On the induced‐fit mechanism of substrate‐enzyme binding structures of nylon‐oligomer hydrolase

We present a detailed computational investigation of the induced‐fit motion in a nylon‐oligomer hydrolase (NylB) upon substrate binding. To this aim, we resort on the recently introduced parallel cascade selection molecular dynamics approach, allowing for an accelerated access to the set of conformational changes from an open‐ to a closed‐state structure to form the enzyme‐substrate complex in a specific induce‐fit mechanism. The structural investigation is quantitatively complemented by free energy analyses within the umbrella sampling algorithm accompanied by weighted histogram analysis. We find that the stabilization free energy is about 1.4 kcal/mol, whereas the highest free energy barrier to be overcome is about 2.3 kcal/mol. Conversely, the energetic contribution for the substrate binding is about 20 kcal/mol, as estimated from Generalized Born/Surface Area. This means that the open‐close induced‐fit motion could occur frequently once the substrate binds to the open state of NylB. © 2014 Wiley Periodicals, Inc.     

C-S bond cleavage of pyridine-2-thiol: a new functionality of quadruply bridged dinuclear platinum and palladium complexes

Treatment of pyridine-2-thiol (pytH) with H(2) (60 atm) in the presence of 5-methylpyridine-2-thiolate (5-mpyt)-bridged dinuclear Pt(III), Pt(II), or Pd(II) complexes (1 mol %) in DMF at 150 degrees C for 72 h leads to the formation of pyridine in 3-51% yield. From the (1)H NMR study of the exchange reactions and of the products under D(2) pressure, it is suggested that the catalytic reaction involves bimetallic activation of the pyt ligand followed by the liberation of pyridine and H(2)S.     

Preparation and characterization of silica-pillared derivatives from kanemite

The silica-pillared derivatives from kanemite (NaHSi(2)O(5).3H(2)O) were prepared by intercalation of dialkyldimethylammonium (DADMA) ion and pillaring with tetraethylorthosilicate. The formation of silica pillars between the silicate sheets was demonstrated by X-ray diffraction, (29)Si CP/MAS NMR, and TEM observation. The basal spacing depended on the chain length of DADMA. Nitrogen adsorption study showed that the specific surface area was enlarged over 1000 m(2) g(-1) by the pillaring and that the pore size was in the micropore region. Water and benzene adsorption isotherms revealed that the surface properties of the pillared derivatives show hydrophobic character.     

Drawing of poly(p-phenylene sulfide) by solid-state coextrusion

The effects of drawing temperature on the physical and mechanical properties of poly(p-phenylene sulfide) have been studied. A melt-quenched film was drawn by solid-state coextrusion both below (75°C) and above (95 and 110°C) the glass transition temperature T_g (85°C) of PPS. The maximum extrusion draw ratio (EDR_max) increased from 3.4 to 5.6 with increasing extrusion temperature T_e from 75 to 110°C. It was found that extrusion drawing just above the T_g of PPS (95°C) produced more stress-induced crystals. A high efficiency of draw in the amorphous region was achieved by extrusion at T_e-75°C. The tensile modulus at EDR_max decreased from 5.1 to 3.5 GPa with increasing T_e from 75 to 110°C. The low efficiency of draw for the samples extruded at 110°C is explained in terms of disentanglement and chain slippage during drawing due to a less effective network.     

Development of high-radiation-sensitive polymer gel for magnetic resonance imaging in three-dimensional dosimetry

We developed a high radiation sensitive polymer gel by modifying the amounts of the gel components and the temperature for the gel preparation. We evaluated its relaxation time linearity against dose and compared the measured dose distribution with the calculated one. For the relaxation time-dose linearity, irradiations were carried out with a linear accelerator using 6 MV photons and doses ranging from 0-5.0 Gy. The relationship between dose and R(2) value (reciprocal of T(2) relaxation time) was measured and it had good linearity over a wide range (0.3-5 Gy). The measured dose distributions were in good agreement with calculated ones. Since the present gel has higher sensitivity and it is synthesized more easily at lower cost than conventional polymer gels, we expect to see improved three-dimensional (3D) dosimetry using it.     

Sigmasigma* transition in anti,cisoid alternating oligosilanes: clear-cut evidence for suppression of conjugation effect by a cisoid turn

On the basis of the UV absorption spectra of the anti,cisoid alternating oligosilanes, the first experimental clear-cut evidence was presented for the generally accepted idea that the sigma conjugation in polysilanes does not effectively extend through a tetrasilane fragment with a small dihedral angle such as a cisoid turn.     

Influence of shell strength on shape transformation of micron-sized,monodisperse, hollow polymer particles

Micron-sized, monodisperse, non-spherical polymer particles with "rugby ball" and "red blood corpuscle"-like shapes were produced by seeded polymerization of the dispersion of (divinylbenzene/vinylbiphenyl/xylene)-swollen polystyrene particles prepared by utilizing the dynamic swelling method which the authors proposed in 1991. Their non-spherical shapes were based on buckling of the shell of the resultant hollow particles. In this article, the reversible shape transformation of the hollow composite polymer particle between spherical and such non-spherical shapes was studied in detail by controlling the shell strength. A part of the shell was buckled by external pressure which was caused by evaporation of xylene from the hollow when the shell had the tensile modulus below the critical value calculated from the pressure-buckling relationship of a spherical shell proposed by Uemura. The plasticization of the shell by a good solvent was one of key factors for the shape transformation.