A nucleophilic substitution reaction in microemulsions based on either an alcohol ethoxylate or a sugar surfactant

A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.

¹²⁷I NMR studies, as well as quadrupole splitting experiments performed by ²H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.

The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles.     

Sparse generalized Fourier transforms

Block-diagonalization of sparse equivariant discretization matrices is studied. Such matrices typically arise when partial differential equations that evolve in symmetric geometries are discretized via the finite element method or via finite differences. By considering sparse equivariant matrices as equivariant graphs, we identify a condition for when block-diagonalization via a sparse variant of a generalized Fourier transform (GFT) becomes particularly simple and fast. Characterizations for finite element triangulations of a symmetric domain are given, and formulas for assembling the block-diagonalized matrix directly are presented. It is emphasized that the GFT preserves symmetric (Hermitian) properties of an equivariant matrix. By simulating the heat equation at the surface of a sphere discretized by an icosahedral grid, it is demonstrated that the block-diagonalization is beneficial. The gain is significant for a direct method, and modest for an iterative method. A comparison with a block-diagonalization approach based upon the continuous formulation is made. It is found that the sparse GFT method is an appropriate way to discretize the resulting continuous subsystems, since the spectrum and the symmetry are preserved. AMS subject classification (2000)  43A30, 65T99, 20B25     

Glottal airflow and transglottal air pressure measurements for male and female speakers in soft, normal, and loud voice

Measurements on the inverse filtered airflow waveform (the "glottal waveform") and of estimated average transglottal pressure and glottal airflow were made from noninvasive recordings of productions of syllable sequences in soft, normal, and loud voice for 25 male and 20 female speakers. Statistical analyses showed that with change from normal to loud voice, both males and females produced loud voice with increased pressure, accompanied by increased ac flow and increased maximum airflow declination rate. With change from normal voice, soft voice was produced with decreased pressure, ac flow and maximum airflow declination rate, and increased dc and average flow. Within the loudness conditions, there was no significant male-female difference in air pressure. Several glottal waveform parameters separated males and females in normal and loud voice. The data indicate higher ac flow and higher maximum airflow declination rate for males. In soft voice, the male and female glottal waveforms were more alike, and there was no significant difference in maximum airflow declination rate. The dc flow did not differ significantly between males and females. Possible relevance to biomechanical differences and differences in voice source characteristics between males and females and across loudness conditions is discussed.     

Heterogemini Surfactants Based on Fatty Acid Synthesis and Interfacial Properties

A series of novel nonionic surfactants based on fatty acids, each with two hydrophilic and two hydrophobic groups in the molecule (so-called Gemini surfactants), have been synthesized. The hydrophobic part of the surfactant, made from oleylnitrile, has a double bond in the middle of the chain to which the hydrophilic part is attached. One of the hydrophilic groups is a methyl-capped polyoxyethylene chain with 11 or 16 oxyethylene units, whereas the other is a secondary hydroxyl group. The reason for using the nitrile derivative of the fatty acid instead of a more conventional derivative such as an ester or amide is to achieve good hydrolytic stability, which is often demanded for cleaning applications. The cmc values of the surfactants were determined to be 0.2 and 0.4 mM for NIHG550 and NIHG750, respectively, using tensiometry and fluorescence. Pulsed-field gradient spin-echo NMR measurements gave similar but slightly higher values. The micelle size of NIHG750 was estimated to be on the order of 40 ?, as calculated from the self-diffusion coefficient. The dynamic surface tension, gamma(t), was measured in the range 1 ms-1 s using a maximum bubble pressure instrument and analyzed in terms of asymptotic solutions to the Ward and Tordai equation. The results suggest that at the beginning the adsorption is essentially diffusion-controlled. However, close to equilibrium, the DST decays are not consistent with a diffusion-controlled adsorption mechanism. One important result from the present work is that the heterogeminis seem to align better than conventional surfactants at the air-liquid and solid-liquid interfaces. Copyright 2001 Academic Press.     

Phase-transfer agents as catalysts for a nucleophilic substitution reaction in microemulsions

The reaction between 4-tert-butylbenzyl bromide and potassium iodide was carried out in microemulsions based on different nonionic surfactants, and the reaction rates were compared with those obtained in two-phase systems with added phase-transfer agent, either a quaternary ammonium salt or a crown ether. The reactions were relatively fast in the microemulsions and extremely sluggish in the two-phase systems without additional phase-transfer agent. Addition of a phase-transfer agent did not accelerate the reaction when a hydrocarbon was used as organic solvent, neither in the two-phase system nor in the microemulsion. When a chlorinated hydrocarbon was used as solvent, phase-transfer catalysis became effective and the rate obtained in the two-phase system with an equimolar amount of phase-transfer agent added was higher than that obtained in the microemulsion. When a catalytic amount of phase-transfer agent was used, the rate in the two-phase system was about the same as the rate obtained in the microemulsion without the phase-transfer agent. The combined approach, that is, use of a microemulsion as the reaction medium and addition of a phase-transfer agent, gave the highest reaction rate. The quaternary ammonium salt (tetrabutylammonium hydrogen sulfate) was a more efficient catalyst in the microemulsion system than the crown ether ([18]crown-6).     

Dependence of the activity of a rhizopus lipase on microemulsion composition

Enzymatic hydrolysis of a model triglyceride, palm oil, was carried out with lipase fromRhizopus sp. in microemulsions with varying water content. The microemulsions were based on a nonionic surfactant, pentaethylene glycol monododecyl ether (C12 EO5), buffered water solution and an oil component consisting of isooctane and palm oil at a weight ratio of 20:1. The structure of the microemulsions was characterized using Fourier transform pulsed-gradient spin-echo¹H NMR. The rate of reaction decreased as the water content of the reaction medium was increased. The self-diffusion coefficient of water, D_w was found to be constant within the interval 1–20% water. The difference in reactivity is believed to be due to a difference in structure of the palisade layer between water and hydrocarbon microdomains. The nonionic surfactant was demonstrated to be unsuitable for enzymatic reactions since only partial hydrolysis was obtained in all experiments. The surfactant, however, did not cause enzyme deactivation, even at very high concentrations.     

PRIOR EXPOSURE OF HUMAN CELLS TO NEAR UV-RADIATION GIVES A DECREASE IN THE AMOUNT OF THE UNSCHEDULED DNA-SYNTHESIS INDUCED BY FAR UV-RADIATION

Pretreatment of human cells with near UV radiation (UVA) in fluences exceeding 5 × 10⁴ Jm⁻² caused a decrease in the amount of the unscheduled DNA synthesis induced by far UV radiation (UVC). The DNA repair synthesis, as measured by the incorporation of [³H] -thymidine, is reduced by nearly a factor of 2 for a UVA radiation exposure of 1.5 × 10⁵ Jm⁻². Since solar UVA fluence rate is rather independent of latitude, this figure corresponds to a UVA exposure time of 50-60 min from noon sunlight in the summer time.