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.

Verificação e análise dos fatos estilizados no mercado de ações brasileiro

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Development of practical HPLC methods for the separation and determination of eggplant steroidal glycoalkaloids and their aglycones

A practical set of HPLC methods was developed for the separation and determination of the eggplant steroidal glycoalkaloids, solanine, chaconine, solasonine, solamargine, and their aglycones, solasodine and solanidine. A gradient method was initially developed, but proved to be neither robust nor practical. Three separate isocratic methods using acetonitrile and ammonium dihydrogen phosphate were developed and shown to be more repeatable, less subject to fluctuations in mobile phase composition, and less time consuming. The effect of adjusting buffer pH, column temperature, and buffer type (triethylammonium phosphate vs. ammonium dihydrogen phosphate) were evaluated. It was also discovered that, by addition of 10% methanol to the acetonitrile portion of the mobile phase, more control over the separations was possible. The use of methanol as a mobile phase entrainer greatly improved separations in some cases and its effectiveness was also dependent upon column temperature. Assessments of the method recovery, limit of detection, and limit of quantitation were made using extracts from S. melongena and S. linnaeanum.

MATHEMATICA notebook for computing tetrahedral finite element shape functions and matrices for the Helmholtz equation

A MATHEMATICA notebook to compute the elements of the matrices which arise in the solution of the Helmholtz equation by the finite element method (nodal approximation) for tetrahedral elements of any approximation order is presented. The results of the notebook enable a fast computational implementation of finite element codes for high order simplex 3D elements reducing the overheads due to implementation and test of the complex mathematical expressions obtained from the analytical integrations. These matrices can be used in a large number of applications related to physical phenomena described by the Poisson, Laplace and Schrodinger equations with anisotropic physical properties.

On the dissimilarity between the algorithms for computing the symmetric energy-momentum tensor in ordinary field theory and general relativity

The recipe used to compute the symmetric energy-momentum tensor in the framework of ordinary field theory bears little resemblance to that used in the context of general relativity, if any. We show that if one stal ts fi om the field equations instead of the Lagrangian density, one obtains a unified algorithm for computing the symmetric energy-momentum tensor in the sense that it can be used for both usual field theory and general relativity.

The efficacy of the self-adjusting file and ProTaper for removal of calcium hydroxide from root canals

Objective: The goal of this study was to evaluate the efficacy of the Self-Adjusting File (SAF) and ProTaper for removing calcium hydroxide [Ca(OH)2] from root canals. Material And Methods: Thirty-six human mandibular incisors were instrumented with the ProTaper system up to instrument F2 and filled with a Ca(OH)2-based dressing. After 7 days, specimens were distributed in two groups (n=15) according to the method of Ca(OH)2 removal. Group I (SAF) was irrigated with 5 mL of NaOCl and SAF was used for 30 seconds under constant irrigation with 5 mL of NaOCl using the Vatea irrigation device, followed by irrigation with 3 mL of EDTA and 5 mL of NaOCl. Group II (ProTaper) was irrigated with 5 mL of NaOCl, the F2 instrument was used for 30 seconds, followed by irrigation with 5 mL of NaOCl, 3 mL of EDTA, and 5 mL of NaOCl. In 3 teeth Ca(OH)2 was not removed (positive control) and in 3 teeth canals were not filled with Ca(OH)2 (negative control). Teeth were sectioned and prepared for the scanning electron microscopy. The amounts of residual Ca(OH)2 were evaluated in the middle and apical thirds using a 5-score system. Results: None of the techniques completely removed the Ca(OH)2 dressing. No difference was observed between SAF and ProTaper in removing Ca(OH)2 in the middle (P=0.11) and the apical (P=0.23) thirds. Conclusion: The SAF system showed similar efficacy to rotary instrument for removal of Ca(OH)2 from mandibular incisor root canals.

Entropy effect in quantum computing and information: an open-source environment simulation

The technologies are rapidly developing, but some of them present in the computers, as for instance their processing capacity, are reaching their physical limits. It is up to quantum computation offer solutions to these limitations and issues that may arise. In the field of information security, encryption is of paramount importance, being then the development of quantum methods instead of the classics, given the computational power offered by quantum computing. In the quantum world, the physical states are interrelated, thus occurring phenomenon called entanglement. This study presents both a theoretical essay on the merits of quantum mechanics, computing, information, cryptography and quantum entropy, and some simulations, implementing in C language the effects of entropy of entanglement of photons in a data transmission, using Von Neumann entropy and Tsallis entropy.