青霉素G钾盐在CTAB胶束中的水解及其抑制

以紫外光谱法研究了青霉素G钾盐(Pen-K)在十六烷基三甲基溴化铵（CTAB）胶束体系中的水解反应, 并探讨了水解反应机理.结果表明, CTAB胶束对Pen-K的水解具有抑制作用; Pen-K在CTAB胶束体系水解时,体系pH值的变化与在水中相似, 表明H＋浓度对这种抑制作用影响较小.红外光谱和微极性研究表明,部分Pen-K钾盐定位于CTAB胶束栅栏层中, 增加了其稳定性.     

Effect of molecular structure on the solute-micelle and solute-stationary phase binding constants in micellar liquid chromatography

The effects of molecular structure on the solute-micelle and solute-stationary phase binding constants in micellar liquid chromatography (MLC) have been investigated. The following points have been observed. (1) There is quite a good linear relationship between the solute-micelle and solute-stationary phase binding constants in MLC with the cationic (CTAB) and anionic surfactants as the additives, which means that the contribution of physico-chemical properties of solutes on the solute-micelle and solute-stationary phase binding constants acts in a parallel way. (2) Good quantitative relationships between the solute-micelle and solute-stationary phase binding constants and the solvatochromic parameters have been obtained, which indicates that the distribution mechanism of the neutral solutes in MLC is determined via their molecular interactions. Both the cavity process and the hydrogen bond interaction play a very important role in the retention of neutral solutes in MLC. The contribution of the hydrogen bond interaction, especially the hydrogen donor ability of the solutes on those binding constants in anionic and cationic surfactant MLC, is determined in a different way. (3) Linear regression analysis of the solute-micelle and solute-stationary phase binding constants between the cationic and anionic surfactant MLC has been carried out. The obtained results suggest that the transfer of the non-polar solutes from the aqueous phase to the anionic and cationic surfactant micelles acts in a parallel way, but that of the polar solutes in a different way. A model of micelles with three different sites of solubilization, i.e., (1) the core of the micelle, (2) the surface of the micelle and (3) the palisade layer of the micelle, has been used to successfully explain the observed results. Finally, the retention behavior of solutes in MLC is compared with that in reversed-phase liquid chromatography (RP-LC). It has been observed that there is no difference in separation selectivity for the non-polar solutes between MLC and RP-LC; however, for the polar solutes, MLC provides a different separation selectivity compared to that in RP-LC.     

Non-ionic amphiphilic block copolymers by RAFT-polymerization and their self-organization

Water-soluble, amphiphilic diblock copolymers were synthesized by reversible addition fragmentation chain transfer polymerization. They consist of poly(butyl acrylate) as hydrophobic block with a low glass transition temperature and three different nonionic water-soluble blocks, namely, the classical hydrophilic block poly(dimethylacrylamide), the strongly hydrophilic poly(acryloyloxyethyl methylsulfoxide), and the thermally sensitive poly(N-acryloylpyrrolidine). Aqueous micellar solutions of the block copolymers were prepared and characterized by static and dynamic light scattering analysis (DLS and SLS). No critical micelle concentration could be detected. The micellization was thermodynamically favored, although kinetically slow, exhibiting a marked dependence on the preparation conditions. The polymers formed micelles with a hydrodynamic diameter from 20 to 100 nm, which were stable upon dilution. The micellar size was correlated with the composition of the block copolymers and their overall molar mass. The micelles formed with the two most hydrophilic blocks were particularly stable upon temperature cycles, whereas the thermally sensitive poly(N-acryloylpyrrolidine) block showed a temperature-induced precipitation. According to combined SLS and DLS analysis, the micelles exhibited an elongated shape such as rods or worms. It should be noted that the block copolymers with the most hydrophilic poly(sulfoxide) block formed inverse micelles in certain organic solvents.     

Micelles as pseudo-stationary phases in micellar electrokinetic chromatography

This review article describes some general comments on micellar electrokinetic chromatography (MEKC) from the viewpoint of pseudo-stationary phases and presents a compiled list of surfactants used for MEKC, prepared from published papers. We tried to give comments on some typical surfactants from the practical point of view.     

Synthesis of the composite material of polyaniline/NiO/sodium dodecylbenzenesulfonate in micelles

The composite material of polyaniline/NiO/sodium dodecylbenzenesulfonate (SDBS) is synthesized in SDBS micelles. The composite material has satisfactory conductivity and thermostability, and the particle length, width, and thickness are about 200–500 m, 3–5 m, and 40–96 nm, respectively.     

Dynamic light scattering and cryogenic transmission electron microscopy investigations on metallo-supramolecular aqueous micelles: evidence of secondary aggregation

Metallo-supramolecular diblock copolymers consisting of a polystyrene (PS) block connected to a poly(ethylene oxide) (PEO) block by a bis(terpyridine)ruthenium complex (PS₂₀-[Ru]-PEO _y ) were used to prepare aqueous micelles. The length of the PS block was kept constant, while two PEOs of different molecular weight were used. The resulting hydrated micelles and aggregates were characterized by a combination of cryogenic transmission electron microscopy (cryo-TEM) and dynamic light scattering measurements. The results were compared to those obtained for a covalent counterpart (PS₂₂-b-PEO₇₀). Cryogenic transmission electron microscopy allowed visualization of the PS core of the micelles. Moreover, the aggregates result from clustering of individual micelles.     

Interaction of Sodium Dodecyl Sulfate with Poly(ethyleneimine) in Bulk Solution and at the Air-Solution Interface

Interaction of sodium dodecyl sulfate (SDS) with the cationic polyelectrolyte poly(ethyleneimine) (PEI) was investigated in this study. Turbidity measurements were performed in order to analyze the interaction and complex formation in bulk solution as a function of polymer concentration and pH. Surface tension measurements were made to investigate the properties of SDS/PEI/water mixtures at air/solution interface. Results revealed that SDS/PEI complexes form in solution depending on the surfactant and polymer concentration. A decrease was observed in surface tension values in the presence of SDS/PEI mixtures compared to the values of pure SDS solutions. Both solution and interfacial properties exhibited pH dependent behavior. A shift was seen in the critical micelle concentration of SDS solutions as a function of PEI concentration and solution pH. Monovalent and divalent salt additions showed some influence on the interfacial properties of SDS solutions in the presence of PEI.     

Micellar Mediated Halodecarboxylation of α,β‐Unsaturated Aliphatic and Aromatic Carboxylic Acids—A Novel Green Hunsdiecker–Borodin Reaction

A Novel Hunsdiecker‐Borodin reaction (HBR) has been carried out efficiently with α,β‐unsaturated aliphatic and aromatic carboxylic acids by using N‐halo succinimides such as N‐chloro succinimide (NCS), N‐bromo succinimide (NBS), and N‐iodo succinimide (NIS) under micellar media. The reaction with α,β‐unsaturated aromatic carboxylic acids afforded β‐halo styrenes in excellent yield while α,β‐unsaturated aliphatic carboxylic acids underwent decarboxylation and to give corresponding halo derivatives. The reactions are dramatically accelerated in micellar media. This procedure works efficiently in CTAB (cetyl trimethyl ammonium bromide), SDS (sodium dodecyl sulfate), and TX (Triton‐X‐100) media under stirred conditions at room temperature. At reflux temperatures the yield of reaction products were further enhanced from good to excellent.     

The intragastrointestinal fate of paclitaxel-loaded micelles: Implications on oral drug delivery

The goal of the present study is to elucidate the intragastrointestinal fate of micellar delivery systems by monitoring fluorescently labeled different micelles and the model drug paclitaxel (PTX). Both in vitro and ex vivo leakage studies showed fast PTX release in fluids while micelles remained intact, except in fed-state simulated intestinal fluid and fasted-state pig intestinal fluid, thus referring to the intact absorption of micelles and PTX leakage in the gastrointestinal tract with d-α-tocopherol polyethylene glycol 1000 succinate (TPGS) micelles showing higher stability than other micelles. All groups of micelles were absorbed intact in Caco-2 and Caco-2/HT29-MTX cell models and the absorption of TPGS micelles was found to be higher than other micelles. The transport of the micelles across Caco-2/Raji (1.6%–3.5%), Caco-2 (0.8%–1%), and Caco-2/HT29-MTX (0.58%–1%) cell monolayers further verified the absorption of micelles and their subsequent transport; however, more TPGS micelles transported across cell monolayers than other groups. Moreover, the histological examination also confirmed that micelles entered the enterocytes and were transported to basolateral tissues and TPGS showed the stronger ability of penetration than other groups. Thus, these results are succinctly presenting the absorption of intact micelles in GIT confirmed by imaging evidence with prior leakage of the drug, uptake by enterocytes and the transport of micelles that survive the digestion by enterocytes and mainly by microfold cells in material nature dependent way with TPGS showing better results than other groups. In conclusion, these results identify the mechanism by which the gastrointestinal tract processes micelles and point to the likely use of this approach in the design of micelles-based therapies.     

Catalytic effect of CTAB on the interaction of dipeptide glycyl-tyrosine (Gly-Tyr) with ninhydrin

The effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) on the interaction of dipeptide glycyl-tyrosine (Gly-Tyr) with ninhydrin under varying conditions has been studied spectrophotometrically at 70 °C and pH 5.0. The reaction followed first- and fractional-order kinetics with respect to [Gly-Tyr] and [ninhydrin], respectively. Increase in total concentration of CTAB from 0 to 70 × 10⁻³ mol dm⁻³ resulted in an increase in the pseudo-first-order rate constant (k_ψ) by a factor of ca. 3. Quantitative kinetic analysis of k_ψ − [CTAB] data was performed on the basis of pseudo-phase model of the micelles (proposed by Menger and Portnoy and developed by Bunton) and Piszkiewicz model. A possible mechanism has been proposed and the kinetic data have been used to evaluate the micellar binding constants K_S (268 mol⁻¹ dm³ for Gly-Tyr) and K_N (64 mol⁻¹ dm³ for ninhydrin).