Modulating the electronic structure of amino acids: interaction of model lewis acids with anthranilic acid

On the basis of theoretical B3LYP calculations, Yáñez and co-workers (J. Chem. Theory Comput. 2012, 8, 2293) illustrated that beryllium ions are capable of significantly modulating (changing) the electronic structures of imidazole. In this computational organic chemistry study, the interaction of this β-amino acid and five model Lewis acids (BeF1+, Be2+, AlF2(1+), AlF2+, and Al3+) were investigated. Several aspects were addressed: natural bond orbitals, including second order perturbation analysis of intra-molecular charge delocalization and the natural population analysis atomic charges; molecular geometries; selected infrared stretching frequencies (C-N, C-O, and N-H), and selected ¹H-NMR chemical shifts. The data illustrate that this interaction can weaken the H-O bond and goes beyond strengthening the intra-molecular hydrogen bond (N...H-O) to cause a spontaneous transfer of the proton to the nitrogen atom in five cases generating zwitterion structures. Many new features are observed. Most importantly, the zwitterion structures include a stabilizing hydrogen bond (N-H...O) that varies in relative strength according to the Lewis acid. These findings explain the experimental observations of α-amino acids (for example: J. Am. Chem. Soc. 2001, 123, 3577) and are the first reported fundamental electronic structure characterization of β-amino acids in zwitterion form.

Bartlett-Lewis of rectangular pulse modified model: estimate of parameters for simulation of precipitation in sub-hourly duration

The Bartlett-Lewis Rectangular Pulse Modified (BLPRM) model simulates the precipitous slide in the hourly and sub-hourly and has six parameters for each of the twelve months of the year. This study aimed to evaluate the behavior of precipitation series in the duration of 15 min, obtained by simulation using the model BLPRM in situations: (a) where the parameters are estimated from a combination of statistics, creating five different sets; (b) suitability of the model to generate rain. To adjust the parameters were used rain gauge records of Pelotas/RS/Brazil, which statistics were estimated - mean, variance, covariance, autocorrelation coefficient of lag 1, the proportion of dry days in the period considered. The results showed that the parameters related to the time of onset of precipitation (λ) and intensities (μx) were the most stable and the most unstable were ν parameter, related to rain duration. The BLPRM model adequately represented the mean, variance, and proportion of the dry period of the series of precipitation lasting 15 min and, the time dependence of the heights of rain, represented autocorrelation coefficient of the first retardation was statistically less simulated series suitability for the duration of 15 min.

Modeling changes in organic carbon stocks for distinct soils in southeastern brazil after four eucalyptus rotations using the century model

Soil organic matter (SOM) plays an important role in carbon (C) cycle and soil quality. Considering the complexity of factors that control SOM cycling and the long time it usually takes to observe changes in SOM stocks, modeling constitutes a very important tool to understand SOM cycling in forest soils. The following hypotheses were tested: (i) soil organic carbon (SOC) stocks would be higher after several rotations of eucalyptus than in low-productivity pastures; (ii) SOC values simulated by the Century model would describe the data better than the mean of observations. So, the aims of the current study were: (i) to evaluate the SOM dynamics using the Century model to simulate the changes of C stocks for two eucalyptus chronosequences in the Rio Doce Valley, Minas Gerais State, Brazil; and (ii) to compare the C stocks simulated by Century with the C stocks measured in soils of different Orders and regions of the Rio Doce Valley growing eucalyptus. In Belo Oriente (BO), short-rotation eucalyptus plantations had been cultivated for 4.0; 13.0, 22.0, 32.0 and 34.0 years, at a lower elevation and in a warmer climate, while in Virginópolis (VG), these time periods were 8.0, 19.0 and 33.0 years, at a higher elevation and in a milder climate. Soil samples were collected from the 0-20 cm layer to estimate C stocks. Results indicate that the C stocks simulated by the Century model decreased after 37 years of poorly managed pastures in areas previously covered by native forest in the regions of BO and VG. The substitution of poorly managed pastures by eucalyptus in the early 1970´s led to an average increase of C of 0.28 and 0.42 t ha-1 year-1 in BO and VG, respectively. The measured C stocks under eucalyptus in distinct soil Orders and independent regions with variable edapho-climate conditions were not far from the values estimated by the Century model (root mean square error - RMSE = 20.9; model efficiency - EF = 0.29) despite the opposite result obtained with the statistical procedure to test the identity of analytical methods. Only for lower soil C stocks, the model over-estimated the C stock in the 0-20 cm layer. Thus, the Century model is highly promising to detect changes in C stocks in distinct soil orders under eucalyptus, as well as to indicate the impact of harvest residue management on SOM in future rotations.

The immunomodulator glatiramer acetate influences spinal motoneuron plasticity during the course of multiple sclerosis in an animal model

The immunomodulador glatiramer acetate (GA) has been shown to significantly reduce the severity of symptoms during the course of multiple sclerosis and in its animal model - experimental autoimmune encephalomyelitis (EAE). Since GA may influence the response of non-neuronal cells in the spinal cord, it is possible that, to some extent, this drug affects the synaptic changes induced during the exacerbation of EAE. In the present study, we investigated whether GA has a positive influence on the loss of inputs to the motoneurons during the course of EAE in rats. Lewis rats were subjected to EAE associated with GA or placebo treatment. The animals were sacrificed after 15 days of treatment and the spinal cords processed for immunohistochemical analysis and transmission electron microscopy. A correlation between the synaptic changes and glial activation was obtained by performing labeling of synaptophysin and glial fibrillary acidic protein using immunohistochemical analysis. Ultrastructural analysis of the terminals apposed to alpha motoneurons was also performed by electron transmission microscopy. Interestingly, although the GA treatment preserved synaptophysin labeling, it did not significantly reduce the glial reaction, indicating that inflammatory activity was still present. Also, ultrastructural analysis showed that GA treatment significantly prevented retraction of both F and S type terminals compared to placebo. The present results indicate that the immunomodulator GA has an influence on the stability of nerve terminals in the spinal cord, which in turn may contribute to its neuroprotective effects during the course of multiple sclerosis.