Protolytic properties of some bis(dimethylaminomethyl)phenols in the presence of surfactants

Aggregation and protolytic properties of bis(dimethylaminomethyl)phenols containing methyl (HA) and nonyl (HL) substituents at the benzene ring are studied in aqueous solutions of isopropanol and various surfactants with potentiometric titration, tensiometry, and mathematical modeling of equilibria. Monomers, dimers, and tetramers of HA and HL are found. It is shown that the degree of compound aggregation depends on the solution concentration and pH. Sodium dodecyl sulfate and HA form associates, whereas SDS and HL form mixed micelles at the CMC-1 and CMC-2 critical micellization concentrations. In micellar solutions of Triton X-100 and cetyltrimethylammonium bromide, the mixed micelles are not found via tensiometry. Protonated species of tetramer, dimer, and monomer of investigated compounds are revealed, depending on the acidity of the medium. Phenolate forms of HA and HL do not exist under experimental conditions. Apparent protonation constants are determined and it is shown that, for the HA compound that does not form micelles, the protonation constants of the same-type species increase in the presence of the three surfactants used as compared to the water-isopropanol solution. Decreasing constants of analogous HL forms in the solutions of CTAB, nonionic surfactant (C _Tx = 10 mM), and SDS (pH > 7) are attributed to the formation of associates or mixed micelles of this compound and surfactants under experimental conditions.     

Expansion over a system of shifts of pyramidal functions

A method for approximation of functions of two variables by a linear combination of nonnegative piecewise linear functions with a compact support is presented. The crucial idea of this method consists in an “integral” calculation method for the coefficients. The accuracy of the approximation in the spaces of continuous and integrable functions is proved to have the same order as the best approximation by piecewise linear functions.     

Quantum dissociation of a vortex-antivortex pair in a long josephson junction

The thermal and the quantum dissociation of a single vortex-antivortex (VAV) pair in an annular Josephson junction is experimentally observed and theoretically analyzed. In our experiments, the VAV pair is confined in a pinning potential controlled by external magnetic field and bias current. The dissociation of the pinned VAV pair manifests itself in a switching of the Josephson junction from the superconducting to the resistive state. The observed temperature and field dependence of the switching current distribution is in agreement with the analysis. The crossover from the thermal to the macroscopic quantum tunneling mechanism of dissociation occurs at a temperature of about 100 mK. We also predict the specific magnetic field dependence of the oscillatory energy levels of the pinned VAV state.     

Novel self-assembling system based on resorcinarene and cationic surfactant

Mixed association of calix[4]resorcinarene with ethyl sulfonate groups on the lower rim and dimethylaminomethyl groups on the upper rim (CR) and cationic surfactant 4-aza-1-hexadecyl-azoniabicyclo[2.2.2]octane bromide (DABCO-16) is studied by methods of tensiometry, conductometry, potentiometry and NMR spectroscopy at fixed CR concentration and varied surfactant concentration. Beyond ca. 0.4 mM of DABCO-16, mixed aggregates enriched by CR are proved to be formed due to electrostatic forces, while beyond ca. 5 mM, aggregates enriched by surfactant occur due to the hydrophobic effect. Spectrophotometry monitoring of the solubilization of a hydrophobic dye, Orange OT, demonstrated that only the second type of mixed aggregate enriched by DABCO-16 is capable of binding the organic probe, while the mixed system where the surfactant is a minor component shows no binding capacity towards Orange OT. This finding can be used for the design of nanocontainers with controllable binding/release properties.     

Catalytic Effect of Micellar Systems Based on Hydroxypiperidinium Surfactants in the Hydrolysis of a p-Nitrophenyl Phosphonate

Kinetics and Catalysis - The aggregation behavior, solubilization effect, and catalytic activity of hexadecylpiperidinium surfactants (including ones functionalized with hydroxyl substituents) have...