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

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.

O imposto territorial rural e os municípios: o impacto nas receitas municipais e a renúncia fiscal

O artigo reúne uma análise do impacto da arrecadação do Imposto Territorial Rural no período de 1995 a 1997 nos municípios paulistas de Bragança Paulista, Franca e Porto Ferreira frente à composição das receitas municipais. A análise é realizada com base nas legislações do imposto vigentes no período e realiza comparações de arrecadação e projeções tendo como referência os valores da terra nua arbitrados pela Secretaria da Receita Federal (SRF) e pesquisados pelo Instituto de Economia Agrícola da Secretaria de Estado dos Negócios da Agricultura e Abastecimento de São Paulo. Os resultados da pesquisa indicam percentuais de evasão fiscal que atingiram de 18% a 52% e inadimplência de até 31% e esse perfil de evasão se acentua quando a partir de 1996 a SRF deixa de estabelecer o valor da terra nua mínimo (VTNm) e passa a tomar como referência apenas os valores declarados pelo contribuinte.

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.

Hard tissue formation adjacent to implants of various size and configuration immediately placed into extraction sockets: an experimental study in dogs

ObjectivesTo evaluate the influence of implant size and configuration on osseointegration in implants immediately placed into extraction sockets.Material and methodsImplants were installed immediately into extraction sockets in the mandibles of six Labrador dogs. In the control sites, cylindrical transmucosal implants (3.3 mm diameter) were installed, while in the test sites, larger and conical (root formed, 5 mm diameter) implants were installed. After 4 months of healing, the resorptive patterns of the alveolar crest were evaluated histomorphometrically.ResultsWith one exception, all implants were integrated in mineralized bone, mainly composed of mature lamellar bone. The alveolar crest underwent resorption at the control as well as at the test implants. This resorption was more pronounced at the buccal aspects and significantly greater at the test (2.7 +/- 0.4 mm) than at the control implants (1.5 +/- 0.6 mm). However, the control implants were associated with residual defects that were deeper at the lingual than at the buccal aspects, while these defects were virtually absent at test implants.ConclusionsThe installment of root formed wide implants immediately into extraction sockets will not prevent the resorption of the alveolar crest. In contrast, this resorption is more marked both at the buccal and lingual aspects of root formed wide than at standard cylindrical implants.To cite this article:Caneva M, Salata LA, de Souza SS, Bressan E, Botticelli D, Lang NP. Hard tissue formation adjacent to implants of various size and configuration immediately placed into extraction sockets: an experimental study in dogs.Clin. Oral Impl. Res. 21, 2010; 885-895.doi: 10.1111/j.1600-0501.2010.01931.x.

A stochastic shift model for economically designed charts constrained by the process stage configuration

An economic model including the labor resource and the process stage configuration is proposed to design g charts allowing for all the design parameters to be varied in an adaptive way. A random shift size is considered during the economic design selection. The results obtained for a benchmark of 64 process stage scenarios show that the activities configuration and some process operating parameters influence the selection of the best control chart strategy: to model the random shift size, its exact distribution can be approximately fitted by a discrete distribution obtained from a relatively small sample of historical data. However, an accurate estimation of the inspection costs associated to the SPC activities is far from being achieved. An illustrative example shows the implementation of the proposed economic model in a real industrial case. (C) 2011 Elsevier B.V. All rights reserved.

Territorial hypothesis predicts the trade-off between reproductive opportunities and parental care in three species of damselfishes (Pomacentridae: Actinopterygii)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Territorial behaviour and dominance hierarchy of Anthracothorax nigricollis Vieillot 1817 (Aves: Trochilidae) on food resources

Dominant species are those which delimit and defend territories from other individuals of the same or different species. Subordinate species are those which, furtive and sneakily, use sources of nectar from other individuals. This study aimed to describe the aggressive interactions between species of hummingbirds, define which species are dominant and which are subordinate, investigate if the sharing of resources occurs during the visits, and compare the behaviour of the dominant species in different strata (tree, arbustive and herbaceous). The species observed interacting with Anthracothorax nigricollis Vieillot 1817 were Phaethornis pretrei Lesson and Delattrer 1839, Thalurania furcata Gmelin 1788, and Polytmus guainumbi Pallas 1764. Nine behavioural acts grouped into four categories were identified and described. The dominant species is A. nigricollis (with 0.9 of the attacks), followed by T. furcata (with 0.07) and P. pretrei (with 0.03). The resource sharing was seen only in the shrub layer, in C. surinamensis, in which there was intraspecific and interspecific sharing. A. nigricollis showed higher interspecific toleration, T. furcata (0.27) and P. pretrei (0.55) than intraspecific A. nigricollis (0.18). The frequency of occurrence of behaviours expressed by A. nigricollis in the three vegetation strata differed significantly.

Avaliação de fatores de risco de cães sororreagentes à leptospira spp. e sua distribuição espacial, em área territorial urbana

We aimed to evaluate the risk factor of serum reactive dogs to antileptospire agglutinin and their spatial distribution in an urban area. We collected 1,000 blood samples from dogs at 20 immunization centers, homogeneously distributed in the urban area (32 km²) of Botucatu, Sao Paulo, Brazil. Diagnosis was made by microscopic serum agglutination using 24 serovars of Leptospira spp. Statistical analysis was performed by Goodman's test with 5% of significance. Spatial clusters were tested by spatial scan statistic using SaTScan. We found that 17.9% dogs reacted to Leptospira spp. (p<0.0001). Dogs with street access (22.14%) were more reactive (p<0.05) than those without (14.83%). The scan test indicated only one significant cluster influenced by age. Incorporating each one of the co-variables gender, breed, and street access to age, we found that street access was the most important. Street access and age were the most important risk factors in the large number of reactive animals in the cluster, with the castellonis serovar being the most reactive in urban dogs. The identification of a cluster with more reactive dogs than expected allows local preventive measures to be taken.

Investigação soroepidemiológica de leptospirose canina na área territorial urbana de Botucatu, São Paulo, Brasil

Leptospirosis was seroepidemiologically investigated in 775 dogs from Botucatu, state of Sao Paulo, in blood samples collected during the annual anti-rabies vaccination campaign. The samples were collected from 14 out of the 45 vaccination stations geographically distributed in five different municipal districts, with a territorial urban area of 31Km2. Samples were taken from 449 males and 326 females; 564 were of undetermined breed, and 211 were pedigree animals; ages ranged from 3 months to 20 years. Diagnosis included the microscopic serum agglutination tests using 12 Leptospira spp serovars. Serological results and epidemiological variables were compared using Goodman and chi-square tests, with χ=0.05. There were 119 (15.3%) positive samples for 11 serovars; the most important was canicola with 48 (40.3%), followed by pyrogenes 41 (34.5%). Statistical analysis showed significant difference for: breed, 17.7% positive in undetermined breeds and 9.0% in pedigrees; and sex, 18.4% positive in males and 11.0% in females. There was no statistically significant difference in relation to age with uniform distribution of positives.

Zoneamento geoambiental aplicado ao planejamento da gestão ambiental e territorial do município de Colorado D'Oeste, RO

This research is based on the physical characterization of the environment to support definition of the best land use for the county of Colorado D'Oeste, in State of Rondônia, Brazil. Remote sensing and geoprocessing techniques were applied to support the preparation of a Geoenvironmental Zoning, which was used to define strategies of territorial and environmental management in that county. Digital and analogical remote sensing products, acquired by satellites, and additional cartographic and thematic maps allowed a morphostructural analysis to define low and high structural associated study site tectonic. Subsequently, this information was used to support analysis of the physiographic compartmentation of the study area. Based on this study information, it is possible to define geoenvironmental subzones and local hidrological regime, soils, mineral components, texture, color, and sedimentary materials. By integrating previous described information, a synthesis cartographic map generated. Accordingly, this Cartographic Sheet spatially defined the best land use over the study area, indicates zones for conservation, agricultural, and regeneration (areas that should be recovered). Finally, the results of this research can contribute and support governmental and non-governmental organization and local communities could improve land use and soil management, avoiding natural resource destruction and future land scarcity in the county of Colorado D'Oeste.

Crystallographic portrayal of different conformational states of a Lys49 phospholipase A2 homologue: Insights into structural determinants for myotoxicity and dimeric configuration

Catalytically inactive phospholipase A2 (PLA2) homologues play key roles in the pathogenesis induced by snake envenomation, causing extensive tissue damage via a mechanism still unknown. Although, the amino acid residues directly involved in catalysis are conserved, the substitution of Asp49 by Arg/Lys/Gln or Ser prevents the binding of the essential calcium ion and hence these proteins are incapable of hydrolyzing phospholipids. In this work, the crystal structure of a Lys49-PLA2 homologue from Bothrops brazili (MTX-II) was solved in two conformational states: (a) native, with Lys49 singly coordinated by the backbone oxygen atom of Val31 and (b) complexed with tetraethylene glycol (TTEG). Interestingly, the TTEG molecule was observed in two different coordination cages depending on the orientation of the nominal calcium-binding loop and of the residue Lys49. These structural observations indicate a direct role for the residue Lys49 in the functioning of a catalytically inactive PLA2 homologue suggesting a contribution of the active site-like region in the expression of pharmacological effects such as myotoxicity and edema formation. Despite the several crystal structures of Lys49-PLA2 homologues already determined, their biological assembly remains controversial with two possible conformations. The extended dimer with the hydrophobic channel exposed to the solvent and the compact dimer in which the active site-like region is occluded by the dimeric interface. In the MTX-II crystal packing analysis was found only the extended dimer as a possible stable quaternary arrangement. © 2012 Elsevier B.V.

Abordagens de descoberta de conhecimento em bases de dados aplicadas ao Cadastro Territorial Multifinalitário

Pós-graduação em Ciências Cartográficas - FCT