Mechanism of Reaction of Flavone Derivatives with Hydroxyl Radical by Semiempirical Methods

Semiempirical quantum-chemical calculations were used to study the reactivity of the C² = C³ bond in flavones in reaction with hydroxyl radical. The preferred pathway was found to be addition of the radical by C³. Increased reactivity in the reaction in question of the hydroxy groups on C³ and C⁴' in polyhydroxyflavones was revealed.     

Exact phase diagrams for an Ising model on a two-layer Bethe lattice

Using an iteration technique, we obtain exact expressions for the free energy and the magnetization of an Ising model on a two-layer Bethe lattice with intralayer coupling constants J1 and J2 for the first and the second layer, respectively, and interlayer coupling constant J3 between the two layers; the Ising spins also couple with external magnetic fields, which are different in the two layers. We obtain exact phase diagrams for the system and find that when /J3/-->0, DeltaT(c) identical with[T(c)(J3)-T(c)(0)]/T(c)(0) approximately [J3]/J(1)/(1/psi), where T(c)(J3) is the phase-transition temperature for the system with interlayer coupling constant J3 and the shift exponent psi is 1 for J(1)=J(2) and is 0.5 for J1 not equal to J2. Such results are consistent with predictions of a scaling theory. We also derive equations for DeltaT(c) when /J3/ approaches infinity.     

Mechanistic insight into the nitrosylation of the [4Fe-4S] cluster of WhiB-like proteins

The reactivity of protein bound iron-sulfur clusters with nitric oxide (NO) is well documented, but little is known about the actual mechanism of cluster nitrosylation. Here, we report studies of members of the Wbl family of [4Fe-4S] containing proteins, which play key roles in regulating developmental processes in actinomycetes, including Streptomyces and Mycobacteria, and have been shown to be NO responsive. Streptomyces coelicolor WhiD and Mycobacterium tuberculosis WhiB1 react extremely rapidly with NO in a multiphasic reaction involving, remarkably, 8 NO molecules per [4Fe-4S] cluster. The reaction is 10(4)-fold faster than that observed with O(2) and is by far the most rapid iron-sulfur cluster nitrosylation reaction reported to date. An overall stoichiometry of [Fe(4)S(4)(Cys)(4)](2-) + 8NO → 2[Fe(I)(2)(NO)(4)(Cys)(2)](0) + S(2-) + 3S(0) has been established by determination of the sulfur products and their oxidation states. Kinetic analysis leads to a four-step mechanism that accounts for the observed NO dependence. DFT calculations suggest the possibility that the nitrosylation product is a novel cluster [Fe(I)(4)(NO)(8)(Cys)(4)](0) derived by dimerization of a pair of Roussin's red ester (RRE) complexes.     

A general approach for prediction of motional EPR spectra from Molecular Dynamics (MD) simulations: application to spin labelled protein

A general approach for the prediction of EPR spectra directly and completely from single dynamical trajectories generated from Molecular Dynamics (MD) simulations is described. The approach is applicable to an arbitrary system of electron and nuclear spins described by a general form of the spin-Hamiltonian for the entire motional range. It is shown that for a reliable simulation of motional EPR spectra only a single truncated dynamical trajectory generated until the point when correlation functions of rotational dynamics are completely relaxed is required. The simulation algorithm is based on a combination of the propagation of the spin density matrix in the Liouville space for this initial time interval and the use of well defined parameters calculated entirely from the dynamical trajectory for prediction of the evolution of the spin density matrix at longer times. A new approach is illustrated with the application to a nitroxide spin label MTSL attached to the protein sperm whale myoglobin. It is shown that simulation of the EPR spectrum, which is in excellent agreement with experiment, can be achieved from a single MD trajectory. Calculations reveal the complex nature of the dynamics of a spin label which is a superposition of the fast librational motions within dihedral states, of slow rotameric dynamics among different conformational states of the nitroxide tether and of the slow rotational diffusion of the protein itself. The significance of the slow rotameric dynamics of the nitroxide tether on the overall shape of the EPR spectrum is analysed and discussed.     

Magnetic circular dichroism evidence for a weakly coupled heme-radical pair at the active site of cytochrome cd1, a nitrite reductase

In nitrite-treated cytochrome cd1 nitrite reductase, heme d1 is electron paramagnetic resonance silent but paramagnetic. Analysis of the unusual temperature dependence of the magnetic circular dichroism spectra unambiguously demonstrates that the heme d1 is not in the oxoferryl (FeIV=O) state but is low-spin FeIII weakly coupled to a radical species. This species could be either a protein-bound radical generated by a nitrite ion reacting with a heme group resulting in a one-electron oxidation of an amino acid residue, possibly tyrosine or tryptophan, adjacent to heme d1, or a heme d1 FeIIINO complex.     

Study of Retention Ability of Nucleopore Membranes

The influence of pore sizes of nucleopore membranes and their shapes on the retention of polystyrene particles of 40–100 nm in size was studied. The interrelation between structural parameters of the nucleopore membranes found by various methods and the efficiency of filtration of calibrated particles were analyzed. The potential and limitations of the procedure for determining the efficiency of filtration of nanosized latex particles was demonstrated; the procedure was based on UV absorption spectroscopy.     

A new promising method for processing of serpentinites

A new thermal-acid method for processing of serpentinized ultrabasic rocks was developed. The method makes it possible to recover, in a very short time and in good yield, magnesium and iron(III) in the form of salts (hydroxides or oxides) and two varieties of SiO₂ as an aqua silica gel and light silica.