Structure and absolute configuration of a secolignan from Peperomia blanda

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

Albendazole sulfoxide enantiomers: Preparative chiral separation and absolute stereochemistry

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

Structure Elucidation and Absolute Stereochemistry of Isomeric Monoterpene Chromane Esters

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

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

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

Cytotoxic non-aromatic B-ring flavanones from Piper carniconnectivum C. DC.

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

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

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)

Conformational basis for the biological activity of TOAC-labeled angiotensin II and bradykinin: Electron paramagnetic resonance, circular dichroism, and fluorescence studies

N-Terminally and internally labeled analogues of the hormones angiotensin (AII, DRVYIHPF) and bradykinin (BK, RPPGFSPFR) were synthesized containing the paramagnetic amino acid 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4- carboxylic acid (TOAC). TOAC replaced Asp 1 (TOAC 1-AII) and Val 3 (TOAC 3-AII) in AII and was inserted prior to Arg 1 (TOAC 0-BK) and replacing Pro 3 (TOAC 3-BK) in BK. The peptide conformational properties were examined as a function of trifluoroethanol (TFE) content and pH. Electron paramagnetic resonance spectra were sensitive to both variables and showed that internally labeled analogues yielded rotational correlation times (TC) considerably larger than N-terminally labeled ones, evincing the greater freedom of motion of the N-terminus. In TFE, τ C increased due to viscosity effects. Calculation of τ Cpeptide/τ CTOAC ratios indicated that the peptides acquired more folded conformations. Circular dichroism spectra showed that, except for TOAC 1-AII in TFE, the N-terminally labeled analogues displayed a conformational behavior similar to that of the parent peptides. In contrast, under all conditions, the TOAC 3 derivatives acquired more restricted conformations. Fluorescence spectra of All and its derivatives were especially sensitive to the ionization of Tyr 4. Fluorescence quenching by the nitroxide moiety was much more pronounced for TOAC 3-AII The conformational behavior of the TOAC derivatives bears excellent correlation with their biological activity, since, while the N-terminally labeled peptides were partially active, their internally labeled counterparts were inactive [Nakaie, C. R., et al., Peptides 2002, 23, 65-70]. The data demonstrate that insertion of TOAC in the middle of the peptide chain induces conformational restrictions that lead to loss of backbone flexibility, not allowing the peptides to acquire their receptor-bound conformation. © 2004 Wiley Periodicals, Inc.

Dicroísmo circular vibracional e eletrônico na determinação da configuração absoluta de benzopiranos de Peperomia obtusifolia e Piper gaudichaudianum (Piperaceae): implicações biológicas e biossintéticas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Biotransformação e sequestro de micromoléculas de Aristolochia giberti por Battus polydamas

Pós-graduação em Química - IQ

Albumin-induced circular dichroism in Congo red: applications for studies of amyloid-like fibril aggregates and binding sites

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

Expression, purification, and circular dichroism analysis of human CDK9

The human cyclin-dependent kinase 9 (CDK9) protein was expressed in E coli BL21 using the pET23a vector at 30 degrees C. Several milligrams of protein were purified from soluble fraction using ionic exchange and ATP-affinity chromatography. The structural quality of recombinant CDK9 and the estimation of its secondary structure were obtained by circular dichroism. Structural models of CDK9 presented 26% of helices in agreement with the spectra by circular dichroism analysis. This is the first report on human CDK9 expression in Escherichia coli and structure analysis and provides the first step for the development of CDK9 inhibitors. (c) 2006 Elsevier B.V. All rights reserved.

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 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.