A joint theoretical and kinetic investigation on the fragmentation of (N-halo)-2-amino cycloalkanecarboxylates

A combined theoretical and experimental study to elucidate the molecular mechanism for the Grob fragmentation of different (N-halo)-2-amino cyclocarboxylates with the nitrogen atom in exocyclic position: (N-Cl)-2-amino cyclopropanecarboxylate (1), (N-Cl)-2-amino cyclobutanecarboxylate (2), (N-Cl)-2-amino cyclopentanecarboxylate (3) and (N-Cl)-2-amino cyclohexanecarboxylate (4), and the corresponding acyclic compounds, (N-Cl)-2-amino isobutyric acid (A), (N-Cl)-2-amino butyric acid (B), has been carried out. The kinetics of decomposition for these compounds and related bromine derivatives were experimentally determined by conventional and stopped-flow UV spectrophotometry. The reaction products have been analyzed by GC and spectrophotometry. Theoretical analysis is based in the localization of stationary points (reactants and transition structures) on the potential energy surface. Calculations were carried out at B3LYP/6-31+G* and MP2/6-31+G* computing methods in the gas phase, while solvent effects have been included by means the self-consistent reaction field theory, PCM continuum model, at MP2/6-31+G* and MP4/6-31+G*//MP2/6-31+G* calculation levels. Based on both experimental and theoretical results, the different Grob fragmentation processes show a global synchronicity index close to 0.9, corresponding to a nearly concerted process. At the TSs, the N-Cl bond breaking is more advanced than the C-C cleavage process. An antiperiplanar configuration of these bonds is reached at the TSs, and this geometrical arrangement is the key factor governing the decomposition. In the case of 1 and 2 the ring strain prevents this spatial disposition, leading to a larger value of the activation barrier. Natural population analysis shows that the polarization of the N-Cl and C-C bonds along the bond-breaking process can be considered the driving force for the decomposition and that a negative charge flows from the carboxylate group to the chlorine atom to assist the reaction pathway. A comparison of theoretical and experimental results shows the relevance of calculation level and the inclusion of solvent effects for determining accurate unimolecular rate coefficients for the decomposition process. © 2002 Published by Elsevier Science B.V.

Comparação quantitativa da comunidade de aves de um fragmento de floresta semidecidual do interior do Estado de São Paulo em intervalo de 30 anos

Poucos estudos avaliaram em longo prazo a variação no tamanho populacional das espécies de aves em fragmentos florestais. Para avaliar a riqueza e a abundância específica da comunidade de aves de um remanescente de mata semidecidual do interior do Estado de São Paulo, sudeste do Brasil, foi conduzido o censo da avifauna florestal utilizando-se a metodologia de contagem em transecção. Estes resultados foram comparados com levantamento realizado na mesma localidade 30 anos antes, e as aves foram classificadas de acordo com suas categorias alimentares com a finalidade de associá-las à tendência ao aumento/diminuição de suas abundâncias após este intervalo de tempo. Embora tenha havido predominância de espécies com diminuição populacional, todas as categorias tróficas analisadas apresentaram também espécies com aumento em suas abundâncias. A maioria das espécies com propensão a deslocarem-se entre fragmentos apresentou diminuição em suas abundâncias. Sugerimos que, em relação a suas abundâncias específicas, as categorias tróficas são igualmente afetadas pelos processos da fragmentação, e que a regeneração florestal sofrida pelo remanescente pode ter resultado na perda de espécies de bordas. Espécies cujas abundâncias tenham reduzido neste intervalo de tempo podem sofrer extinção local futuramente.

Aggregates in the strength and gravity regime: Particles sizes in Saturn's rings

Particles in Saturn's main rings range in size from dust to kilometer-sized objects. Their size distribution is thought to be a result of competing accretion and fragmentation processes. While growth is naturally limited in tidal environments, frequent collisions among these objects may contribute to both accretion and fragmentation. As ring particles are primarily made of water ice attractive surface forces like adhesion could significantly influence these processes, finally determining the resulting size distribution. Here, we derive analytic expressions for the specific self-energy Q and related specific break-up energy Q(star) of aggregates. These expressions can be used for any aggregate type composed of monomeric constituents. We compare these expressions to numerical experiments where we create aggregates of various types including: regular packings like the face-centered cubic (fcc), Ballistic Particle Cluster Aggregates (BPCA), and modified BPCAs including e.g. different constituent size distributions. We show that accounting for attractive surface forces such as adhesion a simple approach is able to: (a) generally account for the size dependence of the specific break-up energy for fragmentation to occur reported in the literature, namely the division into "strength" and "gravity" regimes and (b) estimate the maximum aggregate size in a collisional ensemble to be on the order of a few tens of meters, consistent with the maximum particle size observed in Saturn's rings of about 10 m. (c) 2012 Elsevier B.V. All rights reserved.

Diversidade da herpetofauna de uma área de Mata Atlântica do estado de Alagoas: a reserva particular da usina Porto Rico, Campo Alegre

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

Efeito de borda em um fragmento de floresta estacional semidecidual no interior do Estado de São Paulo

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

Regeneração natural em ecounidades maduras e em reorganização de fragmentos de Floresta Estacional Semidecídua

The Atlantic Rainforest biome has been going through fragmentation processes caused by agriculture and urbanization in green areas. Structural studies associated with the silvigenetic approach allow the understanding of what the past has caused in the present structure and predict future conditions of disturbed fragments. The objective of this study was to compare the composition and diversity of arboreous natural regeneration of steady-state and reorganization ecounits in two Seasonal Semideciduous Forest fragments. The hypothesis was that specific composition varies in these two different ecounits due to differential adaptation of species in canopy gaps and closed canopy. The survey was made in three areas with different perturbation backgrounds of 0,5 ha each. 60 permanent plots of 4m² each (2m x 2m) were stablished along the studied fragments following the proportion of ecounits presented in a previous mapping. Each plot was divided in 4 sub-plots of 1m² and arboreous individuals between 0,20m and 1,30m height were sampled and posteriorly separated in two height classes: I) individuals between 0,20m and 0,50m height (2m² sampling) and II) individuals between 0,51m and 1,30m height (4m² sampling). It was sampled 338 individuals from 53 families and 23 species. The Shannon index was 3,26 (Area A), 2,27 (Area B) and 2,42 (Area C) whereas Areas B and C values are considered low in our state Semidecidous Forests. Steady-state ecounits presented the highest values for abundance and species richness. Chi-square test pointed out species’ selection for determined ecounits in the studied community. Rarefaction method analysis showed diversity increase in steady-state ecounits and a stablishment in species richness curves for reorganization ecounits

Efeitos da desconexão de habitat na diversidade funcional de anfíbios anuros (Amphibia: Anura) na Mata Atlântica

Amphibian populations worldwide have been suffering declines generated by habitat degradation, loss, fragmentation and habitat split. With habitat loss and fragmentation in the landscape comes habitat split, which is the separation between the adult anuran habitat and breeding sites, forcing individuals to move through matrix during breeding seasons. Thus, habitat split increases the chance of extinction of amphibians with aquatic larval development and acts as a filter in the selection of species having great influence on species richness and community structure. The use of functional diversity allows us to consider the identity and characteristics of each species to understand the effects of fragmentation processes. The objective of this study was to estimate the effects of habitat split, as well as habitat loss in the landscape, on amphibians functional diversity (FD) and species richness (S). We selected 26 landscapes from a database with anuran surveys of Brazilian Atlantic Forest. For each landscape we calculated DF, S and landscape metrics at multiple scales. To calculate the DF we considered traits that influenced species use and persistence in the landscape. We refined maps of forest remnants and water bodies for metrics calculation. To relate DF and S (response variables) to landscape variables (explanatory variables), we used a model selection approach, fitting generalized linear models (GLMS) and making your selection with AICc. We compared the effect of model absence and models with habitat split, habitat amount and habitat connectivity effects, as well as their interaction. The most plausible models for S were the sum and interaction between habitat split in 7.5 km scale. For anurans with terrestrial development, habitat amount was the only plausible explanatory variable, in the 5 km scale. For anurans with aquatic larvae habitat amount in larger scales and the addition of habitat amount and habitat split were plausible...

Nucleolar cycle and chromatoid body formation Is there a relationship between these two processes during spermatogenesis of Dendropsophus minutus (Amphibia, Anura)?

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Quantum tunneling fragmentation model

A nonthermal quantum mechanical statistical fragmentation model based on tunneling of particles through potential barriers is studied in compact two- and three-dimensional systems. It is shown that this fragmentation dynamics gives origin to several static and dynamic scaling relations. The critical exponents are found and compared with those obtained in classical statistical models of fragmentation of general interest, in particular with thermal fragmentation involving classical processes over potential barriers. Besides its general theoretical interest, the fragmentation dynamics discussed here is complementary to classical fragmentation dynamics of interest in chemical kinetics and can be useful in the study of a number of other dynamic processes such as nuclear fragmentation. ©2000 The American Physical Society.

The influence of niche and neutral processes on a neotropical anuran metacommunity

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

Diferença, dispersão e fragmentação socioespacial: explorações metropolitanas em Brasília e Curitiba = Différence, dispersion et fragmentation sociospatiale : explorations métropolitaines à Brasilia et Curitiba

Pós-graduação em Geografia - FCT