Metal ion-dependent fluorescent dynamics of photoexcited zinc-porphyrin and zinc-myoglobin modified with ethylenediaminetetraacetic acid

The reconstituted zinc-myoglobin (ZnMb) dyads, ZnMb-[M(II)(edta)], have been prepared by incorporating a zinc-porphyrin (ZnP) cofactor modified with ethylenediaminetetraacetic acid (H(4)edta) into apo-Mb. In case of the monomeric ZnP(edta) cofactor coordinated by one pyridine molecule, ZnP(py)(edta), a spontaneous 1:1 complex with a transient metal ion was formed in an aqueous solvent, and the photoexcited singlet state of ZnP, (1)(ZnP)*, was quenched by the [Cu(II)(edta)] moiety through intramolecular photoinduced electron-transfer (ET) reaction. The rate constant for the intramolecular quenching ET (k(q)) at 25 degrees C was successfully obtained as k(q) = 5.1 x 10(9) s(-1). In the case of Co(2+), Ni(2+), and Mn(2+), intersystem crossing by paramagnetic effect was mainly considered between (1)(ZnP)* and the [M(II)(edta)] complex. For the ZnMb-[M(II)(edta)] systems, the intramolecular ET reaction between the excited singlet state of (1)(ZnMb)* and the [Cu(II)(edta)] moieties provided the slower quenching rate constant, k(q) = 2.1 x 10(8) s(-1), compared with that of the ZnP(py)(edta) one. Kinetic studies also presented the efficient fluorescence quenching of the (1)(ZnMb)*-[Co(II)(edta)] dyad. Our study clearly demonstrates that wrapping of the ZnP cofactor by the apoprotein matrix and synthetic manipulation at the Mb surface ensure metal ion-sensitive fluorescent dynamics of ZnMb and provides valuable information to elucidate the complicated mechanism of the biological photoinduced ET reactions of hemoproteins.     

Non-vanishing of the twisted cohomology on the complement of hypersurfaces

Generically, the cohomology with coefficients in a local system of rank one on the complement in of the union of a finite number of hypersurfaces vanishes except in the highest dimension. We study the non-generic case, in which the cohomology in other dimensions does not vanish. When the hypersurfaces are hyperplanes, many examples of this kind are known. In this paper, we consider the case in which the hypersurfaces need not be hyperplanes. We prove that the hypersurfaces given by some particular linear systems have non-vanishing local system cohomologies.

     

A new leishmanicidal saponin from Brunfelsia grandiflora

A new furostan-type saponin (1) was isolated from the methanolic extract of Brunfelsia grandiflora leaves, together with four known compounds. The chemical structure of 1 was determined by spectroscopic analysis and chemical reaction to be 26-O-beta-D-glucopyranosyl 22alpha-methoxyfurost-3beta,26-diol 3-O-beta-D-xylopyranosyl(1-->3)-{beta-D-glucopyranosyl(1-->2)}-beta-D-glucopyranosyl(1-->4)-beta-D-glucopyranoside. Compound 1 showed potent leishmanicidal activity in vitro against Leishmania major.     

Determination of (R)-xanthoanthrafil, a phosphodiesterase-5 inhibitor, in a dietary supplement promoted for sexual enhancement

We describe here the first case of the finding of xanthoanthrafil, a phosphodiesterase-5 inhibitor, in a dietary supplement. A methanol extract of the supplement product was first analyzed by TLC and HPLC. The results indicated that the extract contained an unknown compound. The molecular weight of the compound was 389 and the accurate mass showed its elemental composition to be C(19)H(23)N(3)O(6). Combined with this data, NMR analysis revealed the planar structure of the unknown compound to be N-(3,4-dimethoxybenzyl)-2-(1-hydroxypropan-2-ylamino)-5-nitrobenzamide. The R-configuration of this compound had been synthesized as a phosphodiesterase-5 inhibitor, formerly reported as FR226807 by Fujisawa Pharmaceutical Co., Ltd. The absolute configuration of the isolated compound was estimated to have R-configuration by its optical rotation. Considering its general properties, this compound is renamed as (R)-xanthoanthrafil with the agreement of Astellas Pharma Inc. which is the successor of Fujisawa Pharmaceutical Co., Ltd. Quantitative analysis revealed that the content of (R)-xanthoanthrafil in the product was about 31 mg/capsule.     

Structure-based engineering of a plant type III polyketide synthase: formation of an unnatural nonaketide naphthopyrone

Pentaketide chromone synthase (PCS) from Aloe arborescens is a novel plant-specific type III polyketide synthase (PKS) that produces 5,7-dihydroxy-2-methylchromone from five molecules of malonyl-CoA. On the basis of the crystal structures of wild-type and M207G mutant PCS, the F80A/Y82A/M207G triple mutant was constructed and shown to produce an unnatural novel nonaketide naphthopyrone by sequential condensations of nine molecules of malonyl-CoA. This is the first demonstration of the formation of a nonaketide by the structurally simple type III PKS. A homology model predicted that the active-site cavity volume of the triple mutant is increased to 4 times that of the wild-type PCS.     

Nitrile-promoted Rh-catalyzed intermolecular hydroacylation of olefins with salicylaldehyde

Rh-catalyzed intermolecular hydroacylation between salicylaldehyde and alkenylnitriles proceeded at room temperature to preferentially give normal-hydroacylated products. Addition of CH3CN and NaOAc accelerated the Rh-catalyzed hydroacylation of monoolefins to exclusively produce the normal-hydroacylated products under mild reaction conditions. Plausible mechanisms for the regioselections are also described.     

Electrochemically assisted visible light photocatalysis in a heterosupramolecular system consisting of alpha-Fe2O3 and surfactant molecular assembly

The synergy of an anodic-biased alpha-Fe2O3 film and a cationic surfactant molecular assembly leads to a high visible light induced activity for 2-naphthol oxidation and high stability. An abrupt increase in the photocatalytic activity at a surfactant concentration of ca. 0.2 mmol dm(-3) results from the adsolubilization of 2-naphthol into the hydrophobic nanospace of the surfactant bilayer formed on the alpha-Fe2O3 surface. Also, the surfactant bilayer provides sustainable photocurrent during the reaction.     

A finite element analysis of mach reflection by using the Boussinesq equation

The numerical analysis of ‘Mach reflection’, which is the reflection of an obliquely incident solitary wave by a vertical wall, is presented. For the mathematical model of the analysis, the two-dimensional Boussinesq equation is used. In order to solve the equation in space, the finite element method based on the linear triangular element and the conventional Galerkin method is applied. The combination of explicit and semi-implicit schemes is employed for the time integration. Moreover, one of the treatments for the open boundary condition, in which the analytical solution of the linearized Boussinesq equation in the outside domain is linked to the discrete values of velocity and water elevation in the inside domain, is applied for the modeling of the Mach reflection problem. © 1998 John Wiley & Sons, Ltd.     

Differences between PREMIER combustion in a natural gas spark-ignition engine and knocking with pressure oscillations

PREMIER (PREmixed Mixture Ignition in the End-gas Region) combustion occurs with auto-ignition in the end-gas region when the main combustion flame propagation is nearly finished. Auto-ignition is triggered by the increases in pressure and temperature induced by the main combustion flame. Similarly to engine knocking, heat is released in two stages when engines undergo this type of combustion. This pattern of heat release does not occur during normal combustion. However, engine knocking induces pressure oscillations that cause fatal damage to engines, whereas PREMIER combustion does not. The purpose of this study was to elucidate PREMIER combustion in natural gas spark-ignition engines, and differentiate the causes of knocking and PREMIER combustion. We applied combustion visualization and in-cylinder pressure analysis using a compression–expansion machine (CEM) to investigate the auto-ignition characteristics in the end-gas region of a natural gas spark-ignition engine. We occasionally observed knocking accompanied by pressure oscillations under the spark timings and initial gas conditions used to generate PREMIER combustion. No pressure oscillations were observed during normal and PREMIER combustion. Auto-ignition in the end-gas region was found to induce a secondary increase in pressure before the combustion flame reached the cylinder wall, during both knocking and PREMIER combustion. The auto-ignited flame area spread faster during knocking than during PREMIER combustion. This caused a sudden pressure difference and imbalance between the flame propagation region and the end-gas region, followed by a pressure oscillation.     

8-Endo selective Friedel-Crafts cyclization of vinyloxiranes with Co2(CO)6-complexed acetylene

An 8-endo selective Friedel-Crafts cyclization of vinyloxirane 8 with Co₂(CO)₆-complexed benzeneacetylene was found to give poly-functional eight-membered cyclic compound 9 in high yields.