Micellar nanocontainers based on sterically hindered cationic phosphonium amphiphiles

Russian Chemical Bulletin - Self-aggregation processes in an H2O—DMF (10%) medium were studied for a homologous series of tri-tert-butyl(n-alkyl)phosphonium tetrafluoroborates (PIL-n, where n...     

Micellar and pre-micellar aggregates of oxyethylated calixarenes studied by ESR of spin probes and cyclic voltammetry

The critical micelle formation concentrations of oxyethylated calixarenes 9CO8 and 9CO16 were determined by the spin probe ESR method. A decrease in the current passing through the system was revealed during the electrochemical oxidation of the probe in the presence of 9CO8. The current decrease depends on the amphiphile concentration and is due to the fact that the surface of micellar and pre-micellar aggregates impedes the access of charged particles to the probe. The pre-micellar aggregation phase was found by ESR and electrochemistry of spin probes. The concentrations of amphiphilic substances, at which structural rearrangements for pre-micellar aggregation are observed, were elucidated.     

Volatile profiling reveals intracellular metabolic changes in <Emphasis Type="Italic">Aspergillus parasiticus</Emphasis>: <Emphasis Type="Italic">veA</Emphasis> regulates branched chain amino acid and ethanol metabolism

Background  

Filamentous fungi in the genus Aspergillus produce a variety of natural products, including aflatoxin, the most potent naturally occurring carcinogen known. Aflatoxin biosynthesis, one of the most highly characterized secondary metabolic pathways, offers a model system to study secondary metabolism in eukaryotes. To control or customize biosynthesis of natural products we must understand how secondary metabolism integrates into the overall cellular metabolic network. By applying a metabolomics approach we analyzed volatile compounds synthesized by Aspergillus parasiticus in an attempt to define the association of secondary metabolism with other metabolic and cellular processes.     

Regulation of the rate of hydrolysis of phosphorus acid esters in organized systems based on amphiphilic pyrimidinophanes

The aggregation and catalytic activity of supramolecular systems based on new macrocyclic dimeric surfactants (pyrimidinophanes) was studied both in the absence and in the presence of polyethyleneimine (PEI). It was found that the critical micelle concentrations measured by tensiometry were independent of the structure of surfactants. The morphology of aggregates was responsible for various characters of the catalytic effects of pyrimidinophanes in the hydrolysis of phosphonic acid esters. A less hydrophobic pyrimidinophane exhibited a typical effect of cationic surfactants to accelerate the reaction both in the absence and in the presence of PEI. Unlike cationic micelles, a heminal-type pyrimidinophane exhibited an anomalous behavior: it had no effect on the rates of hydrolysis of the substrates and did not inhibit the hydrolysis. Upon the addition of lanthanum ions, the catalytic activity of dimeric surfactants increased. The overall catalytic effect due to the action of supramolecular systems based on pyrimidinophanes, PEI, and lanthanum ions can increase the rates of hydrolysis of the substrates by three orders of magnitude, as compared with that of alkaline hydrolysis.     

Systems based on nonionic amphiphilic compounds: aggregation and catalytic properties

The micellization properties, solubilization capability, and catalytic effect of conventional nonionic surfactants and amphiphilic compounds of oligomeric (Tyloxapol) and polymeric (Synperonic F-68, Pluronic F-127) structure were compared. The systems studied demonstrate a marked catalytic effect toward basic hydrolysis of p-nitrophenyl laurate, which exceeds the effect of aqueous alkali solutions by two orders of magnitude. Correlations between the solubilization capacity of aggregates and their catalytic effect were observed. The maximum efficiency was found for the Tyloxapol solution. The synergetic enhancement of the catalytic effect was observed for the mixed Tyloxapol-cetyltrimethylammonium bromide systems in the presence of small amounts of cationic surfactant     

Inhibition of Alkaline Hydrolysis of Ethyl p-Nitrophenyl (Chloromethyl)phosphonate in the System Cationic Surfactant-Water-Electrolyte

The rate of alkaline hydrolysis of ethyl p-nitrophenyl (chloromethyl)phosphonate in micellar solutions of cationic surfactants decreases with increasing concentration of chloride, bromide, and salicylate ions. In the presence of electrolytes, the critical micell concentration of surfactants and the surface potential of micelles also decrease.     

Supramolecular catalytic systems based on calix[4]resorcinarene for nucleophilic substitution in phosphorous acid esters

The aggregation and catalytic effect in the reaction of hydrolytic decomposition of phosphorous acid esters are studied for series of systems such as calixarene (CA)-sodium dodecyl sulfate (SDS), CA-poly(ethylene imine) (PEI), SDS-PEI, and CA-SDS-PEI. Using dynamic light scattering, sizes of aggregates are determined, cloud point is estimated, and catalytic effect is studied. Data obtained are consistent with the assumption of the joint aggregation in systems studied. The possibility of the passage from 20-fold inhibiting effect to the catalysis (higher than the order of magnitude) of studied reaction by the immobilization of anionic nanoaggregates (nanoreactors) on a catalytically active polymer matrix is demonstrated. The possibility of the passage from microheterogeneous to heterogeneous system and the separation of catalyst from the products are established.     

Short-range order and twins in ordered titanium monoxide

The structure of annealed titanium monoxide TiO_1.087 containing monoclinic ordered phase Ti₅O₅ was studied by electron diffraction. Along with the set of structural, superstructural, and extra reflections, the diffraction pattern of titanium monoxide shows a set of plane diffuse fringes in the (112)_B1* section of the reciprocal lattice of the basis cubic structure B1. It is shown that some of the extra reflections are due to the twinning of the monoclinic superstructure along the (?1?11) plane of the reciprocal lattice of the basis cubic structure. The diffuse contours enclose plane areas of the reciprocal space with the fixed values of wave vectors K₁₀₀ ～ ±(h+0.07)k₁₀₀, K₀₁₀ ～ ±(k+0.07)k₀₁₀, and K₀₀₁ ～± (l+0.07)k₀₀₁ of the B1 structure. Their appearance is associated with the short-range displacement order.