Mechanistic insights into the reaction between VO2+ and propene based on a DFT study

Calculations based on density functional theory have been carried out to investigate the free energy profiles at singlet and triplet electronic states associated with the gas-phase ion/molecule reactions of VO2++ ((1)A(1)/(3)A) with propene. The complex potential energy Surfaces, including Six reaction pathways (three dehydrogenation and three oxygen transfer processes), have been explored and analyzed. Along dehydrogenation reactive channels, three final products can be obtained: V(OH)(2)(+) ((1)Sigma(+)/(3)Sigma(-)) and allene (path Dehl), being the most kinetically and thermodynamically favorable reaction pathway, V(OH)(2)(+) ((1)Sigma(+)/(3)Sigma(-)) and propyne (path Deh2),and VO2+ ((1)A(1)/(3)A) and H-2 plus allene (path Deh3). The oxyoenation processes can yield its final products Vo(+) ((1)Delta/(3)Sigma) and acetone (path Ox1), VO+ ((1)Delta/(3)Sigma 2) and propanaldehyde (path Ox2), and VO+ ((1)Delta/(3)Sigma) and H-2 and propenaldehyde (path Ox3). Both paths Deh1 and Deh2 are associated with two consecutive hydrogen transfer processes from carbon atoms of the propene fragment to vanadyl oxygen atoms, while in path Deh3 the second hydrogen migration takes place to the vanadiurn atorn followed by the formation ola hydrogen molecule. Both paths Ox1 and Ox2 comprise an intramolecular hydrogen transfer between the ethylenic moiety of the propene fragment, while two consecutive hydrogen transfer processes take place from the propene fragment to oxygen and vanadium atoms of the vanadyl moiety along path Ox3. Three crossing points between both electronic states take place along path Deh1 (CP-Deh1) and path Deh2 (CP-Deh2) and in the entrance channel of oxidation processes (CP-Ox). A comparison with previous works on related reactions VO2+ + C2H4, VO2 + C2H6, and VO2+ + C3H8 allows us to rationalize the different reactivity patterns.

Oxygen mobility in SmBa2Cu3O7-delta measured by anelastic spectroscopy

Anelastic spectroscopy has been performed on a sample of superconducting oxide SmBa2Cu3O7-delta (SBCO) using a torsion pendulum operating with frequency around 10 Hz. A thermally activated relaxation peak is observed near 500 K with the activation enthalpy of 1.55 +/- 0.03 eV and the pre-exponential factor of approximately 10(-15) s, which is attributed to the mobility of non-stoichiometric oxygen by jumps in positions O1 and O5 of the lattice. (c) 2006 Elsevier B.V. All rights reserved.

Nitric oxide and anglotensin II receptors mediate the pressor effect of angiotensin II: A study in conscious and zoletil-anesthetized rats

The circumventricular structures of the central nervous system and nitric oxide are involved in arterial blood pressure control, and general anesthesia may stimulate the central renin-angiotensin system. We therefore investigated the central role of angiotensin 11 and nitric oxide on the regulation of systemic arterial blood pressure in conscious and anesthetized rats. METHODS: Rats with stainless steel cannulae implanted into their lateral ventricle were studied. We injected the AT(1) and AT(2) angiotensin 11 receptor antagonists, losartan and PD123319, L-NAME, 7-nitroindazole (nitric oxide synthetase inhibitors), and FK409 (nitric oxide donor agent) into the lateral ventricles. Mean arterial blood pressure (MAP) was recorded in conscious and zoletil-anesthetized rats. RESULTS: Mean +/- (SEM) baseline MAP was 117.5 +/- 2 mm Hg. Angiotensin II injected into the brain lateral ventricle increased MAP from 136.5 +/- 2 min Hg to 138.5 +/- 4 mm Hg (Delta 16 +/- 3 mm Hg to Delta 21 +/- 3 mm Hg) for all experimental groups versus control from 116 +/- 2 mm Hg to 120 +/- 3 mm Hg (Delta 3 +/- 1 mm Hg to A5 +/- 2 mm Hg) (P < 0.05). L-NAME or 7-nitroindazole enhanced the angiotensin II pressor effect (P < 0.05). Prior injection of losartan and PD123319 decreased the angiotensin 11 pressor effect and the enhancement effect of L-NAME and 7-nitroindazole (P < 0.05). Zoletil anesthesia did not interfere with the effects of angiotensin 11, AT,, AT2 antagonists, or nitric oxide synthetase inhibitors. CONCLUSIONS: Endogenous nitric oxide functions tonically as a central inhibitory modulator of the angiotensinergic system. AT, and AT2 receptors influence the angiotensin 11 central control of arterial blood pressure. Zoletil anesthesia did not interfere with these effects. (Anesth Analg 2007;105:1293-7)

Ghost poles in the nucleon propagator in the linear sigma model approach and its role in pi N low-energy theorems

Complex mass poles, or ghost poles, are present in the Hartree-Fock solution of the Schwinger-Dyson equation for the nucleon propagator in renormalizable models with Yukawa-type meson-nucleon couplings, as shown many years ago by Brown, Puff and Wilets (BPW), These ghosts violate basic theorems of quantum field theory and their origin is related to the ultraviolet behavior of the model interactions, Recently, Krein et.al, proved that the ghosts disappear when vertex corrections are included in a self-consistent way, softening the interaction sufficiently in the ultraviolet region. In previous studies of pi N scattering using ''dressed'' nucleon propagator and bare vertices, did by Nutt and Wilets in the 70's (NW), it was found that if these poles are explicitly included, the value of the isospin-even amplitude A((+)) is satisfied within 20% at threshold. The absence of a theoretical explanation for the ghosts and the lack of chiral symmetry in these previous studies led us to re-investigate the subject using the approach of the linear sigma-model and study the interplay of low-energy theorems for pi N scattering and ghost poles. For bare interaction vertices we find that ghosts are present in this model as well and that the A((+)) value is badly described, As a first approach to remove these complex poles, we dress the vertices with phenomenological form factors and a reasonable agreement with experiment is achieved, In order to fix the two cutoff parameters, we use the A((+)) value for the chiral limit (m(pi) --> 0) and the experimental value of the isoscalar scattering length, Finally, we test our model by calculating the phase shifts for the S waves and we find a good agreement at threshold. (C) 1997 Elsevier B.V. B.V.

Shiitake (Lentinula edodes (Berkeley) Pegler) extracts as a modulator of micronuclei induced in HEp-2 cells

Shiitake (Lentinula edodes (Berkeley) Pegler) is one of the most consumed mushrooms, for both therapeutic purposes and as food, therefore, the study of its biological properties is of great interest for producers and consumers. Aqueous extracts of the shiitake mushroom (L. edodes (Berkeley) Pegler) were evaluated by the micronucleus test (MN) in HEp-2 cells in vitro, to analyze their possible mutagenic and antimutagenic activities. None of the three extract concentrations tested (0.5, 1.0 and 1.5 mg/mL) presented mutagenicity at any of the preparation temperatures (4 degrees C, 22 +/- 2 degrees C and 60 degrees C). In the antimutagenicity evaluation, all extract concentrations at all preparation temperatures presented a strong protective activity for the HEp-2 cells in response to the alkylating agent methyl methanesulfonate (MMS) in the different treatment protocols: pre-treatment, simultaneous treatment and post-treatment. The extracts prepared at 22 +/- 2 degrees C presented the lowest frequencies of MN in the evaluations of mutagenicity and antimutagenicity, indicating these as the best option for potential therapeutic use. (c) 2006 Elsevier Ltd. All rights reserved.

THE ALGEBRA OF NONLOCAL CHARGES IN NONLINEAR SIGMA-MODELS

We obtain the exact classical algebra obeyed by the conserved non-local charges in bosonic non-linear sigma models. Part of the computation is specialized for a symmetry group O(N). As it turns out the algebra corresponds to a cubic deformation of the Kac-Moody algebra. We generalize the results for the presence of a Wess-Zumino term. The algebra is very similar to the previous one, now containing a calculable correction of order one unit lower. The relation with Yangians and the role of the results in the context of Lie-Poisson algebras are also discussed.

DFT study of the reaction between VO2+ and C2H6

The molecular mechanisms of the reaction VO2+ ((1)A(1)/(3)A'') + C2H6 ((1)A(g)) to yield V(OH)(2)(+) ((1)Sigma(+)/(3)Sigma(-)) + C2H4 ((1)A(g)) and/or VO+ ((1)Delta/(3)Sigma) + H2O ((1)A(1)) + C2H4 (Ag-1) have been investigated with density functional theory (DFT) at the B3LYP/6-311G(2d,p) level. Calculations including geometry optimization, vibrational analysis, and Gibbs free energy for the stationary points on the reactive potential energy surfaces at both the singlet (s) and first excited triplet (t) electronic states have been carried out. The most thermodynamically and kinetically favorable pathway is the formation of t-V(OH)(2)(+) + C2H4 along a four-step molecular mechanism (insertion, two consecutive hydrogen transfers, and elimination). A crossing point between s and t electronic states has been characterized. A comparison with previous works on VO2+ + C2H4 (Gracia et al. J. Phys. Chem. A 2003, 107, 3107-3120) and VO2+ + C3H8 (Engeser et al. Organometallics 2003, 22, 3933-3943) reactions allows us a rationalization of the different reactivity patterns. The catalytic role of water molecules in the tautomerization process between hydrated oxide cation, VO(H2O)(+,) and dihydroxide cation, V(OH)(2)(+), is achieved by a water-assisted mechanism.

A Family of Autoconnected Transformers for 12-and 18-Pulse Converters-Generalization for Delta and Wye Topologies

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Measurement of the differential cross section d sigma/dt in elastic p(p)over-bar scattering at root s=1.96 TeV

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Bound state solution of the grassmannian nonlinear sigma model with fermions

We construct the S-matrix for bound state (gauge-invariant) scattering for nonlinear sigma models defined on the manifold SU(n) S(U(p)⊗U(n-p)) with fermions. It is not possible to compute gauge non-singlet matrix elements. In the present language, constraints from higher conservation laws determine the bound state solution. An alternative derivation is also presented. © 1988.

Analytical expressions for the FM and AM responses of an integrated laser-modulator

The need for low-chirp and compact transmitters for high-bit-rate optical links has led to the development of integrated laser electroabsorption modulators (ILM). We have investigated feedback effects inducing frequency chirp by developing a model treating the ILM as a whole and obtained analytical expressions of the FM and AM responses. The variation of the frequency chirp with the residual facet reflectivity of the modulator section is calculated. The model predicts the unusual peak in the measured frequency responses and has been used to define design rules.

Optimized delta expansion for relativistic nuclear models: Renormalization of vacuum fluctuations

We use the optimized linear δ expansion and functional methods to study vacuum contributions in nuclear matter up to the lowest non-trivial order which includes exchange terms. We show that well known results (MFT, RHA and HF) can be easily reproduced when appropriate limits are taken. Neglecting vacuum contributions we explicitly show that the δ expansion goes beyond the traditional loop approximation previously used to study two loop vacuum contributions in nuclear matter. We then evaluate and renormalize vacuum exchange contributions showing that they are numerically very large, as predicted by the ordinary loop approximation.

N = 2 sigma models for Ramond-Ramond backgrounds

Using the U(4) hybrid formalism, manifestly N = (2,2) worldsheet supersymmetric sigma models are constructed for the type-IIB superstring in Ramond-Ramond backgrounds. The Kahler potential in these N = 2 sigma models depends on four chiral and antichiral bosonic superfields and two chiral and antichiral fermionic superfields. When the Kahler potential is quadratic, the model is a free conformal field theory which describes a flat ten-dimensional target space with Ramond-Ramond flux and non-constant dilaton. For more general Kahler potentials, the model describes curved target spaces with Ramond-Ramond flux that are not plane-wave backgrounds. Ricci-flatness of the Kahler metric implies the on-shell conditions for the background up to the usual four-loop conformal anomaly. © SISSA/ISAS 2002.

GDP 4.0 transfer to SGP 3.0 for SCIAMACHY no2 column processing: Verification with SDOAS / GDOAS prototype algorithms and delta-validation with NDACC / UV-visible network data

Until mid 2006, SCIAMACHY data processors for the operational retrieval of nitrogen dioxide (NO2) column data were based on the historical version 2 of the GOME Data Processor (GDP). On top of known problems inherent to GDP 2, ground-based validations of SCIAMACHY NO2 data revealed issues specific to SCIAMACHY, like a large cloud-dependent offset occurring at Northern latitudes. In 2006, the GDOAS prototype algorithm of the improved GDP version 4 was transferred to the off-line SCIAMACHY Ground Processor (SGP) version 3.0. In parallel, the calibration of SCIAMACHY radiometric data was upgraded. Before operational switch-on of SGP 3.0 and public release of upgraded SCIAMACHY NO2 data, we have investigated the accuracy of the algorithm transfer: (a) by checking the consistency of SGP 3.0 with prototype algorithms; and (b) by comparing SGP 3.0 NO2 data with ground-based observations reported by the WMO/GAW NDACC network of UV-visible DOAS/SAOZ spectrometers. This delta-validation study concludes that SGP 3.0 is a significant improvement with respect to the previous processor IPF 5.04. For three particular SCIAMACHY states, the study reveals unexplained features in the slant columns and air mass factors, although the quantitative impact on SGP 3.0 vertical columns is not significant.