Re-examination of the anion derivatives of isoflavones by radical fragmentation in negative electrospray ionization tandem mass spectrometry: experimental and computational studies

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

Temporary fragmentation of a marginal lake and its effects on zooplankton community structure and organization

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

Extracapsular cataract extraction in horses by nuclear fragmentation using adapted instruments

Estudou-se a técnica de núcleo-fragmentação para a extração da lente em seis eqüinos adultos, utilizando-se instrumentais cirúrgicos adaptados. Nas avaliações pós-operatórias, verificou-se diminuição da pressão intra-ocular, em todos os animais, nos primeiros dias de pós-operatório e, ainda, fotofobia, blefarospasmo, edema de córnea e iridociclites, em graus diversos. Observou-se produção de fibrina que, na maioria dos casos, localizava-se na porção axial da pupila, dificultando ou impedindo a visão.

A study of habitat fragmentation in Southeastern Brazil using remote sensing and geographic information systems (GIS)

The purpose of this work was to study fragmentation of forest formations (mesophytic forest, riparian woodland and savannah vegetation (cerrado)) in a 15,774-ha study area located in the Municipal District of Botucatu in Southeastern Brazil (São Paulo State). A land use and land cover map was made from a color composition of a Landsat-5 thematic mapper (TM) image. The edge effect caused by habitat fragmentation was assessed by overlaying, on a geographic information system (GIS), the land use and land cover data with the spectral ratio. The degree of habitat fragmentation was analyzed by deriving: 1. mean patch area and perimeter; 2. patch number and density; 3. perimeter-area ratio, fractal dimension (D), and shape diversity index (SI); and 4. distance between patches and dispersion index (R). In addition, the following relationships were modeled: 1. distribution of natural vegetation patch sizes; 2. perimeter-area relationship and the number and area of natural vegetation patches; 3. edge effect caused by habitat fragmentation, the values of R indicated that savannah patches (R = 0.86) were aggregated while patches of natural vegetation as a whole (R = 1.02) were randomly dispersed in the landscape. There was a high frequency of small patches in the landscape whereas large patches were rare. In the perimeter-area relationship, there was no sign of scale distinction in the patch shapes, In the patch number-landscape area relationship, D, though apparently scale-dependent, tends to be constant as area increases. This phenomenon was correlated with the tendency to reach a constant density as the working scale was increased, on the edge effect analysis, the edge-center distance was properly estimated by a model in which the edge-center distance was considered a function of the to;al patch area and the SI. (C) 1997 Elsevier B.V. B.V.

DYNAMICAL SCALING IN FRAGMENTATION

The dynamics of a fragmentation model is examined from the point of view of numerical simulation and rate equations. The model includes effects of temperature. The number n (s,t) of fragments of size s at time t is obtained and is found to obey the scaling form n(s,t) approximately s(-tau)t(omegasgamma e(-rhot) f(s/t(z)) where f(x) is a crossover function satisfying f(x) congruent-to 1 for x much less than and f(x) much less than 1 for x much greater than 1. The dependence of the critical exponents tau, omega, gamma and z on space dimensionality d is studied from d = 1 to 5. The result of the dynamics on fractal and nonfractal objects as well as on square and triangular lattices is also examined.

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.

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.

Atlantic forest fragmentation and genetic diversity of an isolated population of the Blue-manakin, Chiroxiphia caudata (Pipridae), assessed by microsatellite analyses

Habitat fragmentation is predicted to restrict gene flow, which can result in the loss of genetic variation and inbreeding depression. The Brazilian Atlantic forest has experienced extensive loss of habitats since European settlement five centuries ago, and many bird populations and species are vanishing. Genetic variability analysis in fragmented populations could be important in determining their long-term viability and for guiding management plans. Here we analyzed genetic diversity of a small understory bird, the Blue-manakins Chiroxiphia caudata (Pipridae), from an Atlantic forest fragment (112 ha) isolated 73 years ago, and from a 10,000 ha continuous forest tract (control), using orthologous microsatellite loci. Three of the nine loci tested were polymorphic. No statistically significant heterozygote loss was detected for the fragment population. Although genetic diversity, which was estimated by expected heterozygosity and allelic richness, has been lower in the fragment population in relation to the control, it was not statistically significant, suggesting that this 112 ha fragment can be sufficient to maintain a blue-manakin population large enough to avoid stochastic effects, such as inbreeding and/or genetic drift. Alternatively, it is possible that 73 years of isolation did not accumulate sufficient generations for these effects to be detected. However, some alleles have been likely lost, specially the rare ones, what is expected from genetic drift for such a small and isolated population. A high genetic differentiation was detected between populations by comparing both allelic and genotypic distributions. Only future studies in continuous areas are likely to answer if such a structure was caused by the isolation resulted from the forest fragmentation or by natural population structure.

Trade, investment and fragmentation of the global market: is Latin America lagging behind?

Includes bibliography

Les jeunes et les sentiments d'appartenance en Amérique Latine: causes et risques de la fragmentation sociale

Inclut la bibliographie

Youth and feelings of belonging in Latin America: causes and risks of social fragmentation

Includes bibliography

Effects of liver S9 enzymes on somalargine and solasodine cytotoxicity and mass spectrometric fragmentation

The steroidal glycoalkaloid solamargine and its parent aglycone solasodine, isolated from Solanum palinacanthum, were studied in vitro for cytotoxicity and biotransformation by the hepatic S9 fraction as the metabolic activating system. The MTT uptake assay was used to determine viability after 24 h in RAW 264.7 mouse macrophage-like and SiHa cells exposed to various concentrations of the alkaloids in the presence and absence of the hepatic S9 microsomal fraction. The dose-response curves were established for solamargine and solasodine in the presence and absence of external metabolizing system. From these data, the cytotoxic index (CI50) was calculated with mean values of 7.2 and 13.6 μg/mL for Raw cells and 8.6 and 26.0 μg/mL for SiHa cells, respectively. Mass spectrometry was performed to compare the fragmentation patterns of the alkaloids to predict metabolism by the S9 fraction. The mass spectra demonstrated a distinct fragmentation patterns for solamargine and solasodine after the addition of the S9 fraction. In the present study, we demonstrate that the cytotoxic effect of solamargine and solasodine and their metabolites prepared in vitro by biotransformation with the S9 fraction are comparable. These findings suggest that the metabolic activation system S9 fraction may fail to suppress the cytotoxicity of these alkaloids. © 2013 Springer-Verlag Berlin Heidelberg.

A statistical model of aggregate fragmentation

Processo FAPESP: 11/08171-3