A theoretical study on the gas phase reactions of the anions NbO3-, NbO5-, and NbO2(0H)(2)(-) with H2O and O-2

The potential energy surfaces at the singlet (s) and the triplet (t) electronic states associated with the gas-phase ion/molecule reactions of NbO3-, NbO5-, and NbO2(OH)(2)(-) with H2O and O-2 have been investigated by means of DFT calculations at the B3LYP level. An analysis of the results points out that the most favorable reactive channel comprises s-NbO3- reacting with H2O to give an ion-molecule complex s-NbO3(H2O)without a barrier. From this minima, an intramolecular hydrogen transfer takes place between the incoming water molecule and an oxygen atom of the NbO3- fragment to render the most stable minimum, s-NbO2(OH)(2)(-). This oxyhydroxide system reacts with O-2 along a barrierless process to obtain the triplet t-NbO4(OH)(2)(-)-A intermediate, and the crossing point, CP1, between s and t electronic states has been characterized. The next step is the hydrogen-transfer process between the oxygen atom of a hydroxyl group and the one adjacent oxygen atom to render a minimum with the two OH groups near each other, t-NbO4(OH)(2)(-)-B. From this point, the last hydrogen migration takes place, to obtain the product complex, t-NbO5(H2O)(-), that can be connected with the singlet separated products, s-NbO5- and H2O. Therefore, a second crossing point, CP2, has been localized. The nature of the chemical bonding of the key minima (NbO3-, NbO2(OH)(2)(-), NbO4(OH)(2)(-)-B, and NbO5-) in both electronic states of the reaction and an interaction with O-2 has been studied by topological analysis of Becke-Edgecombe electron-localization function (ELF) and atoms-in-molecules (AIM) methodology. The niobium-oxygen interactions are characterized as unshared-electron (ionic) interactions and some oxygen-oxygen interactions as protocovalent bonds.

Supersymmetry flows, semi-symmetric space sine-Gordon models and the Pohlmeyer reduction

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of precursor solution on the formation of perovskite phase of Pb(Mg-1/Nb-3(2/3))O-3 thin films

Precursor solutions for Pb(Mg1/3Nb2/3)O-3 (PMN) synthesis were obtained by Pechini's method. The influence of the concentration of organic materials on the phase formation has been studied. For this purpose, PMN solutions were prepared with different precursors and were characterized by thermogravimetric and differential thermal analysis. The obtained solutions were deposited onto a Si (100) substrate by dip coating and pre-treated in a hot plate at 300 degreesC for 1 h. The films were annealed at 600, 700, 800 and 900 degreesC for 1 h and characterized by X-ray diffraction. The perovskite phase was formed after annealing at 600 and 700 degreesC when the solution of PMN was prepared with a lower amount of organic material and starting with mobium oxide. By increasing the temperature to 800 or 900 degreesC, only the formation of pyrochlore phase was observed. With the solution prepared from mobium ethoxide, only the presence of pyrochlore phase was observed independently of the annealing temperature. (C) 2002 Elsevier B.V. B.V. All rights reserved.

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.

Voltage regulator modeling for the three-phase power flow in distribution networks

In this paper a three-phase power flow for electrical distribution systems considering different models of voltage regulators is presented. A voltage regulator (VR) is an equipment that maintains the voltage level in a predefined value in a distribution line in spite of the load variations within its nominal power. Three different types of connections are analyzed: 1) wye-connected regulators, 2) open delta-connected regulators and 3) closed delta-connected regulators. To calculate the power flow, the three-phase backward/forward sweep algorithm is used. The methodology is tested on the IEEE 34 bus distribution system. ©2008 IEEE.

Efficiency evaluation of ZrB2 incorporation in the MgB 2 matrix phase using high-energy milling

The present study suggests the use of high energy ball milling to mix (to dope) the phase MgB2 with the AlB2 crystalline structure compound, ZrB2, with the same C32 hexagonal structure than MgB 2, in different concentrations, enabling the maintenance of the crystalline phase structures practically unaffected and the efficient mixture with the dopant. The high energy ball milling was performed with different ball-to-powder ratios. The analysis of the transformation and formation of phases was accomplished by X-ray diffractometry (XRD), using the Rietveld method, and scanning electron microscopy. As the high energy ball milling reduced the crystallinity of the milled compounds, also reducing the size of the particles, the XRD analysis were influenced, and they could be used as comparative and control method of the milling. Aiming the recovery of crystallinity, homogenization and final phase formation, heat treatments were performed, enabling that crystalline phases, changed during milling, could be obtained again in the final product. © (2010) Trans Tech Publications.

Transmission network expansion planning considering phase-shifter transformers

This paper presents a novel mathematical model for the transmission network expansion planning problem. Main idea is to consider phase-shifter (PS) transformers as a new element of the transmission system expansion together with other traditional components such as transmission lines and conventional transformers. In this way, PS are added in order to redistribute active power flows in the system and, consequently, to diminish the total investment costs due to new transmission lines. Proposed mathematical model presents the structure of a mixed-integer nonlinear programming (MINLP) problem and is based on the standard DC model. In this paper, there is also applied a specialized genetic algorithm aimed at optimizing the allocation of candidate components in the network. Results obtained from computational simulations carried out with IEEE-24 bus system show an outstanding performance of the proposed methodology and model, indicating the technical viability of using these nonconventional devices during the planning process. Copyright © 2012 Celso T. Miasaki et al.

Robust control applied to power flow control in single-phase inverter with LCL filter, using droop control and D-stability

This paper proposes a new methodology to control the power flow between a distributed generator (DG) and the electrical power distribution grid. It is used the droop voltage control to manage the active and reactive power. Through this control a sinusoidal voltage reference is generated to be tracked by voltage loop and this loop generates the current reference for the current loop. The proposed control introduces feed-forward states improving the control performance in order to obtain high quality for the current injected to the grid. The controllers were obtained through the linear matrix inequalities (LMI) using the D-stability analysis to allocate the closed-loop controller poles. Therefore, the results show quick transient response with low oscillations. Thus, this paper presents the proposed control technique, the main simulation results and a prototype with 1000VA was developed in the laboratory in order to demonstrate the feasibility of the proposed control. © 2012 IEEE.

Three-dimensional transient complex free surface flows: Numerical simulation of XPP fluid

In this paper we present a finite difference MAC-type approach for solving three-dimensional viscoelastic incompressible free surface flows governed by the eXtended Pom-Pom (XPP) model, considering a wide range of parameters. The numerical formulation presented in this work is an extension to three-dimensions of our implicit technique [Journal of Non-Newtonian Fluid Mechanics 166 (2011) 165-179] for solving two-dimensional viscoelastic free surface flows. To enhance the stability of the numerical method, we employ a combination of the projection method with an implicit technique for treating the pressure on the free surfaces. The differential constitutive equation of the fluid is solved using a second-order Runge-Kutta scheme. The numerical technique is validated by performing a mesh refinement study on a pipe flow, and the numerical results presented include the simulation of two complex viscoelastic free surface flows: extrudate-swell problem and jet buckling phenomenon. © 2013 Elsevier B.V.

Phase transition from a d(x(2)-y(2)) to d(x(2)-y(2))+id(xy) superconductor

The temperature dependencies of specific heat and spin susceptibility of a coupled dx2-y2 + idxy superconductor in the presence of a weak dxy component are investigated in the tight-binding model (1) on square lattice and (2) on a lattice with orthorhombic distortion. As the temperature is lowered past the critical temperature Tc, first a less ordered dx2-y2 superconductor is created, which changes to a more ordered dx2-y2 + idxy superconductor at Tcl(< Tc). This manifests in two second order phase transitions identified by two jumps in specific heat at Tc and Tc1. The temperature dependencies of the superconducting observables exhibit a change from power-law to exponential behavior as temperature is lowered below Tc1 and confirm the new phase transition. © 1998 Published by Elsevier Science B.V. All rights reserved.

Gas-phase reactivity of protonated 2-oxazoline derivatives: mass spectrometry and computational studies

RATIONALE: Oxazolines have attracted the attention of researchers worldwide due to their versatility as carboxylic acid protecting groups, chiral auxiliaries, and ligands for asymmetric catalysis. Electrospray ionization tandem mass spectrometric (ESI-MS/MS) analysis of five 2-oxazoline derivatives has been conducted, in order to understand the influence of the side chain on the gas-phase dissociation of these protonated compounds under collision-induced dissociation (CID) conditions. METHODS: Mass spectrometric analyses were conducted in a quadrupole time-of-flight (Q-TOF) spectrometer fitted with electrospray ionization source. Protonation sites have been proposed on the basis of the gas-phase basicity, proton affinity, atomic charges, and a molecular electrostatic potential map obtained on the basis of the quantum chemistry calculations at the B3LYP/6-31 + G(d, p) and G2(MP2) levels. RESULTS: Analysis of the atomic charges, gas-phase basicity and proton affinities values indicates that the nitrogen atom is a possible proton acceptor site. On the basis of these results, two main fragmentation processes have been suggested: one taking place via neutral elimination of the oxazoline moiety (99 u) and another occurring by sequential elimination of neutral fragments with 72 u and 27 u. These processes should lead to formation of R+. CONCLUSIONS: The ESI-MS/MS experiments have shown that the side chain could affect the dissociation mechanism of protonated 2-oxazoline derivatives. For the compound that exhibits a hydroxyl at the lateral chain, water loss has been suggested to happen through an E2-type elimination, in an exothermic step. Copyright (C) 2012 John Wiley & Sons, Ltd.

Evaluation of the Effects of a Preoperative 2-Hour Fast With Maltodextrine and Glutamine on Insulin Resistance, Acute-Phase Response, Nitrogen Balance, and Serum Glutathione After Laparoscopic Cholecystectomy: A Controlled Randomized Trial

Background: Prolonged preoperative fasting increases insulin resistance (IR). The authors investigated whether an abbreviated preoperative fast with glutamine (GLN) plus a carbohydrate (CHO)-based beverage would improve the organic response after surgery. Methods: Forty-eight female patients (19-62 years) were randomized to either standard fasting (control group) or to fasting with 1 of 3 different beverages before video-cholecystectomy. Beverages were consumed 8 hours (400 mL; placebo group: water; GLN group: water with 50 g maltodextrine plus 40 g GLN; and CHO group: water with 50 g maltodextrine) and 2 hours (200 mL; placebo: water; GLN: water with 25 g maltodextrine plus 10 g GLN; and CHO: water with 25 g maltodextrine) before anesthesia. Blood samples were collected pre- and postoperatively. Results: The mean (SEM) postoperative homeostasis model assessment-insulin resistance was greater (P < .05) in control patients (4.3 [1.3]) than in the other groups (placebo, 1.6 [0.3]; CHO, 2.3 [0.4]; and GLN, 1.5 [0.1]). Glutathione was significantly higher (P < .01) in the GLN group than in both CHO and control groups. Interleukin-6 increased in all groups except the GLN group. The C-reactive protein/albumin ratio was higher (P < .05) in controls than in CHO and GLN groups. The nitrogen balance was less negative in GLN (-2.5 [0.8] gN) than in both placebo (-9.0 [2] gN; P = .001) and control (-6.6 [0.4] gN; P = .04) groups. Conclusions Preoperative intake of a GLN-enriched CHO beverage appears to improve IR and antioxidant defenses and decreases the inflammatory response after video-cholecystectomy. (JPEN J Parenter Enteral Nutr. 2012; 36: 43-52)

Fractionation of lemon essential oil by solvent extraction: Phase equilibrium for model systems at T=298.2 K

The fractioning of lemon essential oil can be performed by liquid-liquid extraction using hydrous ethanol as a solvent. A quaternary mixture composed of limonene, gamma-terpinene, beta-pinene, and citral was used to simulate lemon essential oil. In this paper, we present (liquid + liquid) equilibrium data that were experimentally determined for systems containing essential oil compounds, ethanol, and water at T = 298.2 K. The experimental data were correlated using the NRTL and UNIQUAC models, and the mean deviations between calculated and experimental data were less than 0.0053 in all systems, indicating the accuracy of these molecular models in describing our systems. The results show that as the water content in the solvent phase increased, the values of the distribution coefficients decreased, regardless of the type of compound studied. However, the oxygenated compound always showed the highest distribution coefficient among the components of the essential oil, thus making deterpenation of the lemon essential oil a feasible process. (C) 2012 Elsevier Ltd. All rights reserved.

Gas-phase reactivity of 2-hydroxy-1,4-naphthoquinones: a computational and mass spectrometry study of lapachol congeners

In order to understand the influence of alkyl side chains on the gas-phase reactivity of 1,4-naphthoquinone derivatives, some 2-hydroxy-1,4-naphthoquinone derivatives have been prepared and studied by electrospray ionization tandem mass spectrometry in combination with computational quantum chemistry calculations. Protonation and deprotonation sites were suggested on the basis of gas-phase basicity, proton affinity, gas-phase acidity (?Gacid), atomic charges and frontier orbital analyses. The nature of the intramolecular interaction as well as of the hydrogen bond in the systems was investigated by the atoms-in-molecules theory and the natural bond orbital analysis. The results were compared with data published for lapachol (2-hydroxy-3-(3-methyl-2-butenyl)-1,4-naphthoquinone). For the protonated molecules, water elimination was verified to occur at lower proportion when compared with side chain elimination, as evidenced in earlier studies on lapachol. The side chain at position C(3) was found to play important roles in the fragmentation mechanisms of these compounds. Copyright (c) 2012 John Wiley & Sons, Ltd.

Electron collisions with the HCOOH...(H2O)n (n=1, 2 and 3) complexes in liquid phase: the influence on the π* shape resonance of formic acid

In this conference we report cross sections for elastic collisions of low-energy electrons with the HCOOH…(H2O)n complexes, with n = 1, 2 and 3. The scattering cross sections were computed with the Schwinger multichannel method [K. Takatsuka and V. McKoy, Phys. Rev. A 24 , 2473 (1981); Phys. Rev. A 30 , 1734 (1984)] with pseudopotentials [M. H. F. Bettega, L. G. Ferreira, and M. A. P. Lima, Phys. Rev. A 47, 1111 (1993)] in the static-exchange and static-exchange plus polarization approximations, for energies from 0.5 eV to 6 eV. We considered some diÆerent hydrogen-bonded structures for the complexes that were generated with classical Monte Carlo simulations [K. Coutinho and S. Canuto, J. Chem. Phys. 113, 9132, (2000)]. The aim of this work is to investigate the effect of the surrounding water molecules on the π* shape resonance of the solute. Previous theoretical and experimental studies carried out in the gas phase reported a π* state for HCOOH at around 1.9 eV. For the n = 1 case and for all complexes, the stabilization of the resonance was observed (it appears at lower energy compared to the value obtained in the gas phase), as reported previously for the CH2O…H2O complexes [T. C. Freitas, M. A. P. Lima, S. Canuto, and M. H. F. Bettega, Phys. Rev. A 80, 062710 (2009)]. This result indicates that the presence of the solvent may affect the processes related to the π* state, such as the molecular dissociation by electron impact. For the n = 2 case we have observed both stabilization and destabilization of the π* resonance, that is associated with the hydrogen bond donor or acceptor role of the water molecules in the complexes. For the n = 3 case, preliminary static-exchange results show the stabilization of the π* state. We propose an explanation of the stabilization/destabilization of the π* state in terms of the polarization of the solute due to the surrounding water molecules and the net charge in the solute.