反相微乳液中苯酚硝化反应选择性的研究

采用气相色谱内标法研究了苯酚在AOT/异辛烷/水、CTAB/正癸醇/异辛烷/水、DBSA/异辛烷/水3种反相微乳液中进行硝化反应的选择性;考察了表面活性剂种类、反应时间、反应温度以及反相微乳液的含水量等因素对反应选择性的影响.研究结果表明,苯酚在微乳液体系中的硝化反应具有明显的邻位选择性,阴离子表面活性剂DB-SA体系的邻位选择性最高,这与它同时具有微乳催化和酸催化作用有关.     

正负离子表面活性剂反胶团与反相微乳研究

研究了以癸烷为油相的十一烯酸癸胺正负离子表面活性剂体系对水的加溶作用。结果表明此体系在一定组成范围内可以形成均匀透明的反胶团或反相微乳液。升高温度和添加酸、碱、盐可以使形成反胶团或反相微乳的组成范围扩大。在正负离子表面活性剂中加入离子型表面活性剂、特别是负离子型表面活性剂,也有类似的作用。     

乳液中豆油水解产生的振荡反应

通过组份替换,系统地研究了酸强度、金属离子,表面活性剂复配等各种因素对乳液中豆油水解振荡反应的影响并进一步说明了振荡机理.     

MOFs在乳液中的可控生长

金属有机框架(Metal organic frameworks, MOFs)材料是金属离子与有机配体自组装形成的形貌可控的多孔晶体材料。表面活性剂的乳化作用是形成乳液的关键,其自组装形成不同形貌的胶束控制最终产物的形貌。因此,在MOFs的制备中,不同乳液体系中的胶束亦可以作为反应模板,从而调控MOFs的形貌。本文简要介绍了传统乳液、反相微乳液、无皂乳液和Pickering乳液的形成机理和特点。重点综述了近年来MOFs在不同乳液体系中可控生长研究。其中,利用无皂乳液法和Pickering乳液法是构建MOFs复合材料的理想思路。     

农药微乳液物理稳定性的探讨

介绍了微乳液在农药剂型中的研究和应用,分析和探讨了表面活性剂、助表面活性剂、溶剂等组分对微乳形成及物理稳定性的影响。     

光-碱双重可降解阳离子表面活性剂的合成与性能

以香草醛、溴代十二烷、硝酸等为原料,通过O-烷基化、硝化、还原、酯化、成盐五步反应,合成了一种含邻硝基苄酯的可光-碱双重降解的吡啶盐阳离子表面活性剂.中间体与目标产物都进行了1H NMR结构表征;所得阳离子表面活性剂的临界胶束浓度(CMC)值约为0.3 mol·L-1.以该表面活性剂为乳化剂,进行苯乙烯乳液聚合可以得到稳定的乳液,表明该表面活性剂具有良好的乳化性能.将乳液进行紫外光照2h,可明显观察到乳液破乳并变色.经光降解测试证实该表面活性剂可在光作用下降解;发泡测试表明该表面活性剂具备一定的发泡性能;pH降解测试表明表面活性剂可在pH为7～9下实现碱降解.     

十二烷基苯磺酸/异辛烷微乳液中脂肪酶催化合成异丁酸异戊酯

在十二烷基苯磺酸(DBSA)/异辛烷微乳液中进行了脂肪酶催化合成异丁酸异戊酯的反应, 考察了微乳体系的含水量w₀、溶解酶缓冲溶液的pH值、反应温度等因素对酯合成反应转化率的影响; 与前期研究的CTAB微乳体系进行比较发现, DBSA微乳体系中的酯合成反应速率明显增加, 短时间内的转化率显著提高, 在温和条件下反应9 h后, 转化率达90%以上; 通过DBSA体系中有酶与无酶条件下反应进程的比较得知, DBSA作为一种质子酸对酯合成反应具有一定的催化能力; 提出了该体系中微乳催化、酶催化和质子酸催化的三重催化机理.     

阳离子表面活性剂中相微乳的形成和特性

自1943年SdriAn。等人山发现微乳液体系并予以命名以来，对微乳液研究不断深入·微乳液是由油、水、表面活性剂和助表面活性剂组成的各向同性、透明的、热力学稳定的分散体系，微乳液可分为单相微乳液和多相微乳液问．中相微乳液是多相微乳液中，与过剩盐水相和过剩油相达到三相平衡的Winsor皿型微乳液，它在三次采油、日用化工、微环境、酶催化等方面具有特殊重要的应用I‘，‘］．近年来对阴离子表面活性剂中相微乳液的形成和特性进行了较多研究［5。8］．但对阳离子表面活性剂中相微乳液的研究，目前尚未见报导，本文以澳代十四烷基毗…     

适用于痕量金属离子迁移的微乳状液的制备及其迁移条件

研究了以气溶胶ＯＴ为表面活性剂与不同烃类的油性溶剂及不同醇类的助表面活性剂一起制备的油包水型微乳为Ｃｄ６２＋从水相或料相迁移到微乳中的影响，同时还观察了油水比和温度对金属离子迁移的影响，从而确定了适于痕量金属离子迁移的微乳体系和和Ｃｄ＾２＋为规范离子的迁移条件。     

碳氢表面活性剂在超临界CO_2中形成微乳液的研究进展

在超临界CO2中形成微乳液可以克服CO2对高分子量和亲水性物质溶解能力差的缺点。碳氢表面活性剂成本低,对环境友好,利用碳氢表面活性剂形成超临界CO2微乳液有利于工业应用,但绝大部分碳氢表面活性剂不能形成微乳液,所以需要对碳氢表面活性剂进行选择和设计。本文介绍了微乳液的形成、表征和评价,从表面活性剂的亲CO2性能和界面活性两方面,综述了碳氢表面活性剂的设计思路和进展。另外介绍了助表面活性剂对形成超临界CO2微乳液的作用,并对常规碳氢表面活性剂在助表面活性剂的作用下形成超临界CO2微乳液的体系进行了综述。最后,介绍了含碳氢表面活性剂的混合表面活性剂在形成超临界CO2微乳液方面的研究情况。     

AOT-正庚烷微乳状液的制备及迁移痕量金属离子的研究

研究了以二－(2－乙基已基)磺化琥珀酸钠为表面活性剂、以正庚烷为油性溶剂的W/O型微乳状液的形成及迁移痕量金属离子的行为,确定了制乳和迁移的适宜条件.在此条件下,一些金属离子可较完全地从水相或料相迁移到微乳相中,显示出较高的迁移率.     

Oxidation of self-organized nonionic surfactants

Nonionic surfactants containing a polyoxyethylene headgroup are known to slowly undergo oxidative degradation when exposed to air. The oxidation, which starts by abstraction of a hydrogen atom from a methylene group in alpha-position to an ether oxygen, is accelerated by metal ions. Silver ion mediated oxidation of a technical grade surfactant of this type, Brij 30, was investigated in two types of self-assembled systems, a water-in-oil microemulsion and a liquid crystalline phase. It was found that in both systems the longer homologues, i.e., the surfactant homologues that carry a longer polyoxyethylene chain, decompose faster than the shorter homologues. This trend was found to be more pronounced when the surfactant is present in a liquid crystal than in a microemulsion. The difference is explained in terms of differences in accessibility of the polyoxyethylene chains to the silver ions.     

Structural characterization and chemical response of a Ag-coordinated supramolecular gel

Supramolecular gels exhibit potential applications in the areas of sensors, nanodevices, drug and catalyst carriers, and so on. To develop a novel organogel with a multiresponse, we designed a component molecule bearing a pyridyl group for metal coordination and an amide group for the formation of intermolecular hydrogen bonding. A complex building block with a symmetrical structure was selectively constructed by the coordination of a silver cation to the organic component. The coordination existing in the complex and the hydrogen bonding existing between complexes were examined by IR, Raman, and 1H NMR spectroscopy. The gel formation and phase transition were examined by viscosity and differential scanning calorimetry measurements. The selection of metal ions for the formation of a gel has proved to be crucial as only the complex of a binary coordinated metal ion, Ag+, was found to form a gel structure. From the band shift of the L1 solution with different amounts of silver ion, the binding ratio of silver ion to L1 was estimated to be 1:2 and the calculated stability constant was 3.6 x 10(8) M(-2). On the basis of the analysis of X-ray diffraction and transmission electron microscopy results, we proposed a possible stacking structure of the complex in the fibrous aggregates. Of interest is that the organogel exhibits a 3-D network structure of a beltlike fiber composed of ordered lamellar arrangements of the coordinated complex and shows a rapid response to wide chemical stimulations such as anions I-, Br-, and Cl-, gases such as H(2)S and NH(3), and a change of pH.     

Properties and Applications of Cryptand‐22 Surfactant for Ion Transport and Ion Extraction

A non‐ionic cryptand‐22 surfactant consisting of a macrocyclic cryptand‐22 polar head and a long paraffinic chain (C₁₀H₂₁‐Cryptand‐22) was synthesized and characterized. The critical micellar concentration (CMC) of the cryptand surfactant in ROH/H₂O mixed solvent was determined by the pyrene fluorescence probe method. In general, the cmc of the cryptand surfactant increased upon decreasing the polarity of the surfactant solution. The cryptand surfactant also can behave as a pseudo cationic surfactant by protonation of cryptand‐22 or complexation with metal ions. Effects of protonation and metal ions on the cmc of the cryptand surfactant were investigated. A preliminary application of the cryptand surfactant as an ion‐transport carrier for metal ions, e.g., Li⁺, Na⁺, K⁺ and Sr²⁺, through an organic liquid‐membrane was studied. The transport ability of the cryptand surfactant for these metal ions was in the order: K⁺ ≥ Na⁺ < Li⁺ < Sr²⁺. A comparison of the ion‐transport ability of the cryptand surfactant with other macrocyclic polyethers, e.g., dibenzo‐18‐crown‐6, 18‐crown‐6 and benzo‐15‐crown‐5, was studied and discussed. Among these macrocyclic polyethers, the cryptand surfactant was the best ion‐transport carrier for Na⁺, Li⁺ and Sr²⁺ ions. Furthermore, a foam extraction system using the cryptand surfactant to extract the cupric ion was also investigated.     

Metallosurfactants of bioinorganic interest: Coordination-induced self assembly

This review covers selected surfactant ligands that undergo a change in aggregate morphology upon coordination of a metal ion, with a particular focus on coordination-induced micelle-to-vesicle transitions. The surfactants include microbially produced amphiphilic siderophores, as well as synthetic amphiphilic ligands. The mechanism of the metal-induced phase change is considered in light of the coordination chemistry of the metal ions, the nature of the ligands, and changes in molecular geometry that result from metal coordination. Of particular interest are biologically produced amphiphiles that coordinate transition metal ions and amphiphilic ligands of relevance to bioinorganic chemistry.     

A nucleophilic substitution reaction performed in different types of self-assembly structures

A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and potassium iodide has been performed in oil-in-water microemulsions based on various C12Em surfactants, i.e., dodecyl ethoxylate with m number of oxyethylene units. The reaction kinetics was compared with the kinetics of reactions performed in other self-assembly structures based on very similar surfactants and in homogeneous liquids. The reaction was fastest in the micellar system, intermediate in rate in the microemulsions, and most sluggish in the liquid crystalline phase. Reaction in a Winsor I system, i.e., a two-phase system comprising an oil-in-water microemulsion in equilibrium with excess oil, was equally fast as reaction in a one-phase microemulsion. The reactions in microemulsion were surprisingly fast compared to reaction in homogeneous, protic liquids such as methanol and ethanol. The rate was independent of the microstructure of the microemulsion; however, the rate was very dependent on the type of surfactant used. When the C12Em surfactant was replaced by a sugar-based surfactant, octyl glucoside, the reaction was much more sluggish. The high reactivity in microemulsions based on C12Em surfactants is belived to be due to a favorable microenvironment in the reaction zone. The reaction is likely to occur within the surfactant palisade layer, where the water activity is relatively low and where the attacking species, the iodide ion, is poorly hydrated and, hence, more nucleophlic than in a protic solvent such as water or methanol. Sugar surfactants become more hydrated than alcohol ethoxylates and the lower reactivity in the microemulsion based on the sugar surfactant is probably due to a higher water activity in the reaction zone.     

Study and Modeling of Metal Oxide Solubilization in (w/o) Microemulsions

Water-in-oil (w/o) microemulsions are very appealing reaction media due to their ability to provide huge surface of contact between water-soluble and oil-soluble reactants. Their application as reaction media, including the preparation of nanoparticles, is, however, limited to water soluble precursors. In this study, we present a first step scheme in a two-step process for the preparation of metal oxide nanoparticles starting from their water-insoluble metal oxide bulk powder. This step involves solubilizing the metal oxide in the water pools of the microemulsion with the aid of a solubilizing agent. The variables affecting the solubilizing capacity of iron and copper oxides, as examples of important metal oxides, in single HCl-containing AOT/water/isooctane microemulsions were investigated. The effect of the following variables on the solubilization capacity is reported, namely, mixing time, surfactant concentration, water to surfactant mole ratio (R), and the nominal concentration of HCl in the water pool. At 300-rpm, time-invariant concentration of the metals in the microemulsions was achieved in about 6 hours. These values were quoted as the solubilization capacity of the metal oxide at the corresponding conditions. Solubilization capacity increased linearly with the surfactant concentration and R, and portrait a power function with the nominal concentration of HCl in the water pool. A mathematical model previously derived to describe nanoparticle uptake by single microemulsion accurately accounted for the effect of the aforementioned variables on the solubilization capacity.     

Preparation of polyaniline-metal composite nanospheres by in situ microemulsion polymerization

Nanosized metal and polyaniline (PANi) composite spheres have been prepared via the polymerization of aniline using PdCl₂ or HAuCl₄ as the oxidant in a microemulsion system. The oxidization of aniline and the reduction of metal ion happened together during the reaction, yielding PANi and elemental metal simultaneously. The results of FTIR spectra suggested that the oxidation degree of PANi was affected by the initial ratio of metal ions to monomer in the microemulsion system. The PANi–metal nanospheres were characterized using X-ray photoelectron spectroscopy and the conductivity of the composite nanospheres was measured by conventional four-probe method. Scanning and transmission electron microscopy were used to show the morphology of the composites.     

Morphological control of calcium carbonate crystallized in reverse micelle system with anionic surfactants SDS and AOT

The influence of a surfactant over water on the polymorphism and crystal size of calcium carbonate produced by reaction crystallization in microemulsion systems was investigated in a mixing tank reactor. The crystallization was induced by the reaction between two aqueous micelle solutions (Na2CO3-CaCl2) stabilized by anionic surfactants, SDS (sodium dodecyl sulfate) or AOT (sodium bis(2-ethylhexyl) sulfosuccinate). With increasing surfactant ratio to water, the water-in-oil microemulsion was stably developed and the morphology of the calcium carbonate crystallized in the micelles sharply transformed from calcite to vaterite. The influence of SDS on the polymorphism and crystal size of calcium carbonate was much clearer than that of AOT. In addition, with AOT, certain step changes in the morphology and crystal size occurred around a surfactant ratio to water (R=[H2O]/[surfactant]) of 15 due to a two-phase separation of the microemulsion.