Triesterase and Promiscuous Diesterase Activities of a Di‐CoII‐Containing Organophosphate Degrading Enzyme Reaction Mechanisms

The reaction mechanism for the hydrolysis of trimethyl phosphate and of the obtained phosphodiester by the di‐Co^II derivative of organophosphate degrading enzyme from Agrobacterium radiobacter P230(OpdA), have been investigated at density functional level of theory in the framework of the cluster model approach. Both mechanisms proceed by a multistep sequence and each catalytic cycle begins with the nucleophilic attack by a metal‐bound hydroxide on the phosphorus atom of the substrate, leading to the cleavage of the phosphate‐ester bond. Four exchange‐correlation functionals were used to derive the potential energy profiles in protein environments. Although the enzyme is confirmed to work better as triesterase, as revealed by the barrier heights in the rate‐limiting steps of the catalytic processes, its promiscuous ability to hydrolyze also the product of the reaction has been confirmed. The important role played by water molecules and some residues in the outer coordination sphere has been elucidated, while the binuclear Co^II center accomplishes both structural and catalytic functions. To correctly describe the electronic configuration of the d shell of the metal ions, high‐ and low‐spin arrangement jointly with the occurrence of antiferromagnetic coupling, have been herein considered.     

Krylov-Bogolyubov averaging of asymptotically autonomous differential equations

We apply the Krylov and Bogolyubov asymptotic integration procedure to asymptotically autonomous systems. First, we consider linear systems with quasi-periodic coefficient matrix multiplied by a scalar factor vanishing at infinity. Next, we study the asymptotically autonomous Van-der-Pol oscillator.

     

Structure and morphology of laser-ablated WO3 thin films

The structure and surface morphology of WO₃ thin films deposited by a laser-ablation technique have been found to be strongly dependent on the deposition conditions and the nature of the substrate. By precisely controlling the substrate temperature and the oxygen partial pressure, amorphous, polycrystalline, nano-crystalline and iso-epitaxial WO₃ thin films were successfully grown. The structure and surface morphological features of the films from X-ray diffraction and atomic force microscopy data are described in relation to the deposition conditions. PACS 81.15.Fg; 68.55.-a; 68.37.Ps     

v-Triazolines. XXXIX . 1,2,4-Triaryl-3-aminopyrroles. Unusual Reaction Products in the Pyrolysis of 5-Amino-v-triazolines and the Crystal Structure of 2-(3-Morpholin-4-yl-2,4-pyrrol-1-yl)benzonitrile

Pyrolysis of 4-aryl-5-amino-v-triazolines affords, generally, amidines and/or benzanilides. Pyrolysis of 4-aryl-5-morpholino-v-triazolines 6 , together with the expected amidines 7 and/or aryanilides 8 , produced the morpholinopyrroles 9 . The reaction mechanism of this unusual transformation is discussed. Influence of solvent dipole moment in pyrrole formation is suggested. Pyrrole 9a [i.e. 2-(3-morpholin-4-yl-2,4-pyrrol-1-yl)-benzonitrile] has been fully characterized and its molecular structure has been determined by X-ray diffraction analysis.     

The first total synthesis of (R)-convolutamydine A

The first total synthesis of (R)-convolutamydine A has been achieved by the organocatalytic addition of acetone to 4,6-dibromoisatin. The absolute configuration was determined by single crystal X-ray diffraction. DFT studies were used to model the transition states for the aldol reaction and equilibrium geometries of the post-aldol reaction intermediates. The DFT study revealed that the aldol bond forming reaction was considerably endothermic.     

Oscillatory kinetics and mechanism of the chromate catalyzed decomposition of hydrogen peroxide

Oscillatory change of pH occurs during the chromate-catalyzed decomposition of hydrogen peroxide in a weakly acidic medium at elevated temperature and at high initial concentration of hydrogen peroxide. In a closed system, there are only two or three periods, but sustained oscillation occurs in a CSTR. In a CSTR bistability is also found. In closed systems the temperature exhibits a great maximum (up to 15°C increase), in a CSTR sustained oscillation occurs at a constant stationary temperature.     

Large-scale production of cellulose-binding domains. Adsorption studies using CBD-FITC conjugates

A method for the gram-scale production of cellulose-binding domains (CBD) through the proteolytic digestion of a commercial enzymatic preparation (Celluclast) was developed. The CBD obtained, isolated from Trichoderma reesei cellobiohydrolase I, is highly pure and heavily glycosylated. The purified peptide has a molecular weight of 8.43 kDa, comprising the binding module, a part of the linker, and about 30% glycosidic moiety. Its properties may thus be different from recombinant ones expressed in bacteria. CBD-fluorescein isothiocyanate conjugates were used to study the CBD-cellulose interaction. The presence of fluorescent peptides adsorbed on crystalline and amorphous cellulose fibers suggests that amorphous regions have a higher concentration of binding sites. The adsorption is reversible, but desorption is a very slow process.     

Cantor exchange systems and renormalization

We prove a one-to-one correspondence between (i) C¹⁺ conjugacy classes of C^1+H Cantor exchange systems that are C^1+H fixed points of renormalization and (ii) C¹⁺ conjugacy classes of C^1+H diffeomorphisms f with a codimension 1 hyperbolic attractor Λ that admit an invariant measure absolutely continuous with respect to the Hausdorff measure on Λ. However, we prove that there is no C^1+α Cantor exchange system, with bounded geometry, that is a C^1+α fixed point of renormalization with regularity α greater than the Hausdorff dimension of its invariant Cantor set.