The Thermodynamics of Translesion DNA Synthesis Past Major Adducts of Enantiomeric Analogues of Antitumor Cisplatin

The Pt^II-coordination complex [PtCl₂(DAB)] (DAB=2,3-diaminobutane) belongs to a class of cytotoxic cisplatin analogues that contain chiral diamine ligands. Enantiomeric pairs of these compounds have attracted particular interest because they have different effects on different DNA conformations, which, in turn, influences the binding of damaged-DNA-processing enzymes that control downstream effects of the adducts, and thus exhibit different biological activities of the enantiomers. Herein, we studied the translesion synthesis across the major 1,2-d(GG) intrastrand cross-link formed by the R,R and S,S enantiomers of [Pt(DAB)]²⁺ in the TGGT sequence by using the enzyme that catalyzes the polymerization of deoxyribonucleotides into a DNA strand. We also employed differential scanning calorimetry (DSC) to measure the thermodynamic changes associated with replication-bypass past 1,2-d(GG) adducts of the [Pt(DAB)]²⁺ enantiomers. In the sequence TGGT, the 1,2-d(GG) intrastrand cross-links that were formed by the enantiomeric pairs of [Pt(DAB)]²⁺ inhibited DNA polymerization in a chirality-dependent manner. The thermodynamic data helped to understand the effect of the alterations in thermodynamic stability of DNA caused by the Pt-d(GG) adducts upon DNA polymerization across these lesions. Moreover, these data can possibly explain the influence of these alterations on the ability of many DNA polymerases to bypass adducts of antitumor platinum drugs. These results also highlighted the usefulness of DSC in evaluating the impact of DNA adducts of platinum-coordinated compounds on the processing of these lesions by damaged-DNA processing-enzymes.     

Atomic force microscopy characterization of β-casein nanoparticles on mica and graphite

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Synthesis and structure of new chlorine containing calix[4]resorcinols

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α-Diphenylphosphino-N-(pyrazin-2-yl)glycine as a ligand in Ni-catalyzed ethylene oligomerization

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Chemical aspects of the radiation stability of macrocyclic extractants designed for 90Sr separation

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A comparison of numerical and analytical radiative-transfer solutions for plane albedo of natural waters

Several numerical and analytical solutions of the radiative transfer equation (RTE) were compared for plane albedo in a problem of solar light reflection by sea water. The study incorporated the simplest case—a semi-infinite one-dimensional plane—parallel absorbing and scattering homogeneous layer illuminated by a monodirectional light beam. Inelastic processes (such as Raman scattering and fluorescence), polarization and air-water surface refraction-reflection effects, were not considered. Algorithms were based on the invariant imbedding method and two different variants of the discrete ordinate method (DOM). Calculations were performed using parameters across all possible ranges (single-scattering albedo ω₀ and refracted solar zenith angle θ₁), but with a special emphasis on natural waters. All computations were made for two scattering phase functions, which included an almost isotropic Rayleigh phase function and strongly anisotropic double-peaked Fournier-Forand-Mobley phase function. Models were validated using quasi-single-scattering (QSSA) and exponential approximations, which represent the extreme cases of ω₀→0 and ω₀→1, respectively. All methods yielded relative differences within 1.8% for modeled natural waters. An analysis of plane albedo behavior resulted in the development of a new extended QSSA approximation, which when applied in conjunction with the extended Hapke approximation developed earlier, resulted in a maximum relative error of 2.7%. The study results demonstrated that for practical applications, the estimation of inherent optical properties from observed reflectance can best be achieved using an extended Hapke approximation.     

Novel Effectively Carbonaceous and Sulfurated Hydrogen Corrosion Inhibitors on the Basis of Organosulfurphosphorus Compounds

Abstract

Novel ammonium salts of O,O-dialkyl dithiophosphoric acids were obtained by one-pot synthesis from white phosphorus, elemental sulfur, industrial alcohols or phenols, and amines. Long-chain S-alkyl O,O-dialkyldithiophosphonates were prepared by the reaction of red phosphorus with elemental sulfur, alcohols, and the cheap industrial fractions of С₁₆–С₁₈ and С₂₀–С₂₆ of higher α-olefins in the presence of Lewis acid catalyst. The dithiophosphates obtained possess the high anticorrosion activities toward mild steel.     

Phosphorylation of Dienyl Diprenoid Alcohols

Abstract

The reactions of geraniol, nerol, and linalool with N,N-diethylamido O,O-propylenephosphite and diethyl chlorophosphite were studied. On the basis of these studies, new dienyl diprenoid phosphite esters were obtained.

GRAPHICAL ABSTRACT     

Cobalt(II) and cadmium(II) square grids supported with 4,4′‐bipyrazole and accommodating 3‐carboxyadamantane‐1‐carboxylate

In poly[[bis(μ‐4,4′‐bi‐1H‐pyrazole‐κ²N²:N^2′)bis(3‐carboxyadamantane‐1‐carboxylato‐κO¹)cobalt(II)] dihydrate], {[Co(C₁₂H₁₅O₄)₂(C₆H₆N₄)₂]·2H₂O}_n, (I), the Co²⁺ cation lies on an inversion centre and the 4,4′‐bipyrazole (4,4′‐bpz) ligands are also situated across centres of inversion. In its non‐isomorphous cadmium analogue, {[Cd(C₁₂H₁₅O₄)₂(C₆H₆N₄)₂]·2H₂O}_n, (II), the Cd²⁺ cation lies on a twofold axis. In both compounds, the metal cations adopt an octahedral coordination, with four pyrazole N atoms in the equatorial plane [Co—N = 2.156 (2) and 2.162 (2) Å; Cd—N = 2.298 (2) and 2.321 (2) Å] and two axial carboxylate O atoms [Co—O = 2.1547 (18) Å and Cd—O = 2.347 (2) Å]. In both structures, interligand hydrogen bonding [N...O = 2.682 (3)–2.819 (3) Å] is essential for stabilization of the MN₄O₂ environment with its unusually high (for bulky adamantanecarboxylates) number of coordinated N‐donor co‐ligands. The compounds adopt two‐dimensional coordination connectivities and exist as square‐grid [M(4,4′‐bpz)₂]_n networks accommodating monodentate carboxylate ligands. The interlayer linkage is provided by hydrogen bonds from the carboxylic acid groups via the solvent water molecules [O...O = 2.565 (3) and 2.616 (3) Å] to the carboxylate groups in the next layer [O...O = 2.717 (3)–2.841 (3) Å], thereby extending the structures in the third dimension.     

Evaluation of Free Radical-Scavenging Activity of Sea Urchin Pigments Using HPTLC with Post-Chromatographic Derivatization

Chromatographic separation, analysis of in situ radical-scavenging activity, and quantitative analysis of green sea urchin shell pigments were carried out by online HPTLC-DAD and HPTLC-DPPH methods. Methanol:chloroform:acetic acid:water (11:50:5:2, v/v) was selected as the best mobile phase on silica gel plates for the separation of the pigments. Two pigment spots, S1 and S2, were observed on the TLC plates, while echinochrome A was not detected in the pigment extract of green sea urchin shells. Based on the estimated ID₅₀ values, the antiradical activity was S2 (0.043 μg) > S1 (0.058 μg) > echinochrome A (0.134 μg).