Effects of surfactants on enzyme-containing reversed micellar system

With the development of colloid interface and enzyme technologies,enzyme-containing reversed micellar system has been receiving much attention in bioseparation and bioconversion. Because of its high efficiency,it has brought new opportunities for the development of molecular biotechnology. Reversed micelles represent nano-sized aqueous droplets stabilized by surfactant amphiphiles inside the bulk organic solvents. The entrapped enzymes have enhanced activities under those conditions as suited in the lipid b...     

Reactions in micellar systems

The notion of "green chemistry" has encouraged even synthetic organic chemists to include water as a solvent. Incredible selectivities and activities can be achieved through the addition of amphiphiles with a defined structure. The morphology of supramolecular assemblies or associates formed by surfactants vary according to the temperature and concentration. As a rule, reactions are typically conducted using simple spherical aggregates, that is, micelles in the nanometer range. The strong polarity gradient present between the hydrophilic surface and the hydrophobic core of the micelle means that both nonpolar and polar reagents can be solubilized. This solubilization results in reactants becoming more concentrated within the micelle than in the surrounding water phase and leads to an acceleration of the reaction and causes selective effects. The kinetic treatment of reactions in micellar systems can be accomplished by considering them as microheterogeneous two-phase systems.     

Control of separation selectivity in micellar electrokinetic chromatography by modification of the micellar phase with solubilized organic compounds

On the basis of the data on the distribution of various neutral solutes between sodium dodecyl sulfate (SDS) micelles and water, the control of separation selectivity in micellar electrokinetic chromatography (MEKC) by modification of the micellar phase with organic additives has been proposed and applied to the separation of simple model compounds. It was found that the distribution constants between the micelles and water (K_d,mc), which were determined by means of MEKC, of the solutes possessing hydrophilic functional groups are much larger than those between heptane and water (K_d,hep), whereas the K_d,mc values of the solutes possessing no hydropholic groups are comparable to their K_d,hep values. This indicates that the former solutes are preferentially solubilized in the Stern layer of the micelles and that the latter are located in the hydrocarbon core. In MEKC separations of aromatic compounds and metal acetylacetonates, considerable changes in separation selectivity were caused by the addition of compounds possessing both hydrophilic functional groups such as alcohols, phenol and ketones to the SDS micellar solution. The variations of the retention factors of the analytes could be explained in terms of saturation of the solubilization sites in the Stern layer with the modifiers, specific interaction of the modifiers with the analytes via hydrogen bonding in the micelles, and expansion of the core volume with the hydrocarbon parts of the modifiers. Such effects of the micellar modification could improve the resolution as well as the selectivity of MEKC separations.     

表面活性剂在逆胶束酶反应系统中的作用机制

随着胶体界面科学与酶技术的发展,逆胶束酶反应系统作为酶等生物分子的高效分离或催化转化的介质体系,为分子生物技术的发展带来了新的机遇.表面活性剂分子特有的两亲性结构,能使微水相以纳米尺寸的水滴形式稳定在非极性有机溶剂中,为酶的活性保持提供了典型的类生物膜微环境.本文对逆胶束酶反应系统原理做简要介绍,并解析表面活性剂的浓度变化及其构型差异在逆胶束酶反应系统中的作用机制,综述近年来表面活性剂在逆胶束酶领域应用的最新成果,同时探讨了新型功能性表面活性剂在胶束酶学中的应用前景和研究趋势.     

Dye-sensitized photo-oxidation of amino acids in reversed micellar membrane mimetic system

The photochemistry of a novel photosensitizer H[TBC(O'Pr)4P(OH)],and the photo-oxidation of amino acids sensitized by H[TBC(OiPr)4P(OH)] have been investigated in the AOT/H2O/toluene reversed micellar system.Absorption and fluorescence measurements indicate that H[TBC(O'Pr)4P(OH)] can interact with the re versed micelles by adsorption to the micellar surface,resulting in the disaggregation of the sensitizer and the enhance ment of its photoactivity.In micellar solutions,H[TBC(O'Pr)4P(OH)] can efficiently photo-generate O2(Type Ⅱ mechanism) and O2(Type Ⅰ mechanism) as shown by stationary photolysis and ESR spin-trapping techniques Amino acids dissolved in water pools of reversed micelles can be photo-oxidized via Type Ⅱ mechanism as sensitized by H[TBC(O'Pr)4P(OH)].The photo-oxidation of tryptophan follows the first-order kinetics,while that of tyrosine is much slower.Kinetic studies of the photodynamic behavior in this microheterogeneous system shows that the micro-heterogeneity can alter the mechani     

Synthesis and electrophoretic concentration of nanoparticles of CdS in reversed micellar solutions

Stable organosols of cadmium sulfide are obtained via the ion exchange reaction of cadmium nitrate with sodium sulfide in reversed micellar solutions of Brij-30 in n-decane and are characterized by means of spectrophotometry, luminescence, photon correlation spectroscopy (PCS), and transmission electron microscopy (TEM). It is established that adding anionic surfactant AOT to organosols produces double electric layers on the surfaces of nanoparticles and contributes to an additional 50-fold electrophoretic concentration. Electrophoretic concentrates of cadmium sulfide nanoparticles (0.5 M) are obtained in cells with vertical orientation of the electrodes and periodic changes in polarity. The average diameter of the nanoparticles according to TEM data is 5 nm, considerably less than the hydrodynamic diameter found by PCS (70 nm), testifying to the complex structure of a mixed adsorption layer surrounding a nanoparticle.     

Evaluation of solute distribution coefficients in solubilized systems

A theoretical treatment is proposed for the determination of the distribution characteristics of a solubilizate between micellar and aqueous phases from the variation of the critical micelle concentration (CMC) with the molar ratio of components in the system. The theory has been tested by determining the distribution coefficient and free energy of solubilization of n-butanol in the n-butanol/sodium dodecyl sulphate/water system from CMC values determined by conductimetric techniques.     

Luminescent nanocomposite synthesized by sol-gel method in micellar solution of alkyl-polyglycoside with solubilized luminol

It is shown that micellar surfactant solution with solubilized luminophore dye luminol can be used to synthesize silicate nanocomposite with luminescent properties. In the course of its synthesis, micelles perform a dual role, i.e., they solubilize luminol in neutral media, in which it is poorly soluble, and catalyze the sol-gel process, as well act as a template for the silicate forming in situ. It is established that, upon the incorporation of dye into the silicate matrix, its luminescent properties not only retained, but the intensity of fluorescence increases substantially. It is suggested that the approach developed can be used to produce biosencors since, along with dye, it permits us to immobilize enzymes.     

Computer simulations of micellar systems

Works published during the last decade devoted to simulation of micellar solutions of different surfactants are reviewed. The main attention is focused on studying the local structure of spherical and cylindrical micelles and their surface layers in solutions, as well as problems relevant to self-aggregation kinetics.     

Second CMC in surfactant micellar systems

Experimental reports of surfactant systems displaying a second critical micelle concentration (second CMC) have been surveyed. It turns out that surfactant micelles usually show a growth behavior with some typical features. (i) Micelles grow weakly at low surfactant concentrations but may switch to a much stronger growth behavior at higher concentrations. The second CMC is defined as the point of transition from weakly to strongly growing micelles. (ii) Micelles are found to be non-spherically shaped below the second CMC. (iii) At the second CMC micelles are found to be much smaller, with aggregation numbers typically 100–200, than expected for flexible micelles. (iv) Micelles of intermediate size are present in a narrow concentration regime close to the second CMC. (v) Micelles grow much stronger above the second CMC than expected from a sphere-to-rod transition. The conventional spherocylindrical micelle model predicts a smooth growth behavior that contradicts the appearance of a second CMC. Modifying the model by means of including swollen end caps neither account for the presence of micelles with intermediate size, nor the strong growth behavior above the second CMC. Taking into account micelle flexibility is not consistent with the rather low micelle aggregation numbers observed at the second CMC. On the other hand, a recently proposed alternative theoretical approach, the general micelle model, have been demonstrated to take into account basically all features that are typical of experimentally observed micellar growth behaviors.     

Voltammetric behaviour of antimalarial drug artesunate in solubilized systems

The voltammetric behaviour of artesunate is studied at glassy carbon electrode in different buffer systems using square wave, differential pulse and cyclic voltammetric techniques. The peak current is linear with the drug concentration in the range 4.0-40 μg mL(-1) for serum, plasma and urine. The mean percentage recoveries of the drug, urine, plasma and serum samples are 98.6-100.2%. No electroactive interferences from the excipients and endogenous substance could be observed in the pharmaceutical dosage forms and in biological samples.     

Titrations of sulphonamides in cationic micellar systems

A titrimetric determination of some sulphonamides with 0.1 M sodium hydroxide in the presence of hexadecylpyridinium chloride is described. Potentiometric titrations are slow; visual titrations are satisfactory. The pK_a shift can be interpreted in the light of general micellar behaviour.     

Fate of excited probes in micellar systems

This article presents studies on the photophysical and photochemical behavior of probes within micellar systems: organized emulsifier/polymer aggregates; the intra- and interpolymer association of amphiphilic polymers; monomer-swollen micelles (microdroplets); and the interfacial layer. Pyrene (Py) as a probe is particularly attractive because of its ability to measure the polarity of its microenvironment. Dipyme yields information on the microviscosity of micellar systems. Probes such as laurdan and prodan can be used to explore the surface characteristics of micelles or microdroplets. The dansyl group has a special photophysical property that gives information about the local polarity and mobility (viscosity) of the microenvironment. The organized association of amphiphilic polymer and emulsifier introduces a heterogeneity in the local concentration of the reactants. This heterogeneity also results from the attractive interaction between hydrophilic monomer and emulsifier in the case when the monomer carries a positive charge and the counterpart a negative one, and vice versa. Some emulsifiers can bind to the amphiphilic copolymers by simple partitioning between the aqueous phase and the polymer--non-cooperative association. The interaction between micelles (microdroplets) and charged polymers leads to the formation of mixed micelles. Binding emulsifiers to these polymers was detected at emulsifier concentrations much below the critical micellar concentration (CMC). Emulsifiers often interact cooperatively with polymers at the critical aggregation concentration (CAC) below the CMC, forming micelle-like aggregates within the polymer. The CAC can be taken as a measure of interaction between the emulsifier and polymer. A decrease in the monomer fluorescence intensity of probe-labeled polymer results from increased excimer formation, or higher aggregates within the unimolecular polymeric micelles. An increase in the monomer fluorescence intensity of probe-labeled polymer within the micellar system can be ascribed to shielding of the probe chromophores by emulsifier micelles. The quenching of probe emission by (un)charged hydrophilic monomer depends on partitioning of the monomer between the aqueous phase and the micelles. Penetration of reactants into the interfacial layer determines the quenching of the hydrophobic probe by hydrophilic quencher, or vice versa. Quenching depends on the thickness, density and charge of the interfacial layer. Compartmentalization prevents the carbonyl compound and unsaturated monomer from coming into sufficiently close contact to allow singlet or triplet-monomer interaction. All negatively charged carbonyl probe molecules are quenched with significantly lower rates than the parent neutral hydrophobic benzophenone molecules, which were located further inside the aggregates. This results from the different conformation and allocation of reactants within the micellar system. In the reverse micelles, quenching depends on the amount of water in the interfacial layer and the total area of the water/oil interface.     

Dissociation of acids in aqueous micellar systems

Incorporation in charged micelles induces large pKa shifts for a number of acids of varying type. Analysis of the measurements in terms of simple electrostatic theory is reasonably satisfactory in view of uncertainties regarding the net charge on the micelle and the exact character of its surface. The behavior of the long-chain fatty acids, whose mode of incorporation in micelles is least uncertain, confirms the suggestion of others that the effective dielectric constant at the micellar surface is quite low.     

Mixed micellar systems of cleavable surfactants

Previous studies have shown that the alkaline hydrolysis of cleavable ester surfactants is strongly affected by aggregation. The alkaline hydrolysis of the cationic species decyl betainate (DB) is strongly enhanced by micellization, whereas the nonionic species tetra(ethylene glycol)mono-n-octanoate (TEO) is virtually protected when residing in aggregates. In the present work, mixtures of DB and TEO were studied at concentrations above the critical micelle concentration, and the rate of hydrolysis of each surfactant in the presence of the other was assessed. The micellar interaction parameter (beta) was determined from the critical micelle concentrations of various mixtures of the two surfactants. The result (beta = -2.4) indicates a moderate net attraction. The hydrolysis of the surfactants was monitored using 1H NMR. It was shown that the hydrolysis of DB exhibits the main characteristics of the pseudophase ion-exchange model and that the reaction rate decreases with an increasing molar ratio of TEO. There are indications that the hydrolysis rate parallels the expected total counterion binding to the mixed micelles. The hydrolysis of TEO was not affected by the presence of DB. However, complementary experiments showed that it is possible to accelerate or retard the hydrolysis of TEO by coaggregation with stable cationic or anionic surfactants, respectively.     

Contiguous versus segmented hydrophobicity in micellar systems

This paper addresses a question not yet posed systematically in surfactant chemistry: How do the colloidal properties of surfactants respond to insertion of non-hydrocarbon functionalities (i.e., ester groups) within chains that are normally entirely hydrocarbon? In answering this question, two classes of such chain-modified surfactants were discovered. One class forms only small aggregates with noncooperative self-assembly, low foaming, high areas of occupancy at the air/water interface, and weak solid-adsorption and solubilization properties. The other class is much more normal with regard to these properties and, in fact, can even exceed conventional surfactants in mesitylene solubilization. Differences between the two categories of chain-modified surfactants originate from the degree of segmentation of the hydrocarbon and, in particular, upon the location of the longest segment. Segmented hydrophobicity, having in principle a "hydrophobic potential" similar to that of a contiguous hydrophobicity of equal length, can induce aggregation but, concurrently, alters the mode of assembly into films and micelles.     

手性胶束中的不对称Micheal反主尖

本文研究了手性表面活性剂N,N-二甲基-N-十二烷基麻黄素溴化铵及N,N-二甲基-N-十六烷基麻黄素溴化铵所形成的手性胶束体系中,以六氢吡啶作为碱催化剂,硝基甲烷或硫酚对查耳酮类化合物的Michael加成反应.     

Membrane osmometry of aqueous micellar systems

Summary The number average micellar molecular weights,M _n , were determined with the application of membrane osmometry, for various nonionic and a cationic surfactant, in aqueous solutions. These results show that these micelles are monodisperse, as also reported by other investigators. The dependence ofM _n on temperature was also studied. It was found that both the nonionic and the cationic micelles showed an abrupt change in logM versus temperature plots. In the case of nonionics, the abrupt change was observed at approximately 30 °C lower than the cloud-point.Presented at the 25th Colloid-Meeting in Munich, October 13–15, 1971.     

Chemoselective direct amidation of fatty acids with furfurylamine without coupling reagents in reversed micellar microenvironment

Furan heterocyclic compounds derived from renewable sources are popular versatile candidates for the production of multifunctional macromolecular materials. These compounds are also used as hydrophobilization monomers for reversible polyadducts or as versatile building blocks in Diels-Alder reactions. In the present study, an efficient approach to chemoselective acylation of furfurylamine with a series of non-preactivated monocarboxylic or dicarboxylic long-chain fatty acids and some of their functionalized derivatives has been achieved via catalytic direct amidation in reversed micellar medium. A convenient and environmentally friendly method has been developed for furfurylamides via a dehydrative coupling reaction. For this purpose, a new cationic Brønsted-type sulfonic acid catalyst containing a hexadecyl alkyl chain was synthesized and fully characterized. The present catalytic reaction produced the respective N-furfurylamides materials in good to excellent yields. This study also confirms that the direct amidation of carboxylic acids with selected amine compounds can be successfully catalyzed by Brønsted acids. Its simplicity and high atom economy are the main advantages of this method.