Photocontrol of lactate dehydrogenase-spiropyran collagen membrane

Collagen fibrils were modified with β-l-[3,3-dimethyl-6′-nitrospiro-(indoline-2,2′-2H-benzopyran)] propionic anhydride. The spiropyran collagen membrane showed reverse photochromism. Lactate dehydrogenase (LDH, E.C. 1.1.1.27) was entrapped in the spiropyran collagen membrane. The activity of the LDH-spiropyran collagen membrane decreased under visible-light irradiation, and then increased again after incubation in the dark. The optimum pH of the LDH-spiropyran collagen membrane was displaced toward lower pH values under visible-light irradiation. The activity change of the LDH-spiropyran collagen membrane under visible-light irradiation depended on the LDH content.     

New condensing reagents for stereospecific synthesis of dinucleoside monophosphate aryl esters

Condensation of 5′-O-dimethoxytritylnucleoside 3′-O-(o-chlorophenyl) phosphates and 3′-O-benzoylnucleosides with a new condensing reagent, 2,4,6-triisopropylbenzenesulfonyl 5-(pyridin-2-yl) tetrazolide gave o-chlorophenyl ester of protected dinucleoside monophosphates which had a stereospecific configuration. The corresponding mesitylenesulfonyl derivative gave similar results.     

Detecting synchronizations in an asymmetric vocal fold model from time series data

A nonlinear modeling approach is presented for the reconstruction of the synchronization structure in an asymmetric two-mass model from time series data. The asymmetric two-mass model describes a variety of normal and pathological human voices associated with synchronous and desynchronous oscillations of the two asymmetric vocal folds. Our technique recovers the synchronization diagram, which yields the regimes of synchronization as well as desynchronization, which are dependent upon the asymmetry parameter and the subglottal pressure. This allows the prediction of the regime of pathological phonation associated with desynchronization of the vocal folds from a few sets of recorded time series. It is shown that the modeling is quite effective when the time series data are chaotic and if they are taken from a regime of desynchronization. We discuss the applicability of the present approach as a diagnostic tool for voice pathologies.     

Studies of NO adsorption on Pt(110)-(1 x 2) and (1 x 1) surfaces using density functional theory

Adsorption of NO on Pt(110)-(1 x 2) and (1 x 1) surfaces has been investigated by density functional theory (DFT) method (periodic DMol(3)) with full geometry optimization and without symmetry restriction. Adsorption energies, structures, and N-O stretching vibrational frequencies of NO are studied by considering multiple possible adsorption sites and comparing with the experimental data. Adsorption is strongly dependent on both coverage and surface phase. The assignment of adsorption sites has been carried out with precise calculation of vibrational frequencies for NO on various sites. We clearly show the NO site switching on both of the surfaces as found in the experiments: at low coverages, bridge species is formed on the surface, and at high coverages, NO switches to atop sites.     

Observation of the transient rotator phase of n-hexadecane in emulsified droplets with time-resolved two-dimensional small- and wide-angle X-ray scattering

Crystallization of n-hexadecane in emulsion droplets was studied using time-resolved two-dimensional small- and wide-angle x-ray scattering with differential scanning calorimetry (2D-SAXS-WAXS-in situ DSC) which provides information about both nano- and subnanoscale structural change. n-hexadecane in droplets reproducibly crystallized into the stable triclinic phase via a transient-rotator phase. This is in contrast with previous results that the rotator phase of n-hexadecane was observed only occasionally for bulk samples. Thus we confirmed the existence of rotator phase in n-hexadecane, which is important for the study of crystallization of soft materials. We suggest that the rotator phase at the interface of oil and water plays a precursor role for bulk crystallization. This study demonstrates that 2D-SAXS-WAXS-in situ DSC is a powerful tool for the study of a transient phase.     

Concise three-component synthesis of defucogilvocarcin M

[reaction: see text] Concise synthesis of defucogilvocarcin M was achieved via the [2 + 2 + 2] approach to beta-phenylnaphthalene structure.     

A new approach to the synthesis of cyclic ethers via the intermolecular allylation of α-acetoxy ethers and ring-closing metathesis

A concise synthesis of the isolaurepinnacin skeleton 6 was achieved via the intermolecular allylation of the α-acetoxy ether 3 followed by ring-closing metathesis. This methodology was successfully applied to the convergent synthesis of the oxocene 15, an advanced synthetic intermediate for the total synthesis of laurencin.