PICOSECOND LASER PHOTOLYSIS STUDIES OF FLUORESCENCE QUENCHING MECHANISMS OF FLAVIN: A DIRECT OBSERVATION OF INDOLE-FLAVIN SINGLET CHARGE TRANSFER STATE FORMATION IN SOLUTIONS and FLAVOENZYMES

Formation of singlet charge transfer (heteroexcimer) states in the course of the fluorescence quenching of lumiflavin and riboflavin tetrabutyrate by indole and N-methylindole have been directly observed by means of time-resolved absorption spectral measurements using a picosecond laser photolysis method. Similar transient spectra have been observed also in the case of a flavoenzyme, D-amino acid oxidase.     

Development of pyrrole-imidazole polyamide for specific regulation of human aurora kinase-A and -B gene expression

Pyrrole-imidazole polyamide (PIP) is a nuclease-resistant novel compound that inhibits gene expression through binding to the minor groove of DNA. Human aurora kinase-A (AURKA) and -B (AURKB) are important regulators in mitosis during the cell cycle. In this study, two specific PIPs (PIP-A and PIP-B) targeting AURKA and AURKB promoter regions were designed and synthesized, and their biological effects were investigated by several in vitro assays. PIP-A and PIP-B significantly inhibited the promoter activities, mRNA expression, and protein levels of AURKA and AURKB, respectively, in a concentration-dependent manner. Moreover, 1:1 combination treatment with both PIPs demonstrated prominent antiproliferative synergy (CI value [ED(50)] = 0.256) to HeLa cells as a result of inducing apoptosis-mediated severe catastrophe of cell-cycle progression. The novel synthesized PIP-A and PIP-B are potent and specific gene-silencing agents for AURKA and AURKB.     

Solvation dynamics of coumarin 153 in alcohols confined in silica nanochannels

Solvation dynamics in alcohols confined in silica nanochannels was examined by time-resolved fluorescence spectroscopy using coumarin 153 (C153) as a fluorescent probe. Surfactant-templated mesoporous silica was fabricated inside the pores of an anodic alumina membrane. The surfactant was removed by calcination to give mesoporous silica (Cal-NAM) containing one-dimensional (1D) silica nanochannels (diameter, 3.1 nm) whose inner surface was covered with silanol groups. By treating Cal-NAM with trimethylchlorosilane, trimethylsilyl (TMS) groups were formed on the inner surface of the silica nanochannels (TMS-NAM). Fluorescence dynamic Stokes shifts of C153 were measured in alcohols (ethanol, butanol, hexanol, and decanol) confined in the silica nanochannels of Cal- and TMS-NAMs, and the time-dependent fluorescence decay profiles could be best fitted by a biexponential function. The estimated solvent relaxation times were much larger than those observed in bulk alcohols for both Cal- and TMS-NAMs when ethanol or butanol was used as a solvent, indicating that the mobility of these alcohol molecules was restricted within the silica nanochannels. However, hexanol or decanol in Cal- and TMS-NAMs did not cause a remarkable increase in the solvent relaxation time in contrast to ethanol or butanol. Therefore, it was concluded that a relatively rigid assembly of alcohols (an alcohol chain) was formed within the silica nanochannels by hydrogen bonding interaction and van der Waals force between the surface functional groups of the silica nanochannels and alcohol molecules and by the successive interaction between alcohol molecules when alcohol with a short alkyl chain (ethanol or butanol) was used as a solvent.     

Analytical separation of tea catechins and food-related polyphenols by high-speed counter-current chromatography

High-speed counter-current chromatography (HSCCC) using the type-J coil planet centrifuge was applied to compositional analysis of tea catechins and separation of other food-related polyphenols. The HSCCC separation of nine different standard compounds and those from extracts of commercial tea leaves was performed with a two-phase solvent system composed of tert-butyl methyl ether-acetonitrile-0.1% aqueous trifluoroacetic acid (TFA) (2:2:3, v/v/v) by eluting the upper organic phase at a flow rate of 2 ml/min. The main compounds in the extract of non-fermented green tea were found to be monomeric catechins, their galloylated esters and caffeine. In addition to these compounds, oxidized pigments, such as hydrophobic theaflavins (TFs) and polar thearubigins (TRs) were also separated and detected from the extracts of semi-fermented oolong tea and fermented black tea. Furthermore, several food-related polyphenols, such as condensed catechin oligomers (procyanidins), phenolic acids and flavonol glycosides were clearly separated under the same HSCCC condition. These separation profiles of HSCCC provide useful information about the hydrophobic diversity of these bioactive polyphenols present in various types of teas and food products.     

Mechanistic study of the electrodeposition of nanoporous self-assembled ZnO/Eosin Y hybrid thin films: effect of eosin concentration

ZnO films prepared by one-step electrodeposition in the presence of dissolved eosin molecules present an internal nanoporous hybrid structure resulting from self-assembling processes occurring in solution between ZnO and eosin components. This study aims to better understand the underlying growth mechanism, which is still unexplained. The films were deposited by cathodic electrodeposition from an oxygen-saturated aqueous zinc chloride solution. The effects of the addition of 10 to 100 micromol.L(-1) eosin Y, as a sodium salt, on the growth rate and film properties, were systematically studied while all other parameters remained constant (concentrations of zinc salt and supporting electrolyte, applied potential of -1.4 V versus the mercurous sulfate electrode (MSE), temperature of 70 degrees C, rotating disk electrode at 300 rotations per min, and a glass-coated tin oxide electrode). It is shown that the addition of eosin provokes the formation of a nanoporous "cauliflower" structure whose nodule size and composition depend on the eosin concentration in the bath. The growth rate of the hybrid films increases markedly with the eosin concentration. The ZnO and eosin contents of the films are determined for each concentration by chemical analysis. Comparing with thickness determinations, it is shown that the total porosity increases up to 60-65% in volume fraction toward an eosin concentration of 100 micromol.L(-1). The empty pore volume fraction increases up to about 30% at an eosin concentration of about 20 micromol.L(-1) and then decreases. These correlations have been precisely established for the first time. It is shown that the global composition is fixed by the relative rate of deposition for zinc oxide, which is constant, and for the relative rate of eosin inclusion, which is proportional to the concentration in solution. This is explained on the basis of different steps in the growth mechanism, in particular, a diffusion effect limitation for both oxygen and eosin. This variation explains part of the increase in the growth rate. Another contribution is related by the structural effect on the nanoscale leading to the formation of the interpenetrated porous network. Competition between empty and eosin-filled parts of the pore network is evidenced. The formation of the porous network structure could be governed by a diffusion-limited aggregation mechanism. The system may represent a reference case of competing reactions in the electrochemical self-assembly of hybrid nanostructures.     

Photoinduced alignment of polymer liquid crystals containing azobenzene moieties in the side group VII. On He-Ne laser beam irradiation

Photoinduced alignment in a polymer liquid crystal prepared from 6-{1-[4-(2-cyano-4-nitrophenylazo)phenyl]piperazino}hexyl acrylate and 4'-[6-(methacryloyloxy)hexyloxy]-4-cyanobiphenyl was investigated for the first time on irradiation with a polarized He-Ne laser beam at 633 nm. The azobenzene moieties as well as the inert cyanobiphenyl mesogenic units were aligned with the molecular long axis perpendicular to the polarization direction of the irradiation light. Alignment induced on short irradiation was reversible, while that induced under prolonged irradiation was irreversible due to the occurrence of crosslinking which might be caused by photoinduced decomposition of the azobenzene moieties during the photoirradiation process.     

Nickel(II) oxide surface-modified titanium(IV) dioxide as a visible-light-active photocatalyst

The electronic modification of TiO(2) with highly dispersed NiO particles smaller than ca. 2 nm by the chemisorption-calcination-cycle technique has given rise to a high level of visible-light-activity exceeding that of iron oxide-surface modified TiO(2) simultaneously with the UV-light-activity being significantly increased.     

Drug–tea polyphenol interaction

Propericiazine (PCZ) is an antipsychotic agent used for the treatment and the prevention of relapse of schizophrenia. We found that when an oral solution containing PCZ was mixed with a green tea drink, the residual content of PCZ was reduced by forming an insoluble complex between PCZ and tea polyphenol. In this study, the mechanism underlying the incompatibility of PCZ with green tea polyphenol (GTP) in the solution was clarified by isothermal titration microcalorimetry (ITC). Both solutions of 27.4 mM PCZ and 2.2 mM (?)-epigallocatechin gallate (EGCg), which is a main ingredient of GTP, were mixed and then PCZ in the filtrate was reduced to approximately 60 %. According to measurement at 298 K by ITC, PCZ formed an insoluble complex with EGCg at an associate constant (K) of 4.75 × 10² M^?1 exothermically, ΔH = ?40.0 kJ mol^?1. When (?)-epicatechin gallate (ECg) was used as the GTP, PCZ interacted with ECg with K and ΔH values of 3.74 × 10² M^?1 and ?22.1 kJ mol^?1, respectively. On the other hand, little heat of the reaction between PCZ and (?)-epigallocatechin or (?)-epicatechin was observed. The results indicated that the main reason for this incompatibility was the formation of an insoluble complex by PCZ and a gallate-type GTP such as EGCg and ECg in the aqueous solution.     

Cooperative catalytic reactions using distinct transition-metal catalysts: ruthenium- and copper-catalyzed enantioselective propargylic alkylation

The enantioselective propargylic alkylation of propargylic alcohols with β-ketoesters in the presence of a thiolate-bridged diruthenium complex and a copper complex as co-catalyst affords the corresponding propargylic alkylated products in excellent yields as a mixture of two diastereoisomers with high enantioselectivity (up to 95% enantiomeric excess (ee)). The findings reported herein not only open up a new type of enantioselective propargylic substitution reaction, but also a new aspect of cooperative catalytic reactions using distinct transition metals to realize a useful transformation that cannot be achieved by a single catalyst.