NO-donating and hemolytic activity of tetranitrosyl iron complexes with ligands of the 2-mercaptopyridine series

Russian Chemical Bulletin - The NO-donating and hemolytic activity of the binuclear tetranitrosyl iron complexes (TNIC) with thiolate ligands of the composition [Fe2(SR)2(NO)4], where R is...     

Gas-phase fragmentation studies of biotinylated oligomannuronopyranosides under conditions of collisionally activated dissociation

Russian Chemical Bulletin - High-resolution electrospray ionization mass spectra (MS and MS/MS) of a series of glycoconjugates containing biotin and oligomannuronopyranosyl residues linked via a...     

Checking of applicability of conditions for reaching the limiting-current mode to flow-by porous electrodes

For the flow-by porous electrodes, which differ in thickness, specific surface area, solution flow rate, and a ratio between the phase conductivities, the conditions providing the limiting-current mode over the entire electrode surface at nearly 100% current efficiency are determined using the method of successive refinement of total current and profile of its distribution along the solution flow. The used values of electrode thickness L are compared with available estimates for the limiting thickness of porous electrode L _lim derived for the ideal limiting-current mode and calculated using real values of the width of the limiting-current plateau of overall polarization curve, solution conductivity, and the diffusion limiting current in the zone of solution input into the electrode. It is found that these values are close to each other in all cases. The largest error of estimation of L _lim does not exceed 10% indicating that it can be used for preliminary estimation of the conditions for reaching the limiting-current mode for the flow porous electrodes of this type.     

Electrochemical oxidation of thrombin on carbon screen printed electrodes

The electrochemical oxidation of thrombin on the surface of carbon screen printed electrodes was studied. The electrochemical activity of thrombin was predicted, using bioinformation analysis, based on the data about the electrochemical properties of amino acids. The number of potentially electroactive amino acid residues, namely, tyrosine (Tyr), tryptophan (Trp), cysteine (Cys), histidine (His), methionine (Met), and cystine (Cys-Cys) located on the protein surface and orientated by their electroactive groups toward the electrode surface, i.e., accessible for electrochemical oxidation was calculated. The theoretical data were confirmed experimentally by cyclic and square-wave voltammetry. The available data on the protein structure allowed us to attribute the recorded electrochemical signals of thrombin oxidation to certain types of amino acid residue: the oxidation peak with a potential maximum at 0.7–0.8 V (vs. Ag/AgCl) was attributed to the oxidation of the Trp and Tyr residues; the wave in the range 1.0–1.2 V, to the oxidation of His; and the wave at 1.2–1.5 V, to the oxidation of Met and Cys-Cys. The electroanalysis based on the oxidation peak of the Tyr and Trp amino acid residues allowed to detect thrombin up to the concentration of 10^–7 M. The suggested strategy for predicting the electrochemical activity can be used for investigating the properties of many other proteins and peptides and serve as a basis for their quantitative determination when developing various sensor and biosensor devices.     

The synthesis,structure, and electrochemical properties of Li<Subscript>2</Subscript>FeSiO<Subscript>4</Subscript>-based lithium-accumulating electrode material

Different approaches to synthesis of Li₂FeSiO₄-based electrode materials for lithium intercalation, using low-cost and abundant Li-, Si-, and Fe-containing parent substances, are discussed. XRD, SEM, and a laser-diffraction analyzer of particle size were used for structure and morphology characterization of the composite electrode materials. Li₂FeSiO₄ was shown to be the main lithium-accumulating crystalline phase; minor LiFeO₂ and Li₂SiO₃ admixtures are also present. The material microparticles’ average size was shown to vary from tenths of micrometer to 1 μm. Larger objects sized ca. 2–4 μm are the microparticles’ agglomerates. The material electrochemical properties were studied by dc chronopotentiometry (galvanostatic charging–discharging) and cyclic voltammetry with potential linear sweeping. The initial reversible cycled capacity of the best samples is 170 mA h/g. The anodic and cathodic processes manifest obvious hysteresis caused by the presence of several different lithium ion energy states in the material; the transition between the states is kinetically hindered. The dependences of the specific capacity and its stability under cycling on the current load and the conductive carbon component content in the composite were elucidated.     

Regularities of oxygen and water thermal desorption from barium cerate doped by neodymium,samarium, and gadolinium

Processes of thermal desorption of oxygen molecules and water from BaCe_1–x M _x O_3–δ, where M= Nd, Sm, and Gd, presintered in air at the temperature of 650°C are studied. It is found that oxygen is desorbed only from neodymium–doped barium cerate and is almost not evolved from barium cerate doped by samarium and gadolinium. The amount of desorbed oxygen features a square dependence on cationic doping by neodymium. At similar degrees of cationic doping, the amount of water desorbed from neodymium–doped barium cerate is always lower than that from the cerate doped by samarium and gadolinium. The obtained experimental data on thermal desorption and analysis of literature data served as a basis for the conclusion as to the mixed valency of neodymium Nd(III)–Nd(IV) in BaCe_1–x Nd _x O_3–δ. In this case, at similar doping degrees x, the hydration degree of BaCe_1–x Nd _x O_3–δ is lower and the oxygen index is higher than in BaCe1_–x (Sm,Gd) _x O_3–δ. The differences become more pronounced at high degrees of cationic doping and must decrease at an increase in temperature.     

Transport properties of metacomposites in eutectic MAO<Subscript>4</Subscript>–V<Subscript>2</Subscript>O<Subscript>5</Subscript> systems (M = Ca,Sr; A = W,Mo)

Metal molybdates MMoO₄ (M = Ca, Sr) and their composites with vanadium oxide V₂O₅ were synthesized. An X-ray diffraction analysis confirmed that the obtained molybdates were single-phase, and the heterogeneous systems were two-phase. The temperature dependences of the total conductivity of the composites were studied. The ion transport numbers in the {CaMoO₄ · xV₂O₅} composites (x = 1–30 mol %) were studied by the EMF method. The conductivity of the composites at x ≤ 5 mol % was shown to be ionic. The conductivity of the composites was described using the mixing equation.     

The X<Superscript>−</Superscript>···benzohydrazide complexes: the interplay between anion-π and H-bond interactions

The compounds containing the benzohydrazide (BH) nucleus have a variety of biological activities because of various noncovalent intermolecular interactions. The interplay between anion-π and H-bond interactions, which can affect the activity of compounds, has been investigated in ten substituted BH exposed to the chloride ion using the quantum mechanical calculations. The total interaction energy is separated into the anion-π (ΔE _Aπ) and H-bond (ΔE _HB) contributions where both interactions are presented in the complexes. The electron-withdrawing substituents (EWSs) increase |ΔE _Aπ| and decrease |ΔE _HB|, while reversed changes are observed with the electron-donating substituents (EDSs). In addition, the total binding energy (ΔE) becomes more/less negative in the presence of EWSs/EDSs. The synergetic effects of mentioned interactions and substituent effects have also been investigated using the atoms in molecules (AIM), natural bond orbital (NBO) and molecular electrostatic potential (MEP) analyses. A good correlation is found between the energy data and the Hammett constants, the minimum of electrostatic potential (V _min) and the results of population analyses.     

DFT studies on the acid-catalyzed Curtius reaction: the Schmidt reaction

The Schmidt reaction is the acid-catalyzed analogue of the Curtius reaction and is extensively used in organic synthesis. In this work, the mechanism of this reaction has been explored using DFT calculations at the B3LYP/6-311+G(d,p) level. Protonated formyl azide may undergo rearrangement to the product, protonated isocyanic acid, with simultaneous extrusion of molecular nitrogen (concerted mechanism), or undergo rearrangement to the anti conformer, followed by removal of nitrogen to form the nitrenium ion, which then rearranges to the final product, protonated isocyanic acid (step-wise mechanism). Like the Curtius reaction, it is found that the concerted pathway is definitely preferred. The key role of acidification in decreasing the overall energy barrier is more highlighted in case of phenyl substitution, with negligible effect on the lower homologues. For methoxy and amine substituents, there is very little difference in the activation energies of the concerted and step-wise reactions, with the former being still slightly preferred. Unlike the parent compound, the rearrangement of substituted nitrenium ion in some cases involves side reactions like C-H insertion and cyclization.