Electrochemistry and spectroelectrochemistry of meso-substituted free-base corroles in nonaqueous media: reactions of (Cor)H3, [(Cor)H4]+, and [(Cor)H2]-

Eleven free-base corroles with different electron-donating or electron-withdrawing meso substituents were characterized as to their electrochemistry and UV-visible spectroscopy in benzonitrile (PhCN) or pyridine containing tetra-n-butylammonium perchlorate (0.1 M). Six forms of the compounds with different numbers of protons and/or oxidation states were spectroscopically identified and are represented as (Cor)H3, (.Cor)H2, [(Cor)H2]-, [(.Cor)H2]2-, [(Cor)H4]+, and [(.Cor)H4]2+, where Cor is a trianionic corrole macrocycle. The electrochemistry and UV-visible properties are a function of corrole basicity, solvent basicity, and types or sizes of the meso substituents, and the compounds could be subdivided into one of two different groups, one of which comprises sterically hindered corroles and another that does not. The electroactive species in PhCN is (Cor)H3, whereas in pyridine, one inner proton dissociates, generating a mixture of (Cor)H3, [(Cor)H2]-, and pyH+. The addition of one electron to [(Cor)H2]- reversibly gives the [(.Cor)H2]2- pi-anion radical, whereas a reversible oxidation of the same species gives the neutral radical (.Cor)H2. The first one-electron reduction of (Cor)H3 occurs at the macrocycle in PhCN, but the initial product rapidly converts to [(Cor)H2]-, which undergoes additional reversible redox reactions at the conjugated pi-ring system. The first oxidation of (Cor)H3 in PhCN leads to a mixture of (.Cor)H2 and [(Cor)H4]+, both of which could be further oxidized or reduced. The UV-visible spectra of [(Cor)H4]+ were measured in PhCN after titrations with trifluoroacetic acid, after which selected samples were examined as to their electrochemistry. The HOMO-LUMO gaps of [(Cor)H2]-, (Cor)H3, and [(Cor)H4]+ were also determined.     

Modeling of Anticancer Sulfonamide Derivatives Lipophilicity by Chemometric and Quantitative Structure-Retention Relationships Approaches

Sulfonamides are a classic group of chemotherapeutic drugs with a broad spectrum of pharmacological action, including anticancer activity. In this work, reversed-phase high-performance liquid chromatography and biomimetic chromatography were applied to characterize the lipophilicity of sulfonamide derivatives with proven anticancer activities against human colon cancer. Chromatographically determined lipophilicity parameters were compared with obtained logP, employing various computational approaches. Similarities and dissimilarities between experimental and computational logP were studied using principal component analysis, cluster analysis, and the sum of ranking differences. Furthermore, quantitative structure–retention relationship modeling was applied to understand the influences of sulfonamide’s molecular properties on lipophilicity and affinity to phospholipids.     

Thermal behavior of ethylene copolymers with di- and tri-alkenylsilsesquioxane comonomers synthesized by post-metallocene catalysts

Journal of Thermal Analysis and Calorimetry - This paper reported thermal properties of ethylene copolymers with di- and tri-alkenylsilsesquioxanes (POSS) synthesized by bis(phenoxy-imine) Ti, Zr,...     

Reversible guest-induced magnetic and structural single-crystal-to-single-crystal transformation in microporous coordination network {[Ni(cyclam)]3[W(CN)8]2}n

Planar honeycomb-like coordination network {[Ni(cyclam)]3[W(CN)8]2}n (cyclam = 1,4,8,11-tetraazacyclotetradecane) was obtained in the self-assembly reaction of [Ni(cyclam)]2+ and [W(CN)]83-. Its structure is characterized by void channels along the a axis. The compound shows reversible water adsorption in the temperature range of 25-40 degrees C with the formation of {[Ni(cyclam)]3[W(CN)8]2}n.16nH2O, accompanied by single-crystal-to-single-crystal transformation. The structural transformation significantly changes the character of intraplane magnetic exchange interactions.     

Changes in the gradient percolation transition caused by an Allee effect

The establishment and spreading of biological populations depends crucially on population growth at low densities. The Allee effect is a problem in those populations where the per capita growth rate at low densities is reduced. We examine stochastic spatial models in which the reproduction rate changes across a gradient g so that the population undergoes a 2D-percolation transition. Without the Allee effect, the transition is continuous and the width w of the hull scales as in conventional (i.e., uncorrelated) gradient percolation, w ∝ g(-0.57). However, with a strong Allee effect the transition is first order and w ∝ g(-0.26).     

Determination of the anomeric configuration of glycosyl esters of nucleoside pyrophosphates and polyisoprenyl phosphates by fast-atom bombardment tandem mass spectrometry

Collision-induced dissociation of the deprotonated molecules of glycosyl esters of nucleoside pyrophosphates and polyisoprenyl (dolichyl and polyprenyl) phosphates results in distinct fragmentation patterns that depend on cis-trans configuration of the phosphodiester and 2″ (or 2′, respectively)-hydroxyl groups of the glycosyl residue. At the collision-offset voltage of 0. 5 V, sugar nucleotides with cis configuration produce only one very abundant fragment of nucleoside monophosphate, whereas compounds with trans configuration give weak signals for nucleoside di- and mono-phosphates and their dehydration products. These fragmentation patterns are largely preserved at higher collision energy, with the exception that, for sugar nucleotides with trans configuration, the characteristic signals are much more abundant and a novel diagnostic fragment of [ribosyl(deoxyribosyl)-5′-P₂O₅ — H]^? is generated. In the case of polyisoprenyl-P-sugars, polyisoprenyl phosphate ion is the only fragment observed for compounds with trans configuration, whereas in compounds with cis configuration, this ion is accompanied by another abundant fragment, which is derived from the cleavage across the sugar ring and corresponds to [polyisoprenyl-PO₄-(C₂H₃O)]^?. The relative intensity ratio of the latter ion to the [polyisoprenyl-HPO₄]^? ion is close to 1 for compounds with cis configuration, but it is only about 0. 01 for compounds with trans configuration. This ratio may serve, therefore, as a diagnostic value for determination of the anomeric configuration of glycosyl esters of polyisoprenyl phosphates. It is proposed that the observed differences in fragmentation patterns of cis-trans sugar nucleotides and polyisoprenyl-P-sugars could be explained in terms of kinetic stereoelectronic effect, and a speculative mechanism of fragmentation of compounds with trans configuration is presented. For compounds with cis configuration, formation of a hydrogen bond between the C-2″(2′) hydroxyl and the phosphate group could play a crucial role in directing the specific fragmentation reactions. Consequently, the described empirical rules would hold only for compounds that have a free 2″(2′)-hydroxyl group and no alternative charge location. Owing to its simplicity, sensitivity, and tolerance of impurities, fast-atom bombardment-tandem mass spectrometry represents a suitable method for determination of the anomeric linkage of glycosyl esters of nucleoside pyrophosphates and polyisoprenyl phosphates if the absolute configuration of glycosyl residue is known and the compound fulfills the above-mentioned requirements.     

A Novel Method of High Sensitive Determination of Prednisolone on Renewable Mercury Film Silver Based Electrode

Fast and sensitive method of prednisolone determination at renewable mercury film electrode using differential pulse adsorptive stripping voltammetry (DPAdSV) was successfully developed. The effects of various factors such as: preconcentration potential and time, pulse height, step potential and supporting electrolyte composition were optimized. A linear voltammetric response for analyte was obtained in the concentration range from 0.05 µmol L⁻¹ (18 µg L⁻¹) to 2.25 µmol L⁻¹ (0.81 mg L⁻¹), with a detection limit of 0.01 µmol L⁻¹ for preconcentration time of 20 s. Repeatability of method was determined as RSD % for prednisolone concentration of 0.04 µmol L⁻¹ as 1.6 % (n=9). The proposed method was successfully applied and validated by recovery parameter of prednisolone in simulated sample and pharmaceutical product.