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

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)

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.

Effects of varying curvature and width on the electronic states of GaAs quantum rings

Stationary states of an electron in thin GaAs elliptical quantum rings are calculated within the effective-mass approximation. The width of the ring varies smoothly along the centerline, which is an ellipse. The solutions of the Schrödinger equation with Dirichlet boundary conditions are approximated by a product of longitudinal and transversal wave functions. The ground-state probability density shows peaks: (i) where the curvature is larger in a constant-with ring, and (ii) in thicker parts of a circular ring. For rings of typical dimensions, it is shown that the effects of a varying width may be stronger than those of the varying curvature. Also, a width profile which compensates the main localization effects of the varying curvature is obtained.

Bases epidemiológicas para análise das más oclusões morfológicas como fatores de risco no desenvolvimento das desordens temporomandibulares de origem articular

Dentre as pesquisas empreendidas no campo da epidemiologia, um grupo específico aborda patologias de etiologia desconhecida ou não totalmente compreendidas. É dentro deste grupo que estão situadas as desordens temporomandibulares (DTM). Três estratégias observacionais básicas têm sido utilizadas para abordar o papel etiológico da má oclusão no desenvolvimento das DTM, dentro do repertório epidemiológico. São elas: estudos do tipo transversal, estudos de caso controle e estudos de coorte. Alguns experimentos clínicos são realizados com base na remoção do fator etiológico suspeito. Com base em uma revisão estruturada da literatura, a partir da metodologia empregada nos estudos selecionados, podemos concluir que a definição dos possíveis fatores etiológicos relacionados a subgrupos específicos de DTM é fundamental para que o papel das más oclusões no desenvolvimento destas desordens, embora pareça pequeno quando baseado nas evidências disponíveis, não seja subestimado. Pode ser útil a caracterização de uma oclusão normal como aquela associada como o menor risco para o desenvolvimento de problemas de DTM, mas é provavelmente inapropriada a aplicação destes parâmetros para reverter um problema intra-capsular já estabelecido. O conceito de uma oclusão de baixo fator de risco implicaria em um pequeno desvio entre RC e MIH, pequeno transpasse horizontal, transpasse vertical positivo e ausência de mordida cruzada posterior. Este conceito é compatível com o conceito de oclusão normal defendido por décadas, embora uma variação do normal ao invés de um critério absoluto deva ser permitida. Embora provavelmente seja prudente estabelecer metas morfológicas terapêuticas que busquem o que é observado em oclusões não tratadas julgadas normais ou ideais, o estabelecimento de uma oclusão que alcance todos os critérios gnatológicos, por meio de tratamento ortodôntico, talvez seja impossível e provavelmente desnecessário.

Potentialities and practical limitations of absolute neutron dosimetry using thin films of uranium and thorium applied to the fission track dating

Neutron dosimetry using natural uranium and thorium thin films makes possible that mineral dating by the fission-track method can be accomplished, even when poor thermalized neutron facilities are employed. In this case, the contributions of the fissions of (235)U, (238)U and (232)Th induced by thermal, epithermal and fast neutrons to the population of tracks produced during irradiation are quantified through the combined use of natural uranium and thorium films.If the Th/U ratio of the sample is known, only one irradiation (where the sample and the films of uranium and thorium are present) is necessary to perform the dating. However, if that ratio is unknown, it can be determined through another irradiation where the mineral to be dated and both films are placed inside a cadmium box.Problems related with film manufacturing and calibration are discussed. Special attention is given to the utilization of thin films having very low uranium content. The problems faced suggest that it may be better to substitute these films by uranium doped standard glasses calibrated with thicker uranium films (thickness greater than 1.5 x 10(13) mu m).

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.

Determination of absolute configuration of 1,3-diols by the modified Mosher's method using their di-MTPA esters

1,3-Diols are frequently involved in biologically important compounds and, therefore, determination of the stereochemistry of these structural elements, in particular those in acyclic systems, has been one of the focuses of attention in natural products chemistry. The modified Mosher's method, commonly used for the determination of the absolute configuration of secondary alcohols, was applied to determine the absolute configuration of 1,3-diols with their di-MTPA esters. Several epimeric pairs of syn- and anti-1,3-diols with known absolute configurations were converted to the corresponding di-MTPA esters and the Delta delta values were then calculated. For the acyclic syn-1,3-diols, the Delta delta values were systematically arranged as predicted from the basic concept of the modified Mosher's method, demonstrating that the method is valid for these compounds. In contrast, the Delta delta values were irregularly arranged for the acyclic anti-1,3-diols and, accordingly, this method is not valid for these cases. These results are complementary to those of the previously reported CD exciton chirality method and, hence, the combined use of the modified Mosher's method and the CD exciton chirality method can determine the absolute configuration of the acyclic 1,3-diols. Also, this method is successfully applicable to cyclic 1,3-diols irrespective of their relative stereochemistry. (C) 2002 Wiley-lass, Inc.

SMALLEST UNIVERSE OF NEGATIVE CURVATURE

The smallest known three-dimensional closed manifold of curvature k = -1 was discovered a few years ago by Weeks. This kind of manifold is constructed from a hyperbolic polyhedron with faces pair-wise identified. Here it is used as the comoving spatial section of a Friedmann cosmological model, in the spirit of Ellis and Schreiber's idea of small universes. Its nontrivial global topology has the effect of producing multiple images of single cosmic sources, and this is the basis of an attempt to solve a famous controversy about the redshifts of quasars.

Automatic absolute orientation of scanned aerial photographs

Image orientation is a basic problem in Digital Photogrammetry. While interior and relative orientations were succesfully automated, the same can not be said about absolute orientation. This process can be automated by using an approach based on relational matching and a heuristic that uses the analytical relation between straight features in the object space and its homologous in the image space. A build-in self-diagnosis is also used in this method, that is based on the implementation of data snooping statistic test in the process of spatial resection, using the Iterated Extended Kalman Filtering (IEKF). The aim of this paper is to present the basic principles of the proposed approach and results based on real data.

Effects of direction and curvature on variable error pattern of reaching movements

A number of studies have analyzed various indices of the final position variability in order to provide insight into different levels of neuromotor processing during reaching movements. Yet the possible effects of movement kinematics on variability have often been neglected. The present study was designed to test the effects of movement direction and curvature on the pattern of movement variable errors. Subjects performed series of reaching movements over the same distance and into the same target. However, due either to changes in starting position or to applied obstacles, the movements were performed in different directions or along the trajectories of different curvatures. The pattern of movement variable errors was assessed by means of the principal component analysis applied on the 2-D scatter of movement final positions. The orientation of these ellipses demonstrated changes associated with changes in both movement direction and curvature. However, neither movement direction nor movement curvature affected movement variable errors assessed by area of the ellipses. Therefore it was concluded that the end-point variability depends partly, but not exclusively, on movement kinematics.

Totally visible transparent chloro-sulphide glasses based on Ga2S3-GeS2-CsCI

In this paper, the influence on optical properties of alkali halides such as CsCl in a covalent glassy matrix has been investigated. Chalcogenide glasses belonging to the (GeS2)-(Ga2S3)-CsCI system with high ratio of CsCl present an entire transparency in the visible range. These glasses maintain good transmission up to 12 mu m. Furthermore, the thermo-mechanical properties and the glass hygroscopicity have been investigated as function of the CsCl amount. This new generation of glasses presents a great interest for optical application. They could be used both for passive applications (multi-spectral imaging) and active applications for rare-earth doping due to their good transmission in the visible range, increasing optical pumping possibilities.