Self-assembly of cyclometallated Pd(II) compounds directed by C-H center dot center dot center dot pi interactions: A structural evidence for metalloaromaticity in a cyclopalladated ring

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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)

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.

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)

Alongamento simultâneo do rádio e ulna em cães pelo método de Ilizarov

Com o objetivo de avaliar a funcionalidade de uma montagem do aparelho de Ilizarov para o alongamento simultâneo do rádio e da ulna, foram utilizados 15 cães, sem raça definida, adultos, com peso entre 17 e 27kg. Aplicado um fixador composto de dois anéis e quatro hastes telescópicas, realizaram-se osteotomia subperiosteal diafisária distal do rádio e ulna e distração óssea, iniciada no sexto dia de pós-operatório. Os animais foram divididos em cinco grupos formados cada um por três cães, submetidos às seguintes condutas: A- oito dias de alongamento, B- 15 dias de alongamento, C- 22 dias de alongamento, D- 28 dias de alongamento e oito dias de fase neutra com o fixador e E- 28 dias de alongamento, 60 dias de fase neutra com fixador e 45 dias sem fixador. No período de distração os animais desenvolveram gradual e progressiva contratura em flexão da articulação antebraquiocárpica, que persistiu no grupo E após a remoção do fixador. Conclui-se que no alongamento do antebraço há tendência para o desenvolvimento de contratura, recomendando-se medidas preventivas e fisioterapia.

Correção e prevenção da deformidade em flexão da articulação antebraquiocárpica em cães, decorrente do alongamento do antebraço pelo método de Ilizarov

O objetivo do estudo foi comparar os resultados dos tratamentos cirúrgico e preventivo da deformidade em flexão da articulação antebraquiocárpica, decorrentes do alongamento simultâneo do rádio e ulna pelo método de Ilizarov. Foram utilizados 12 cães, sem raça definida, adultos, com peso entre 19 e 28kg, divididos em quatro grupos segundo os tratamentos: A - alongamento ósseo, B - alongamento ósseo e posterior alongamento tendíneo, C - alongamento ósseo e estabilização da articulação antebraquiocárpica, D - sem alongamento. O fixador básico empregado em todos os grupos foi composto por dois anéis e quatro hastes telescópicas, porém no grupo C foi incluído um semi-anel distal fixando a articulação antebraquiocárpica. Os animais dos grupos A, B e C foram submetidos a 28 dias de alongamento, 60 dias de fase neutra com fixador e 45 dias sem o fixador. Os cães do grupo D, considerados como controle, foram submetidos à fixação e osteotomia e não foram alongados. Mesmo com o emprego de exercícios passivos alternados com esparadrapo estendendo-se dos coxins à porção cranial do anel, os animais dos grupos A e B desenvolveram, durante o período de distração, gradual e progressiva contratura em flexão da articulação antebraquiocárpica, que persistiu mesmo após a remoção do fixador. Nos cães do grupo B, ao término do período sem fixador, efetuaram-se alongamento dos tendões flexores, secção dos tecidos periarticulares e capsulotomia. Eles foram observados por mais 45 dias. O tratamento cirúrgico, tecnicamente difícil de ser feito, permitiu a correção da contratura. No grupo C, o tratamento preventivo com o semi-anel distal evitou a contratura, mas durante a fase de alongamento houve tendência à flexão dos dígitos. Os cães do grupo D não desenvolveram contratura. Foi possível concluir que medidas preventivas, como o emprego do semi-anel nos metacarpianos, são importantes para evitar o desenvolvimento de contratura durante o alongamento do antebraço em cães.

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 note on the horseshoe confinement model: the Poynting-Robertson effect

In the present work we numerically simulated the motion of particles coorbital to a small satellite under the Poynting-Robertson light drag effect in order to verify the symmetry suggested by Dermott et al. (1979, 1980) on their ring confinement model. The results reveal a more complex scenario, especially for very small particles (micrometer sizes), which present chaotic motion. Despite the complexity of the trajectories the particles remain confined inside the coorbital region. However, the dissipative force caused by the solar radiation also includes the radiation pressure component which can change this configuration. Our results show that the inclusion of the radiation pressure, which is not present in the original confinement model, can destroy the configuration in a time much shorter than the survival time predicted for a dust particle in a horseshoe orbit with a satellite.

Moonlets wandering on a leash-ring

Since the Voyager flybys, embedded moonlets have been proposed to explain some of the surprising structures observed in Saturn's narrow F ring. Experiments conducted with the Cassini spacecraft support this suggestion. Images of the F ring show bright compact spots, and seven occultations of stars by the F ring, monitored by ultraviolet and infrared experiments, revealed nine events of high optical depth. These results point to a large number of such objects, but it is not clear whether they are solid moonlets or rather loose particle aggregates. Subsequent images suggested an irregular motion of these objects so that a determination of their orbits consistent with the F ring failed. Some of these features seem to cross the whole ring. Here we show that these observations are explained by chaos in the F ring driven mainly by the 'shepherd' moons Prometheus and Pandora. It is characterized by a rather short Lyapunov time of about a few hundred orbital periods. Despite this chaotic diffusion, more than 93 per cent of the F-ring bodies remain confined within the F ring because of the shepherding, but also because of a weak radial mobility contrasted by an effective longitudinal diffusion. This chaotic stirring of all bodies involved prevents the formation of 'propellers' typical of moonlets, but their frequent ring crossings explain the multiple radial 'streaks' seen in the F ring. The related 'thermal' motion causes more frequent collisions between all bodies which steadily replenish F-ring dust and allow for ongoing fragmentation and re-accretion processes (ring recycling).

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.

Some comments on the F ring-Prometheus-Pandora environment

The system formed by the F ring and two close satellites, Prometheus and Pandora, has been analysed since the time that Voyager visited the planet Saturn. During the ring plane crossing in 1995 the satellites were found in different positions as predicted by the Voyager data. Besides the mutual effects of Prometheus and Pandora, they are also disturbed by a massive F ring. Showalter et al. [Icarus 100 (1992) 394] proposed that, the core of the ring has a mass which corresponds to a moonlet varying in size from 15 to 70 kin in radius which can prevent the ring from spreading due to dissipative forces, such as Poynting-Robertson drag and collisions. We have divided this work into two parts. Firstly we analysed the secular interactions between Prometheus-Pandora and a massive F ring using the secular theory. Our results show the variation in eccentricity and inclination of the satellites and the F ring taking into account a massive ring corresponding to a moonlet of different sizes. There is also a population of dust particles in the ring in the company of moonlets at different sizes [Icarus 109 (1997) 304]. We also analysed the behaviour of these particles under the effects of the Poynting-Robertson drag and radiation pressure. Our results show that the time scale proposed for a dust particle to leave the ring is much shorter than predicted before even in the presence of a coorbital moonlet. This result does not agree with the confinement model proposed by Dermott et al. [Nature 284 (1980) 309]. In 2004, Cassini mission will perform repeated observations of the whole system, including observations of the satellites and the F ring environment. These data will help us to better understand this system. (C) 2003 COSPAR. Published by Elsevier Ltd. All rights reserved.