产物性能。酯基Gemini双季铵盐表面活性剂含有酯基和双季铵盐基,具有高表面活性、吸附、絮凝、抗盐、湿润、乳化、杀菌防腐和易生物分解等优点,应用前景广阔。本文综述了酯基Gemini双季铵盐表面活性剂的合成路线、性能和石油化工的应用状况,结合发展需求对酯基Gemini双季铵盐表面活性剂的未来发展进行了分析和展望。     

Effects of pharmaceutical excipients on cloud points of amphiphilic drugs

The clouding behavior, i.e., formation of phase separation at elevated temperature (the temperature being known as cloud point (CP)), of three amphiphilic drugs, amitriptyline (AMT), clomipramine (CLP) and imipramine (IMP) hydrochlorides in the presence of various additives, like cationic surfactants (conventional and gemini), nonionic surfactants, bile salts, anionic hydrotropes, sodium salts of fatty acids and cyclodextrin has been investigated. These additives are generally used as drug delivery systems. The drugs used are tricyclic antidepressants. All the surfactants increase the CP of mixed micelles formed by cationic (conventional and gemini) and nonionic surfactants. Hydrotropes, bile salts and fatty acid salts, when added in low concentrations, increase the CP, whereas at high concentrations, they decrease it. β-Cyclodextrin behaves as simple sugar and decreases the CP of the drug solutions.     

Computer Simulations of the Formation of Bile Salt Micelles and Bile Salt/DPPC Mixed Micelles in Aqueous Solutions

Brownian dynamics simulations for a coarse-grained model have been performed to study the formation of micelles from bile salts and mixed micelles with dipalmitoyl-phosphatidylcholine (DPPC) in aqueous solutions. The particular association behavior of bile salts as facial surfactants was shown to be caused by their special molecular architecture with a hydrophilic and a hydrophobic side. The experimentally observed smooth transition into the micellar region with increasing concentration is reproduced. Micelle size distributions have been evaluated at different bile salt concentrations. Typical structures of pure bile salt micelles could be identified. The composition and the structure of mixed micelles have been studied in their dependence on the bile salt/lipid concentration ratio in the aqueous solution. We have found that the bile salt fraction in the mixed micelles increases considerably with increasing bile salt/lipid concentration ratio and decreasing micelle size. The structural and thermodynamic features of micelle formation in the aqueous bile salt solutions with DPPC, which we have studied with the coarse-grained model, are in good qualitative agreement with experimental findings.     

Physico-chemical behavior of bile salts

Roles and potential roles of bile salts in the human body and in health have been reviewed. The nomenclature of these biological amphiphiles, the mechanism of their formation in the liver and subsequent structural modifications in the enterohepatic cycle have been summarized. Emphasis has been placed on the controversies surrounding their physico-chemical properties, especially the patterns of their aggregation, and their ability to catalyze hydrolysis pathways in aqueous solution and to stimulate the activity of human milk lipase. The role of bile salts as biological surfactants and their participation in the dissolution of cholesterol gallstones, lipid solubilizatlon and absorption, and their ability to cause lysis of membrane surfaces has been discussed. Where possible, emphasis has been placed on the importance of the presence of monomers or small oligomers on the physico-chemical properties of these steroidal molecules.     

Bile Salts in Chiral Micellar Electrokinetic Chromatography: 2000–2020

Bile salts are naturally occurring chiral surfactants that are able to solubilize hydrophobic compounds. Because of this ability, bile salts were exploited as chiral selectors added to the background solution (BGS) in the chiral micellar electrokinetic chromatography (MEKC) of various small molecules. In this review, we aimed to examine the developments in research on chiral MEKC using bile salts as chiral selectors over the past 20 years. The review begins with a discussion of the aggregation of bile salts in chiral recognition and separation, followed by the use of single bile salts and bile salts with other chiral selectors (i.e., cyclodextrins, proteins and single-stranded DNA aptamers). Advanced techniques such as partial-filling MEKC, stacking and single-drop microextraction were considered. Potential applications to real samples, including enantiomeric impurity analysis, were also discussed.     

Estimation of critical micelle concentrations of bile acids by reversed-phase high performance liquid chromatography

The critical micelle concentration (CMC) for bile salts or other surfactants is defined as that solute concentration at which appreciable changes in such phenomena as light scattering, surface tension, or solubilization of other organic molecules occur, these changes indicating appearance of surfactant aggregates. The CMC thus reflects hydrophobic interactions of the surfactant with itself. The self-association of hydrophobic molecules resembles the partition of a solute into the lipophilic phase in reversed-phase high performance liquid chromatography (RPLC): Both processes can be considered as transfers of a molecule from an aqueous to a lipophilic medium. The critical micelle concentration of a particular bile salt, being a measure of its hydrophobic self-association, should therefore be correlated with its Chromatographic mobility since they are fundamentally related phenomena. Experimentally, significant correlations between these quantities are obtained, both for bile salts andn-alky1 sulfonates, and only microgram amounts of sample are required for RPLC measurements. Among three homologous series of bile salt surfactants, CMC values predicted from RPLC measurements agree, within a standard error of 7%, with CMC values determined directly. This suggests the applicability of reversed-phase liquid chromatography to the micro-scale determination of critical micelle concentrations of bile salts,n-alkyl sulfonates, and other homologous series of surfactants.This work was supported in Part by NIH Grants HL-07878 (W.H.E.) and AI-21873 (B.G.B.) and by a Fulbright Senior Fellowship (B.G.B.). This is paper LXXX in the series Bile Acids by W.H.E.Deceased March 29, 1986     

A potentiometric titration study on the dissociation of bile acids related to the mode of interaction between different head groups of nonionic surfactants with free bile salts upon mixed micelle formation in water

By constructing an elaborate set of potentiometric titration together with data analysis system, apparent acid dissociation indices (pK _a ^app ) for two bile acids were determined in the mixed surfactant system of bile salts (Sodium Deoxycholate, NaDC, and Sodium Chenodeoxycholate, NaCDC) with nonionic surfactants (Hexaethyleneglycol monon-dodecylether, C₁₂E₆, Decanoyl-N-methylglucamide, MEGA-10) in aqueous solution at ionic strength 1.5 as a function of mole fraction in the surfactant mixture. It was found that with increasing the bile salt concentration, pK _a ^app as well as pH showed an abrupt rise at a certain concentration of the bile salt being regardable as a critical micellization concentration (CMC) and reached a constant value at the range sufficiently higher than CMC for each pure bile salt system, meaning that the dissociation degree of carboxyl group in micelle is smaller than that in bulk. In the mixed systems of free bile salts with nonionic surfactants, the dissociation state of carboxyl groups in mixed micelles depends on the species of hydrophilic group of nonionic surfactants as well as on mole fraction in the surfactant mixture.     

Interfacial characterization of beta-lactoglobulin networks: displacement by bile salts

The competitive displacement of a model protein (beta-lactoglobulin) by bile salts from air-water and oil-water interfaces is investigated in vitro under model duodenal digestion conditions. The aim is to understand this process so that interfaces can be designed to control lipid digestion thus improving the nutritional impact of foods. Duodenal digestion has been simulated using a simplified biological system and the protein displacement process monitored by interfacial measurements and atomic force microscopy (AFM). First, the properties of beta-lactoglobulin adsorbed layers at the air-water and the olive oil-water interfaces were analyzed by interfacial tension techniques under physiological conditions (pH 7, 0.15 M NaCl, 10 mM CaCl2, 37 degrees C). The protein film had a lower dilatational modulus (hence formed a weaker network) at the olive oil-water interface compared to the air-water interface. Addition of bile salt (BS) severely decreased the dilatational modulus of the adsorbed beta-lactoglobulin film at both the air-water and olive oil-water interfaces. The data suggest that the bile salts penetrate into, weaken, and break up the interfacial beta-lactoglobulin networks. AFM images of the displacement of spread beta-lactoglobulin at the air-water and the olive oil-water interfaces suggest that displacement occurs via an orogenic mechanism and that the bile salts can almost completely displace the intact protein network under duodenal conditions. Although the bile salts are ionic, the ionic strength is sufficiently high to screen the charge allowing surfactant domain nucleation and growth to occur resulting in displacement. The morphology of the protein networks during displacement is different from those found when conventional surfactants were used, suggesting that the molecular structure of the surfactant is important for the displacement process. The studies also suggest that the nature of the oil phase is important in controlling protein unfolding and interaction at the interface. This in turn affects the strength of the protein network and the ability to resist displacement by surfactants.     

Micellar bile salt mobile phases for the liquid chromatographic separation of routine compounds and optical, geometrical, and structural isomers

Aqueous solutions of bile salts, i.e. sodium cholate (NaC), sodium deoxycholate (NaDC), and sodium taurocholate (NaTC), are characterized and evaluated as reversed-phase liquid chromatographic (RPLC) mobile phases. The separation of the ASTM-recommended RPLC test mix in addition to more than 50 other compounds on a C18 column demonstrates the viability of these bile salts as HPLC mobile phases. The Armstrong-Nome theory was applied and found to adequately describe the partitioning behavior of solutes eluted with these bile salts at low surfactant concentrations. The effect of alcohol additives on chromatographic retention and efficiency was also assessed. Not only are the bile salt molecules rigid and chiral, but they form helical micellar aggregates as well. Consequently, many isomeric compounds can be easily resolved with this mobile phase additive. The base-line resolution of some binaphthyl-type enantiomers with a standard C18 column and the bile salt micellar mobile phases is also demonstrated. In addition, these bile salt mobile phases may be preferable to conventional hydroorganic mobile phase systems for the separation of many classes of routine compounds. A brief prospectus on the future utilization of bile salts in liquid chromatography is presented.     

Synthesis and aqueous solution properties of homologous gemini surfactants with different head groups

A series of homologous gemini surfactants possessing identical hydrophobic chains but different ionic head groups (cationic, anionic, zwitterionic) were synthesized, and their aqueous solution properties were examined. The results showed that the surface activities of gemini surfactants are superior to those of corresponding conventional monomeric surfactants, and molecular arrangements of gemini surfactants at the air-water interface are tighter than those of corresponding conventional surfactants. It was also found that zwitterionic gemini surfactant possesses the highest surface activity among the three surfactants. The behavior at the air-water interface is closely related to the molecular structural features of surfactants, which provide an indication for synthesizing highly-efficient surfactants.