DSC TOPEM® study of high-energy mechanical milling-driven amorphization in β-As4S4-based arsenicals

Journal of Thermal Analysis and Calorimetry - Temperature-modulated DSC TOPEM® method was applied to study amorphization in directly synthesized high-temperature polymorph of tetra-arsenic...     

Recent trends in enzyme engineering aiming to improve bioelectrocatalysis proceeding with direct electron transfer

Among the known types of electrochemical biosensors, the third generation based on the ability of some enzymes to direct electron transfer (DET) is the most promising one. The enzyme property to DET is depending on its capability to electron transfer from enzymatically reduced built-in native cofactor (flavin mononucleotide, flavin adenine dinucleotide, pyrroloquinoline quinone, or heme) to a conductive surface directly for single cofactor enzymes or through a native structural electron acceptor (heme or copper-containing prosthetic groups) for multicofactor enzymes. Thus, there are two possibilities to use such type enzymes: to find a natural source of the enzyme with these properties; or to construct the recombinant chimeric analogs using the gene-engineering techniques. The modern molecular genetics opens the possibility to be independent of million-year natural evolution and engineer the specific enzymes for scientific and technological needs. This brief review is focused mostly on the recent publications on application of DET-capable engineered enzymes for the third-generation electrochemical biosensors.     

The peculiarities of homogeneous nucleation of reactive Cu0 colloidal particles in the presence of functional oligoperoxides

A method is proposed that combines the stage of formation of colloidal metal and metal-oxide particles with the stage of their surface modification by functional surface-active oligoperoxides (FSAP), which are sorbed irreversibly. Investigation of copper particle homogeneous nucleation kinetics witnesses the significant influence of supermolecular micelle-like structures formed by FSAP in solution on the reduction rate of Cu2+ cations caused by a phenomenon analogous to micellar catalysis. The rate constants of copper reduction in different local zones of the process have been determined. Particle homogeneous nucleation kinetics in the presence of surface-active oligoperoxides has been found to correspond to the main regularities of the Michaelis-Menten equation describing micellar catalysis. The carrying out of copper particle formation in distinct zones correlates well with the particle size distribution. The presence of reactive ditertiary peroxidic fragments on the particle surface as a result of FSAP sorption confers reliable protection from oxidation, hydrophobicity, and ability to form free radicals and participate in elementary stages of radical processes.     

Regio- and stereoselectivity of polar [2+3] cycloaddition reactions between (Z)-C-(3,4,5-trimethoxyphenyl)-N-methylnitrone and selected (E)-2-substituted nitroethenes

[2+3] Cycloaddition reactions of the highly reactive (Z)-C-(3,4,5-trimethoxyphenyl)-N-methylnitrone with (E)-2-R-nitroethenes proceed under mild conditions and yield mixtures of stereoisomeric 2-methyl-3-(3,4,5-trimethoxyphenyl)-4-nitro-5-R-isoxazolidines. The effect of regiospecificity of the cycloadditions may be accounted for by the theory of electrophilicity indexes. Stereoselectivity, however, is determined by a compilation of steric and secondary orbital effects.      

Chimera states: the natural link between coherence and incoherence

Chimera states are remarkable spatiotemporal patterns in which coherence coexists with incoherence. As yet, chimera states have been considered as nongeneric, since they emerge only for particular initial conditions. In contrast, we show here that in a network of globally coupled oscillators delayed feedback stimulation with realistic (i.e., spatially decaying) stimulation profile generically induces chimera states. Intriguingly, a bifurcation analysis reveals that these chimera states are the natural link between the coherent and the incoherent states.     

A new semiconducting quaternary mixed halogenide: pentathallium dimercury pentabromide tetraiodide,Tl5Hg2Br5I4

A novel quaternary mixed halogenide, Tl₅Hg₂Br₅I₄, was synthesized by fusion of thallium bromide and mercury iodide in a 5:2 molar ratio. The crystal structure of Tl₅Hg₂Br₅I₄ represents a new series of composite structures described by the general formula nTlBr*mTl₂[HgBr₂I₂]; in this case, n = 4 and m = 8. Electronic structure calculations indicate that the title compound is a semiconductor.     

Spiro[3.3]heptane as a Saturated Benzene Bioisostere**

The spiro[3.3]heptane core, with the non-coplanar exit vectors, was shown to be a saturated benzene bioisostere. This scaffold was incorporated into the anticancer drug sonidegib (instead of the meta-benzene), the anticancer drug vorinostat (instead of the phenyl ring), and the anesthetic drug benzocaine (instead of the para-benzene). The patent-free saturated analogs obtained showed a high potency in the corresponding biological assays.     

Elastic 3-D alignment of rat brain histological images

A three-dimensional wavelet-based algorithm for nonlinear registration of an elastic body model of the brain is developed. Surfaces of external and internal anatomic brain structures are used to guide alignment. The deformation field is represented with a multiresolution wavelet expansion and is modeled by the partial differential equations of linear elasticity. A progressive estimation of the registration parameters and the usage of an adaptive distance map reduce algorithm complexity, thereby providing computational flexibility that allows mapping of large, high resolution datasets. The performance of the algorithm was evaluated on rat brains. The wavelet-based registration method yielded a twofold improvement over affine registration.     

The activity of NaOH buffered by silicate solids in molten sodium acetate-water at 317°C

Silica and sodium acetate are present in the steam generator tube sheet crevices of many nuclear power plants. Trace solutes in the condensate are tremendously concentrated in the crevices by boiling. Sparingly soluble sodium silicates and other solids precipitate from the crevice liquid leaving an extremely concentrated molten mixture of water, sodium acetate and other salts. The precipitates buffer the activity of sodium hydroxide in the superheated liquid that remains. The activity of NaOH corresponding to the buffers quartz/sodium disilicate and sodium disilicate/sodium metasilicate at 317°C has been determined experimentally. The sodium hydroxide content of a sodium acetate-water melt buffered by these reactions was determined bychemical analysis, and the corresponding activity of NaOH at temperature was calculated using the recently published Pitzer-Simonson Model of molten salt-water mixtures. The molten mixture of sodium acetate and water plays the role of solvent in these experiments and calculations. The free energies of formation of solid sodium silicates at 317°C were also determined. The activity of NaOH corresponding to other silicate and phosphate buffers was calculated using published thermodynamic data and estimated from phase diagrams.