Suppression of red cell diffusional water permeability by lipophilic solutes

The inhibitory effect of a series of neutral lipophilic solutes (methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-amylalcohol, n-hexanol, diethylether, nitrobenzene, and pyridine) on the diffusional water permeability (Pd, tot) of bovine erythrocyte membrane at 25 degrees C was studied in comparison to that of p-chloromercuri benzoate (pCMB). Permeability data were obtained by measuring the transmembrane diffusional water exchange time tau(exch) using an 1H-T2 NMR technique. Maximal inhibition by approximately 50% of Pd, tot was produced by 2 mM pCMB which completely blocked the membrane water channels in 20 min, hence suggesting the channel-to-lipid diffusional water permeability ratio of about 1:1. Furthermore, the maximal inhibitory effect of pCMB in combination with the lipophilic solutes was lower than that of pCMB alone. As pCMB does not interfere with the lipid bilayer, and provided that it blocks the water channels in solute presence as well, this confirms that the solutes induce an increase in the lipid-mediated background water permeability contribution (Pd, lipid) by the formation of aqueous leaks in the membrane hydrophobic barrier. However, faster but less efficient in permeability inhibition than pCMB (either alone or combined with solutes) were the lipophilic solutes alone. Taken together, the results indicate that the lipophilic solutes suppress the membrane total permeability Pd, tot by two opposing effects: a reduction of its channel-mediated part (Pd, channel) to the extent exceeding that of a simultaneous Pd, lipid increase. The inhibitory potency of the solutes tested appears to be correlated with their solubility in the membrane medium.     

微铂电极上1-酰基二茂铁动力学参数的测定

本文合成并研究了１－酰基二茂铁在ＣＨ２Ｃｌ２中的伏安行为，测定了它们在ＣＨ２Ｃｌ２中不同支持电解质浓度时的扩散系数，并分明用Ｚ．Ｇａｌｕｓ和Ｋ．Ａｏｋｉ方法计算了两种状态下的电子迁移速率常数。讨论了取代基的诱导效应和共轭效应及其链长对１－酰基二茂铁的动力学性质的影响以及支持电解质及其浓度等因素对伏安曲线的影响。     

Transition state geometry in radical abstraction reactions: comparison of interatomic distances in the intersecting parabolas and Morse curves models with quantum-chemical calculations

Interatomic distances in the transition state were estimated for the reactions of radical abstraction: H^· + H₂, H^· + HCl, H^· + CH₄, N^·H₂ + NH₃, HO^· + H₂O, HO₂ ^· + HOOH, and C^·H₃ + SiH₄. The calculation was performed by the quantum-chemical density functional method or coupled clusters method (QCH), as well as by the methods of intersecting parabolas (IPM) and Morse curves (IMM), using experimental data (activation energies and reaction enthalpies). The results of the latter two methods are close to the quantum-chemical calculation and differ only by the increment a: r(IPM or IMM) = a + r(QCH), where a = –4.5·10^–12 m for IPM and a = +1.9·10^–12 m for IMM.     

Investigations of precipitates in heat treated AgPd30/CuSn6 layers

The subject of the investigations are precipitation zones, which grew as a result of chemical diffusion in AgPd30/CuSn6 bimetals. These precipitation zones have been characterized by metallography, electron probe microanalysis and x-ray diffraction. The growth of precipitation zones in the plating layer and in the substrate layer in dependence on time have been determined. The use of x-ray diffraction alone for the identification of the precipitates could not supply satisfying results in every case. This problem was solved by the application of electron probe microanalysis using a correction method, which allows the estimation of the chemical composition of small particles.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday     

Diffusion current on a nonuniform electrode: Calculation with integral equations

Identity of mathematical problems concerning calculation of the distribution of reactants’ concentrations and the current near the surface of a nonuniform (strip) electrode and distribution of displacements and forces in the case of an elastic layer “antiplane” deformation caused by the punch action. Formulas for calculating the current at a strip electrode are derived for various ratios between the electrode width and the diffusion layer thickness by means of asymptotic methods designed for calculating problems of mechanical contact interactions. It is noted that calculations of the diffusion current for involved activity distributions at the electrode surface may benefit from asymptotic methods of mechanics of contact interactions.     

Effect of NaOH and NaCl on the disodiumn-decane phosphonate micellar aggregation number

The diffusion coefficient of disodiumn-decane phosphonate micelles was studied by polarography at 25°C in NaCl and in NaOH solutions, and the size and aggregation number of the micelles was computed as a function of Na⁺ concentration. All other conditions being equal, the addition of NaCl produces micelles with an aggregation number one order of magnitude larger than the NaOH addition. This is due to the increase of the effective charge per micellized head group produced by the reaction of OH- with the hydrolized head groups which are mainly present as-PO₃H- in the micellar Stern layer.     

室温熔盐二(三氟甲基磺酸酰)亚胺锂-尿素体系的分子动力学模拟

应用分子动力学模拟了25 ℃和50 ℃时新型室温熔盐二(三氟甲基磺酸酰)亚胺锂[LiN(SO2CF3)2, LiTFSI]与尿素(摩尔比为1:3.6)体系的结构与动力学性质. 在两个温度下体系的微观结构基本相同, Li+的配位数约为5, 且都是与溶剂和阴离子中的氧原子发生配位. 对TFSI-的研究表明, 每个TFSI-只提供四个氧中的一个与Li+配位; 而且在Li+的配位层中, TFSI-具有顺、反和gauche 等不同的构象, 并且不同构象出现的几率会随着温度的改变而改变.     

A New Tool in Peptide Engineering: A Photoswitchable Stilbene‐type β‐Hairpin Mimetic

Peptide secondary structure mimetics are important tools in medicinal chemistry, as they provide analogues of endogenous peptides with new physicochemical and pharmacological properties. The development, synthesis, photochemical investigation, and conformational analysis of a stilbene‐type β‐hairpin mimetic capable of light‐triggered conformational changes have been achieved. In addition to standard spectroscopic techniques (nuclear Overhauser effects, amide temperature coefficients, circular dichroism spectroscopy), the applicability of self‐diffusion measurements (longitudinal eddy current delay pulsed‐field gradient spin echo (LED‐PGSE) NMR technique) in conformational studies of oligopeptides is demonstrated. The title compound shows photoisomerization of the stilbene chromophore, resulting in a change in solution conformation between an unfolded structure and a folded β‐hairpin.     

Kinetics and mechanism of gold dissolution in thiourea solutions: Effect of sulfide ions

Chronoamperograms for gold in solutions containing 0.1 M thiourea, 0.5 M H₂SO₄, and catalytically active sulfide ions at the concentration c ₁ from 1 × 10^?5 to 4 × 10^?5 M are obtained at different potentials with the aid of an automated setup intended for renewing the electrode surface directly in the solution by cutting off a thin surface layer of the metal. It is shown that the results of measurements of the current practically coincide at a constant value of the product c ₁ t, where t is the time period elapsed after the renewal of the electrode surface. Such a coincidence testifies to a diffusion nature of processes that hamper accumulation of sulfide ions at the gold surface. This fact permitted the use of a procedure developed previously for the calculation of polarization curves at constant values of surface coverage θ by catalytically active ions. At θ = const, the voltammetric curves for gold in sulfide-containing thiourea solutions are shown to correspond to the Tafel equation. With the surface coverage increasing, the effective values of the exchange current i ₀, transfer coefficient α, and anodic reaction order with respect to thiourea P _a increase from the values i }~ 10^?5 A cm^?2, α }~ 0.12, and P _a = 0.2, which are characteristic of pure solutions, to 2 × 10^?4 A cm^?2, α }~ 0.5, and P _a = 1.1 (at θ }~ 0.5). An interpretation to the established regularities is given.