Further monoterpene chromane esters from Peperomia obtusifolia: VCD determination of the absolute configuration of a new diastereomeric mixture

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Structure and absolute configuration of a secolignan from Peperomia blanda

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Asymmetric microbial reduction of ketones: absolute configuration of trans-4-ethyl-1-(1S-hydroxyethyl)cyclohexanol

A set of five fungal species, Botrytis cinerea, Trichoderma viride and Eutypa lata, and the endophytic fungi Colletotrichum crassipes and Xylaria sp., was used in screening for microbial biocatalysts to detect monooxygenase and alcohol dehydrogenase activities (for the stereoselective reduction of carbonyl compounds). 4-Ethylcyclohexanone and acetophenone were biotransformed by the fungal set. The main reaction pathways involved reduction and hydroxylations at several positions including tertiary carbons. B. cinerea was very effective in the bioreduction of both substrates leading to the chiral alcohol (S)-1-phenylethanol in up to 90% enantiomeric excess, and the cis-trans ratio for 4-ethylcyclohexanol was 0:100. trans-4-Ethyl-1-(1S-hydroxyethyl)cyclohexanol, obtained from biotransformation by means of an acyloin-type reaction, is reported here for the first time. The absolute configurations of the compounds trans-4-ethyl-1-(1S-hydroxyethyl)cyclohexanol and 4-(1S- and 4-(1R-hydroxyethyl)cyclohexanone were determined by NMR analysis of the corresponding Mosher's esters. (C) 2009 Elsevier Ltd. All rights reserved.

Structural study of thin films prepared from tungstate glass matrix by Raman and X-ray absorption spectroscopy

Thin films were prepared using glass precursors obtained in the ternary system NaPO(3)-BaF(2)-WO(3) and the binary system NaPO(3)-WO(3) with high concentrations of WO(3) (above 40% molar). Vitreous samples have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. Several structural characterizations were performed by Raman spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES) at the tungsten L(I) and L(III) absorption edges. XANES investigations showed that tungsten atoms are only sixfold coordinated (octahedral WO(6)) and that these films are free of tungstate tetrahedral units (WO(4)). In addition, Raman spectroscopy allowed identifying a break in the linear phosphate chains as the amount of WO(3) increases and the formation of P-O-W bonds in the films network indicating the intermediary behavior of WO(6) octahedra in the film network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed identifying the presence of W-O and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO(3) concentrated samples (above 40% molar) attributed to the formation of WO(6) clusters. (C) 2008 Elsevier B.V. All rights reserved.

Absolute configuration reassignment of two chromanes from Peperomia obtusifolia (Piperaceae) using VCD and DFT calculations

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Absolute Configuration and Selective Trypanocidal Activity of Gaudichaudianic Acid Enantiomers

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

VCD to determine absolute configuration of natural product molecules: secolignans from Peperomia blanda

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Resolution and Absolute Configuration Assignment of a Natural Racemic Chromane from Peperomia obtusifolia (Piperaceae)

The resolution of the natural racemic chromane 3,4-dihydro-5-hydroxy-2,7-dimethyl-8-(3 ''-methyl-2 ''-butenyl)-2-(4'-methyl-1',3'-pentadienyl)-2H-1-benzopyran-6-carboxylic acid (1) isolated from the leaves of Peperomia obtusifolia has been accomplished using stereoselective HPLC. The absolute coil figuration of the resolved enantiomers was determined by the analysis of optical rotations and CD spectra. The finding of a racemic mixture instead of an enantiomerically pure metabolite raises questions about the final steps in the biosynthesis of this class of natural products, suggesting that the intramolecular chromane ring formation step may not be enzymatically controlled at all in P. obtusifolia. Chirality 21:799-801, 2009. (C) 2008 Wiley-Liss, Inc.

The role of matrix effects on the quantification of abscisic acid and its metabolites in the leaves of Bauhinia variegata L. using liquid chromatography combined with tandem mass spectrometry

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Electron migration in DNA matrix: an electron transfer reaction

Este artigo apresenta uma área de pesquisa atual, ativa e interessante. Descreve a investigação da química de transferência de elétrons (TE) de um modo geral e resultados de TE em DNA em particular. Dois intercalantes de DNA foram utilizados: Ethidium Bromide como doador (D) e Methyl-viologen como receptor (A), o primeiro intercala-se entre as bases do DNA e o último na sua superfície. Utilizando o modelo de Perrin e medidas de Supressão de Fluorescência obteve-se a distância de migração do elétron; aqui a distância foi considerada o espaçamento linear entre as moléculas de doador e receptor ao longo da molécula de DNA. O valor determinado foi de 22,6 ± 1,1 angstrons e o número de pares de bases entre doador e receptor de 6,6. Na literatura os valores encontrados foram de 26 angstrons e de quase 8 pares de bases. Considera-se que a transferência de elétrons em DNA seja mediada através das interações através do espaço entre os elétrons do tipo p contido nos pares de bases.

Monitoring the mean vector and the covariance ­matrix of multivariate processes with sample means and sample ranges

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The absolute configuration of 1-(3 ',4 '-dihydroxycinnamoyl)cyclopentane-2,3-diol from the Amazonian tree Chimarrhis turbinata

An antioxidant, 1-(3',4'-dihydroxycinnamoyl) cyclopentane-2,3-diol [ or ( E)-2,3-dihydroxycyclopentyl-3-(3',4'-dihydroxyphenyl) acrylate ( 1)], and two known trans- and cis-chlorogenic acid methyl esters were isolated from the ethanolic extract of the leaves of Chimarrhis turbinata. The relative configuration of 1 was determined by NMR and by comparison of the circular dichroic spectrum ( CD) with those of the enantiomers of synthetic 3', 4'-dimethoxycinnamoyl analogues. The absolute configuration of one of the synthetic enantiomers was determined using the CD exciton chirality method. This established the structure of naturally occurring 1 as (E)- 2,3-dihydroxycyclopentyl- 3-(3', 4'-dihydroxyphenyl) acrylate.

A new potentiometric ibuprofenate ion sensor immobilized in a graphite matrix for determination of ibuprofen in tablets

The characteristics, performance, and application of an electrode, namely, Pt vertical bar Hg vertical bar Hg-2(IBP)(2)vertical bar Graphite, where IBP stands for ibuprofenate ion, are described. This electrode responds to IBP with sensitivity of (58.6 +/- 0.9) mV decade 1 over the range 5.0 x 10(-5)-1.0 x 10(-1) mol L-1 at pH 6.0-9.0 and a detection limit of 3.8 x 10(-5) mol L-1. The electrode is easily constructed at a relatively low cost with fast response time (within 1530 s) and can be used for a period of 5 months without any considerable divergence in potentials. The proposed sensor displayed good selectivity for ibuprofen in the presence of several substances, especially concerning carboxylate and inorganic anions. It was used for the direct assay of ibuprofen in commercial tablets by means of the standard additions method. The analytical results obtained by using this electrode are in good agreement with those given by the United States Pharmacopeia procedure. (c) 2006 Elsevier B.V. All rights reserved.