Structure of YM-254890, a Novel Gq/11 Inhibitor from Chromobacterium sp. QS3666

The isolation and structure elucidation of YM-254890, a novel G_q/11 inhibitor from Chromobacterium sp. QS3666, is described. The gross structure was determined by one- and two-dimensional NMR studies and mass spectrometry. YM-254890 is a cyclic depsipeptide containing uncommon amino acids; β-hydroxyleucine (two residues), N,O-dimethylthreonine and N-methyldehydroalanine. YM-254890 exists as a mixture of two conformers in a variety of NMR solvents, and the distinction between major and minor conformers appears to lie in the geometry of the amide bond between 3-phenyllactic acid and N-methyldehydroalanine. The absolute stereochemistery was elucidated by Marfey's analysis and chiral HPLC analysis of the acid hydrolysate of YM-254890.     

ESR study of Cu(II) ion complexes adsorbed on interlamellar surfaces of montmorillonite

Oriented films of Cu(II)-montmorillonite before and after adsorption of pyridine, glycine and $\text{b}\text{?}$-alanine showed markedly orientation-dependent ESR spectra. Complex formation of Cu(II) ions with the adsorbates was indicated by changes in ESR parameters. The ESR spectra and parameters suggest that the complexes formed on the interlamellar surfaces of montmorillonite have planar or axially elongated tetragonal structures and that the symmetry axes of the complexes are oriented perpendicularly to the aluminosilicate layers of the clay.     

A facile synthesis of [1,2,4]triazino[3,2-f]purines and [1,2,4]triazepino[3,2-f]purines

[1,2,4]Triazino[3,2-f]purines 3a-e and [1,2,4]triazepino[3,2-f]purine 5 were synthesized by the reaction of 7,8-diamino-1,3-dimethylxanthine 1 with diketones such as glyoxal, diacetyl, dibenzoyl, pyruvic aldehyde dimethyl acetal, phenylglyoxal or acetylacetone in acetic acid in the presence of boric acid or polyphosphoric acid.     

Kinetic study of the quenching reaction of singlet oxygen by flavonoids in ethanol solution

The quenching rate of singlet oxygen (1O2) by seven kinds of flavonoids (flavone, flavonol, chrysin, apigenin, rutin, quercetin, and myricetin) with 2,3-double bonds has been measured spectrophotometrically in ethanol at 35 degrees C. The overall rate constants kQ (= kq + kr, physical quenching + chemical reaction) increased as the number of OH groups substituted to the flavone skeleton (that is, the total electron-donating capacity of flavonoids) increases. The existence of catechol or pyrogallol structure in the B-ring is essential for the 1O2 quenching of flavonoids. Log kQ was found to correlate with their peak oxidation potentials, E(P); the flavonoids that have smaller E(P) values show higher reactivities. Similarly, log kQ values of flavonoids correlate with the energy level of the highest occupied molecular orbital (E(HOMO)), calculated by the PM3 MO method, and the longest wavelength pi pi* excitation energy (E(ex)). The contribution of the chemical reaction (kr) was found to be negligible in these flavonoids. The kQ values of rutin, quercetin, and myricetin [(1.21 approximately 5.12) x 10(8) M(-1) s(-1)] were found to be larger than those of lipids [(0.9 approximately 6.4) x 10(4) M(-1) s(-1)], amino acids (<3.7 x 10(7) M(-1) s(-1)), and DNA (5.1 x 10(5) M(-1) s(-1)). The result suggests that these flavonoids may contribute to the protection of oxidative damage in foods and plants, by quenching 1O2.     

A synthetic approach to (+)-aldosterone and its relatives (2)- a stereoselective synthesis of (+)-trans-4,5-(4-methoxybenzo)- 1β , 7aβ - ( 2α-methoxymethyl- 5 -oxofuro) hydrindane

A stereoselectivity in an intramolecular cycloaddition of the olefinic $\text{o}$-quinodimethanes 13 and 23 generated $\text{in}$$\text{situ}$ from the thermolysis of optically active 4β-[2-(4-methoxybenzocyclobutenyl)ethyl] -5α-methoxymethyl-3-phenyl-thio-methylenefuran-2-ones 12 and 22, respectively, is studied and a stereoselective synthesis of (+)-$\text{trans}$-4,5-( 4-methoxybenzo) -1β,7aβ-(2α-methoxymethyl-5-oxofuro)hydrindane 1 is also described.     

Template functions of particle monolayers on hydrophobic solid substrates

The template function of cationic particle monolayers bearing quaternary ammonium groups on their surfaces towards anionic colloids was investigated in this paper. Monodispersed cationic polymer particles having quaternary ammonium groups were self-organized on octadecylated glass plates through hydrophobic interaction. The morphology of the resulting particle monolayers was changed by tuning hydrophilic–hydrophobic balance of particles to fabricate aggregated type and dispersed type of particle monolayers. Gold and silver colloids were selectively deposited onto the particle monolayers through electrostatic interaction. The deposited gold and silver colloids on particle monolayers showed plasmon absorbance. Fluorescent silica colloids were also selectively deposited on particle monolayers to permit fluorescence labeling of the particle monolayers. Cationic particle monolayers fabricated on hydrophobic solid octadecylated were found to effectively work as templates for the deposition of above mentioned inorganic colloids.     

Synthesis and central nervous system stimulant activity of camphor-1,2,4-benzotriazines fused with five and six-membered heterocycles

Novel camphor-1,2,4-triazines fused with imidazole 2–3 , thiadiazole 4 , 1,2,4-triazole 7 , pyrimidine 9–13 and 1,3,5-triazine 14 , were synthesized starting from (5R,8S)-3-amino-5,9,9-trimethyl-5,6,7,8-tetrahydro-5,8-methano-1,2,4-benzotriazine 1 . Evaluation of central nervous system stimulant activity demonstrated that the presence of a N-N group at C-3 position of 1,2,4-benzotriazine will be essential for the activity.     

Degradation of nitrilotriacetic acid (NTA) by oxidation with lead dioxide suspension

Degradation of nitrilotriacetic acid (NTA) by oxidation with lead dioxide suspension has been studied by differential pulse polarography. The NTA was degraded over the pH range from 4 to 9, with formation of glycine or a mixture of iminodiacetic acid and glycine. After shaking with lead dioxide for 1 hr at 30 degrees and pH ~7, the NTA was almost completely decomposed, the molar reacting ratio of Pb(IV) to NTA being ~17:1; down to 1 x 10(-5)M NTA was decomposed in a shaking time as short as 15 min and at a temperature as low as 5 degrees . The iron(III)-NTA complex was also degraded under the same conditions, and the iron released was adsorbed on the lead dioxide.     

Self-organization of polymer particles on hydrophobic solid substrates in aqueous media. II. Self-organization of cationic polymer particles on polymer films and wettability control with particle monolayers

Self-organization of cationic polymer particles through hydrophobic interaction on polymer films in aqueous system and characteristic properties of the resulting particle monolayers were investigated. Cationic polymer particles bearing quaternary ammonium groups on their surfaces effectively self-organized on polymer films. With an increase of the particle surface charge density, the surface coverage and average aggregate size (N _a) decreased. The surface coverage control was accomplished by tuning the ionic strength of the media. The wettability of polymer films for water was imparted by the formation of particle monolayers on them. Annealing of the particle monolayers resulted in the increase of the adhesive strength, while the wettability for water was lost. Further improvements of both wettability and adhesive strength of particle monolayers were achieved by the immobilization of silica colloids on the particle monolayers. This method would be effective for the hydrophilization of polymer films.     

Hydrosilylation of α,β-unsaturated nitriles and esters catalyzed by tris (triphenylphosphine)chlororhodium

The hydrosilylation of α,β-unsaturated nitriles and esters such as acrylonitrile, crotononitrile, cinnamonitrile, ethyl and methyl acrylate, ethyl and methyl crotonate and ethyl and methyl methacrylate using tris(triphenylphosphine)chlororhodium as a catalyst is described. The hydrosilylation of α,β-unsaturated nitriles provided α-adduct exclusively in high yield except in the case of trichlorosilane which afforded β-adduct with acrylonitrile. On the other hand, the hydrosilylation of α,β-unsaturated esters gave rather complex results. The selectivity of the reactions was dramatically affected by the substituent of the ester group and that on the β-carbon. Thus, the hydrosilylation of ethyl acrylate with triethylsilane afforded a β-adduct, but, that of ethyl crotonate using the same hydrosilane gave a 1,4-adduct exclusively. Possible mechanisms for these reactions are discussed.