Theoretical study of omeprazole behavior: Racemization barrier and decomposition reaction

omeprazole is a substituted benzimidazole which suppresses gastric-acid secretion by means of H+, K+-ATPase inhibition. It is an optically active drug with the sulfur of the sulfoxide being the chiral center. This pro-drug can be easily converted into its respective sulfenamide at low pH. In this work, omeprazole has been studied in relation to racemization barrier and decomposition reaction. Quantum chemistry coupled to PCA chemometric method were used to find all minimum energy structures. Conformational analysis and calculation of racemization barriers were carried out by PM3 semiempirical method (Gaussian 98). The average racemization energy barrier for all minimum energy structures (43.56 kcal mol(-1)) can be related to the velocity constant in Eyring's equation. The enormous half-life time at 100 degrees C (9.04 x 10(4) years) indicates that the process cannot be observed in human time scale. on the other hand, the difference of free energy change (Delta(Delta G) = -266.78 kcal mol(-1)) for the decomposition reaction shows that the process is favorable to the sulfenamide formation. The highly negative Delta(Delta G) obtained for the decomposition reaction shows that this process is extremely exothermic. This result explains why omeprazole decomposes and does not racemize. (C) 2008 Wiley Periodicals, Inc.

Tunneling time through a barrier using the local value of a time operator

A time for a quantum particle to traverse a barrier is obtained for stationary states by setting the local value of a time operator equal to a constant. This time operator, called the tempus operator because it is distinct from the time of evolution, is defined as the operator canonically conjugate to the energy operator. The local value of the tempus operator gives a complex time for a particle to traverse a barrier. The method is applied to a particle with a semiclassical wave function, which gives, in the classical limit, the correct classical traversal time. It is also applied to a quantum particle tunneling through a rectangular barrier. The resulting complex tunneling time is compared with complex tunneling times from other methods.

Tunneling time through a rectangular barrier

In this paper, we discuss the tunneling time of a quantum particle through a rectangular barrier. The reflection and transmission times associated with the wave packets representing the particle are discussed. By using an initial Gaussian momentum distribution, we carry out a comparative analysis of the stationary phases of the incident, reflected, and transmitted wave packets leading to the reflection and transmission times at, and Delta t(T), respectively. In the present treatment of this old and very known problem we take into account the deformations of the reflected and transmitted momentum distributions. These deformations produce a dependence of the reflection and transmission times on the location of the initial wave packet. In a parallel calculation, by numerically monitoring the time evolution of the system, we characterize a reflection and a transmission time. Such times agree with the ones obtained via the stationary phase method. [S1050-2947(98)07912-8].

THE ENERGY BARRIER FOR ELECTRON TRAPPING IN ALXGA1-XAS

Transient decay of persistent photoconductivity measurements are carried out in samples of different compositions. The capture barrier for electron trapping by DX centers is obtained using a method which employs the Brooks-Herring equation for the electronic mobility. The effect of polarization of the screening cloud is analysed using Takimoto's potential and specifies the limits of applicability of the Brooks-Herring equation in AlxGa1-xAs.

Characteristics of Dielectric Barrier Discharge Reactor for Material Treatment

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

Optimal power flow via interior-exterior method

This paper presents a new approach to the resolution of the Optimal Power Flow problem. In this approach the inequality constraints are treated by the Modified Barrier and Primal-Dual Logarithmic Barrier methods. The inequality constraints are transformed into equalities by introducing positive auxiliary variables, which are perturbed by the barrier parameter. A Lagrangian function is associated with the modified problem. The first-order necessary conditions are applied to the Lagrangian, generating a nonlinear system which is solved by Newton's method. The perturbation of the auxiliary variables results in an expansion of the feasible set of the original problem, allowing the limits of the inequality constraints to be reached. Numerical tests on the Brazilian CESP and South-Southeast systems and a comparative test indicated that the new approach efficiently resolves of the Optimal Power Flow problem. © 2007 IEEE.

Treatment of polycarbonate by dielectric barrier discharge (DBD) at atmospheric pressure

Generally most plastic materials are intrinsically hydrophobic, low surface energy materials, and thus do not adhere well to other substances. Surface treatment of polymers by discharge plasmas is of great and increasing industrial application because it can uniformly modify the surface of sample without changing the material bulk properties and is environmentally friendly. The plasma processes that can be conducted under ambient pressure and temperature conditions have attracted special attention because of their easy implementation in industrial processing. Present work deals with surface modification of polycarbonate (PC) by a dielectric barrier discharge (DBD) at atmospheric pressure. The treatment was performed in a parallel plate reactor driven by a 60Hz power supply. The DBD plasmas at atmospheric pressure were generated in air and nitrogen. Material characterization was carried out by contact angle measurements, and X-ray photoelectron spectroscopy (XPS). The surface energy of the polymer surface was calculated from contact angle data by Owens-Wendt method using distilled water and diiodomethane as test liquids. The plasma-induced chemical modifications are associated with incorporation of polar oxygen and nitrogen containing groups on the polymer surface. Due to these surface modifications the DBD-treated polymers become more hydrophilic. Aging behavior of the treated samples revealed that the polymer surfaces were prone to hydrophobic recovery although they did not completely recover their original wetting properties.

Interior-exterior point method with global convergence strategy for solving the reactive optimal power flow problem

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Solving the multiobjective environmental/economic dispatch problem using weighted sum and ε-constraint strategies and a predictor-corrector primal-dual interior point method

This paper proposes a technique for solving the multiobjective environmental/economic dispatch problem using the weighted sum and ε-constraint strategies, which transform the problem into a set of single-objective problems. In the first strategy, the objective function is a weighted sum of the environmental and economic objective functions. The second strategy considers one of the objective functions: in this case, the environmental function, as a problem constraint, bounded above by a constant. A specific predictor-corrector primal-dual interior point method which uses the modified log barrier is proposed for solving the set of single-objective problems generated by such strategies. The purpose of the modified barrier approach is to solve the problem with relaxation of its original feasible region, enabling the method to be initialized with unfeasible points. The tests involving the proposed solution technique indicate i) the efficiency of the proposed method with respect to the initialization with unfeasible points, and ii) its ability to find a set of efficient solutions for the multiobjective environmental/economic dispatch problem.

Optimal reactive power flow via the modified barrier Lagrangian function approach

A new approach called the Modified Barrier Lagrangian Function (MBLF) to solve the Optimal Reactive Power Flow problem is presented. In this approach, the inequality constraints are treated by the Modified Barrier Function (MBF) method, which has a finite convergence property: i.e. the optimal solution in the MBF method can actually be in the bound of the feasible set. Hence, the inequality constraints can be precisely equal to zero. Another property of the MBF method is that the barrier parameter does not need to be driven to zero to attain the solution. Therefore, the conditioning of the involved Hessian matrix is greatly enhanced. In order to show this, a comparative analysis of the numeric conditioning of the Hessian matrix of the MBLF approach, by the decomposition in singular values, is carried out. The feasibility of the proposed approach is also demonstrated with comparative tests to Interior Point Method (IPM) using various IEEE test systems and two networks derived from Brazilian generation/transmission system. The results show that the MBLF method is computationally more attractive than the IPM in terms of speed, number of iterations and numerical conditioning. (C) 2011 Elsevier B.V. All rights reserved.

A method for harvesting unfermented pollen from stingless bees (Hymenoptera, Apidae, Meliponini)

Pollen traps used for harvesting pollen from Apis mellifera do not work for stingless bees, as most species have small entrances and rapidly deposit large quantities of propolis at any barrier in front of the nest. Some stingless beekeepers harvest pollen by removing it directly from pollen pots, but this pollen is normally fermented and unpalatable. The aim of this study was to test a new method for harvesting pollen from stingless bee colonies before it begins to ferment. Colonies of Scaptotrigona depilis were removed and replaced by empty hives, which were occupied by the returning foragers and used for storing pollen and nectar. After one week, the pollen and honey were harvested directly from the storing pots and weighed. On average, the colonies produced 8.7 g of honey and 54.2 g of unfermented pollen (n = 10). This method is a viable option for harvesting unfermented pollen from stingless bees, especially with species that harvest large amounts of pollen. The unfermented pollen of S. depilis was well received in taste tests, receiving higher scores than fermented pollen, and similar scores to A. mellifera pollen, so could have great commercial possibilities. It is also a good method for studying the foraging of stingless bees because the amount of harvested food can be easily and precisely quantified.

Cassava starch biodegradable films: Influence of glycerol and clay nanoparticles content on tensile and barrier properties and glass transition temperature

In this this study, glycerol content and its incorporation method on tensile and barrier properties of biodegradable films (BF) based on cassava starch were analyzed. ANOVA showed that the glycerol incorporation method did not influence the results (P > 0.05), however the glycerol content influenced significantly the tensile and barrier properties of the films (P < 0.05). Films prepared with lower glycerol content presented better tensile and barrier properties than films with higher content. Films were then prepared with addition of clay nanoparticles and their tensile and barrier properties and glass transition temperature were measured. ANOVA indicated that both glycerol and clay nanoparticles influenced significantly the tensile and barrier properties (P < 0.05), diminishing film permeability when clay nanoparticles were present, while the glass transition temperature was not influenced (P > 0.05). (C) 2011 Elsevier Ltd. All rights reserved.

Laser scanning microscopy combined with image restoration to analyse a 3D model of the human epithelial airway barrier

A laser scanning microscope collects information from a thin, focal plane and ignores out of focus information. During the past few years it has become the standard imaging method to characterise cellular morphology and structures in static as well as in living samples. Laser scanning microscopy combined with digital image restoration is an excellent tool for analysing the cellular cytoarchitecture, expression of specific proteins and interactions of various cell types, thus defining valid criteria for the optimisation of cell culture models. We have used this tool to establish and evaluate a three dimensional model of the human epithelial airway wall.

An ONIOM Study of the Bergman Reaction: A Computationally Efficient and Accurate Method for Modeling the Enediyne Anticancer Antibiotics

The Bergman cyclization of large polycyclic enediyne systems that mimic the cores of the enediyne anticancer antibiotics was studied using the ONIOM hybrid method. Tests on small enediynes show that ONIOM can accurately match experimental data. The effect of the triggering reaction in the natural products is investigated, and we support the argument that it is strain effects that lower the cyclization barrier. The barrier for the triggered molecule is very low, leading to a reasonable half-life at biological temperatures. No evidence is found that would suggest a concerted cyclization/H-atom abstraction mechanism is necessary for DNA cleavage.

Development of a method for analysis of ketamine and norketamine enantiomers in equine brain and cerebrospinal fluid by capillary electrophoresis

Ketamine and norketamine are being transported across the blood brain barrier and are also entering from blood into cerebrospinal fluid (CSF). Enantioselective distributions of these compounds in brain and CSF have never been determined. The enantioselective CE based assay previously developed for equine plasma was adapted to the analysis of these compounds in equine brain via use of an acidic pre-extraction of interferences prior to liquid/liquid extraction at alkaline pH. CSF can be treated as plasma. With 100 mg of brain tissue and 0.5 mL of CSF or plasma, assay conditions for up to 30 nmol/g and 6 μM, respectively, of each enantiomer with LOQs of 0.5 nmol/g and 0.1 μM, respectively, were established and the assays were applied to equine samples. CSF and plasma samples analyzed stemmed from anesthetized patient horses and brain, CSF and plasma were obtained from anesthetized horses that were euthanized with an overdose of pentobarbital. Data obtained indicate that ketamine and norketamine enantiomers are penetrating into brain and CSF with those of ketamine being more favorably transported than norketamine, whereas metabolites of norketamine are hindered. More work is required to properly investigate possible stereoselectivities of the ketamine metabolism and transport of metabolites from blood into brain tissue and CSF.