Influence of ethanol on lipid membranes: from lateral pressure profiles to dynamics and partitioning

We have combined experiments with atomic-scale molecular dynamics simulations to consider the influence of ethanol on a variety of lipid membrane properties. We first employed isothermal titration calorimetry together with the solvent-null method to study the partitioning of ethanol molecules into saturated and unsaturated membrane systems. The results show that ethanol partitioning is considerably more favorable in unsaturated bilayers, which are characterized by their more disordered nature compared to their saturated counterparts. Simulation studies at varying ethanol concentrations propose that the partitioning of ethanol depends on its concentration, implying that the partitioning is a nonideal process. To gain further insight into the permeation of alcohols and their influence on lipid dynamics, we also employed molecular dynamics simulations to quantify kinetic events associated with the permeation of alcohols across a membrane, and to characterize the rotational and lateral diffusion of lipids and alcohols in these systems. The simulation results are in agreement with available experimental data and further show that alcohols have a small but non-vanishing effect on the dynamics of lipids in a membrane. The influence of ethanol on the lateral pressure profile of a lipid bilayer is found to be prominent: ethanol reduces the tension at the membrane-water interface and reduces the peaks in the lateral pressure profile close to the membrane-water interface. The changes in the lateral pressure profile are several hundred atmospheres. This supports the hypothesis that anesthetics may act by changing the lateral pressure profile exerted on proteins embedded in membranes.     

Total synthesis of aigialomycin D: surprising chemoselectivity dependence on alkyne structure in nickel-catalyzed cyclizations

The total synthesis of aigialomycin D was carried out using a nickel-catalyzed ynal macrocyclization as a key step. This key step allowed macrocycle assembly and formation of a disubstituted alkene and a secondary hydroxyl stereocenter in a single step, although the stereocenter was formed unselectively. An interesting side reaction involving five-membered-ring synthesis by an aldehyde/styrene cyclization was observed when macrocyclization of an alkynyl silane was attempted. A mechanistic basis for this surprising process is provided.     

Catalyst-free microwave-assisted amination of 2-chloro-5-nitrobenzoic acid

The synthesis of N-substituted 5-nitroanthranilic acid derivatives 3a-w was achieved by a new, mild, microwave-assisted, regioselective amination reaction of 5-nitro-2-chlorobenzoic acid (1a) with a diverse range of aliphatic and aromatic amines 2a-w without added solvent or catalyst. Up to >99% isolated yield was obtained within 5-30 min at 80-120 degrees C. The reaction, which is suitable for upscaling, yielded new compounds that are of considerable interest as useful building blocks and as potential drugs.     

Parents’ Attitudes Toward Mathematics and the Influence on Their Students’ Attitudes toward Mathematics: A Quantitative Study

The purpose of this study was to investigate parents’ attitudes toward mathematics, their students' attitude toward mathematics, and the influence of the parents’ attitude on the students' attitude toward mathematics. Data analyses revealed statistically significant positive correlations between parents’ and students’ attitudes toward mathematics. Additionally, parents’ mathematics attitude significantly predicted students’ attitudes toward mathematics (n=146). By understanding the influence of parents’ attitudes on students’ attitudes toward mathematics, school efforts can be geared toward fostering favorable attitudes toward mathematics among parents.     

Surprising role of aryl halides in nickel-catalyzed reductive aldol reactions

[reaction: see text] A new nickel-catalyzed method for the reductive aldol addition of acrylates and aldehydes has been developed. An unexpected requirement for an aryl iodide additive was found in the process, and the effect was shown to be linked to an initiation step.     

Sorbent coatings for solid-phase microextraction based on mixtures of polymeric ionic liquids

Four polymeric ionic liquids based on two different cations, poly(1‐vinyl‐3‐hexylimidazolium) and poly(1‐vinyl‐3‐hexadecylimidazolium), combined with two different anions, bis[(trifluoromethyl)sulfonyl]imide (NTf) and chloride (Cl^?), were combined in various weight percentages and used as sorbent coatings for solid‐phase microextraction gas chromatography (SPME‐GC). The selectivity of the fiber coatings for 12 test analytes was examined. The extraction efficiency of n‐alcohols increased with an increase in the weight percentage of chloride ion in the sorbent coating. The ability to tune the interactions between the coating material and the analytes was exploited and resulted in distinct changes in the limits of detection for hydrogen‐bonding analytes with varying chloride ion content in the sorbent coating.     

Measurement of absolute absorption cross sections for nitrous acid (HONO) in the near-infrared region by the continuous wave cavity ring-down spectroscopy (cw-CRDS) technique coupled to laser photolysis

Absolute absorption cross sections for selected lines of the OH stretch overtone 2ν(1) of the cis-isomer of nitrous acid HONO have been measured in the range 6623.6-6645.6 cm(-1) using the continuous wave cavity ring-down spectroscopy (cw-CRDS) technique. HONO has been generated by two different, complementary methods: in the first method, HONO has been produced by pulsed photolysis of H(2)O(2)/NO mixture at 248 nm, and in the second method HONO has been produced in a continuous manner by flowing humidified N(2) over 5.2 M HCl and 0.5 M NaNO(2) solutions. Laser photolysis synchronized with the cw-CRDS technique has been used to measure the absorption spectrum of HONO produced in the first method, and a simple cw-CRDS technique has been used in the second method. The first method, very time-consuming, allows for an absolute calibration of the absorption spectrum by comparison with the well-known HO(2) absorption cross section, while the second method is much faster and leads to a better signal-to-noise ratio. The strongest line in this wavelength range has been found at 6642.51 cm(-1) with σ = (5.8 ± 2.2) × 10(-21) cm(2).     

Homopolymerization of ethylene, 1-hexene, styrene and copolymerization of styrene with 1,3-cyclohexadiene using (η⁵-tetramethylcyclopentadienyl)dimethylsilyl(N-Ar')amido-TiCl₂/MAO (Ar'=6-(2-(diethylboryl)phenyl)pyrid-2-yl, biphen-3-yl)

The propensity of a half-sandwich (η?-tetramethylcyclopentadienyl) dimethylsilylamido Ti(IV)-based catalyst bearing an auxiliary diethylboryl-protected pyridyl moiety (Ti-8), activated by methylaluminoxane (MAO) to homopolymerize α-olefins such as ethylene, 1-hexene and styrene as well as to copolymerize styrene with 1,3-cyclo-hexadiene is described. The reactivity of Ti-8 was investigated in comparison to a 6-(2-(diethylboryl)phenyl)pyrid-2-yl-free analogue (Ti-3).