May GSH and L-His contribute to intracellular binding of zinc? Thermodynamic and solution structural study of a ternary complex

GSH and L-His are abundant biomolecules and likely biological ligands for Zn(II) under certain conditions. Potentiometric titrations provide evidence of formation of ternary Zn(II) complexes with GSH and L-His or D-His with slight stereoselectivity in favour of L-His (ca. 1 log unit of stability constant). The solution structure of the ZnH(GSH)(L-His)(H2O) complex at pH 6.8, determined by NMR, includes tridentate L-His, monodentate (sulfur) GSH, and weak interligand interactions. Calculations of competitivity of this complex for Zn(II) binding at pH 7.4 indicate that it is likely to be formed in vivo under conditions of GSH depletion. Otherwise, GSH alone emerges as a likely Zn(II) carrier.     

Stitching pairs of Lévy processes into harnesses

We consider natural exponential families of Lévy processes with randomized parameter. Such processes are Markov, and under suitable assumptions, pairs of such processes with shared randomization can be “stitched together” into a single harness. The stitching consists of deterministic reparametrization of the time for both processes, so that they run on adjacent time intervals, and of the choice of the appropriate law at the boundary.     

The Kinetic Theory of Simple Reacting Spheres: I. Global Existence Result in a Dilute-Gas Case

Existence of global-in-time, spatially inhomogeneous, and L ¹-renormalized solutions is proven for the model of simple reacting spheres under the assumptions that initially the system has a finite total mass, energy, and entropy.     

Synthesis of polyetherols with isocyanuric ring: Kinetics and mechanisms of reactions in the presence of DABCO as catalyst

To establish the mechanism of reaction of formation of oligoetherols with perhydro‐1,3,5‐triazine ring, the kinetics of reaction of isocyanuric acid and 1,3,5‐tris(2‐hydroxyetyl) isocyanurate with ethylene carbonate resulting in formation of polyetherols in the presence of diazabicyclo[2.2.2]octane as a catalyst has been investigated. The kinetic and mechanistic studies revealed that the initial step of reaction is zero order related to ethylene carbonate and the reaction is inhibited by imide groups of isocyanuric acid. The mechanism of reaction was confirmed by spectroscopic and electrochemical methods. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 550–561, 2010     

Bicyclic [b]‐heteroannulated pyridazine derivatives. 9. cyclization reactions of 4,4‐dimethyl‐ and 4‐phenyltetrahydropyridazine‐3,6‐dione 3‐hydrazones with esters of keto dicarboxylic acids

Bis(ethoxycarbonyl)alkylidene derivatives 4 and 5 of the respective title hydrazones were obtained in the reactions with diethyl oxomalonate, diethyl oxosuccinate, diethyl 2‐oxoglutarate, and diethyl oxalo‐propionate as mixtures of geometric isomers with high predominance of one of them. On heating at 160‐200° without any solvent or on refluxing in ethanol 4 cyclized to yield the corresponding pyri‐dazino[6, 1‐c]triazines 6 , whereas heating of 5 gave, depending on the chain length, the corresponding pyra‐zolylpyridazines 8b and 8d or the pyridazinylpyridazine 8c . X‐ray analysis was used to determine the structures of 6 and 8 ; the unit cell of 6c was found to accommodate 16 molecules representing four conforma‐tional varieties. The different behavior of 4 and 5 in the cyclization reactions was interpreted in terms of the tautomeric equilibrium which was shifted towards the enamine form in 4 , and towards the imine form, in 5 . Transmission of a long‐range chirality effect in 4d and 5a‐d manifested itself in the ¹H nmr spectra as the magnetic non‐equivalence of the CH₂ protons in one or both ester ethyl groups.     

Synthesis of betulin derivatives and the determination of their relative lipophilicities using reversed‐phase thin‐layer chromatography

A series of superlipophilic or highly lipophilic semisynthetic betulin derivatives was prepared and their relative lipophilicity was measured by reversed‐phase thin‐layer chromatography (RP‐TLC) at different pH values using 1,4‐dioxane–acetate buffer mixtures as mobile phases. Cholesterol, 17β‐estradiol and pure betulin were used as the reference compounds. Linear relationships were found between R_M values and 1,4‐dioxane concentrations in the mobile phases. LogP values were also calculated with computer programs ACD/LogP (ChemSketch 11.0, Advanced Chemistry Development Inc.) and ClogP (Daylight Chemical Information Systems Inc.). The empirical and theoretical data were compared, and the R_M0 values correlated well with logP. Two of the synthesized betulin derivatives are reported for the first time. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of organofunctional silanes with sterically hindered substituents at silicon atoms

Organofunctional silanes with more sterically hindered substituents at the silicon atom than the typical methoxy (ethoxy) group have lately been frequently used as silane coupling agents, in polymer coupling systems, sol‐gel processes and also as interpenetrating polymer network substrates. New and very efficient synthetic ways leading to organofunctional silanes of the above type with methacryl, amine, chloro and isocyanato functional groups are proposed here. Catalytic transesterification and/or alcoholysis of chloropropyltrialkoxysilanes followed by­nucleophilic substitution has been employed. Copyright © 2001 John Wiley & Sons, Ltd.     

Low-loss geodesic lens: Meridional profile and fabrication tolerances

The most recent formulation of the perfect geodesic lens problem is utilized to evaluate a novel solution. This solution describes a smooth geodesic depression profile with a finite value of its local curvature radius at the edge of the lens. This feature should minimize radiation and scattering losses by the guided modes that take place mainly at the lens boundary. The external rounded section of the proposed lens is described by a simple, explicit expression that considerably eases designing procedure. The presented lens is capable of perfect focusing once the theoretically prescribed ideal depression profile is accurately fabricated. For straightforward examination of the influence of technological grinding errors on the lens focal characteristics, a simple analytical method is proposed and investigated.     

Effect of crown-ether surfactants on flame atomic absorption and flame emission signals of some monovalent cations

Two surface-active and one surface-inactive 18-crown-6 derivatives were synthesized and evaluated for their abilities to enhance flame atomic absorption and flame emission signals of monovalent cations. Enhancement of potassium signals were noted for the surface-active compounds but not for the surface-inactive compound. The critical micelle concentration was determined and compared to the degree of enhancement. Surfactant-induced signal enhancements are not due to the slight or moderate decrease in the size of the aerosol first produced in the nebulizing chamber. Additional mechanistic considerations are discussed.