Theoretical study of the structure and stability of NbxOy, and NbxOy+ (x = 1-3; y = 2-5, 7, 8) clusters

Geometric, thermodynamic and electronic properties of cluster neutrals NbxOy and cations NbxOy+ (x = 1-3; y = 2-5, 7, 8) have been characterized theoretically. A DFT calculation using a hybrid combination of B3LYP with contracted Huzinaga basis sets. Numerical results of the relative stabilities, ionization potentials and band gaps of different clusters are in agreement with experiment. Analysis of dissociation channels supports the more stable building blocks as formed by NbO2, NbO2+ NbO3 and NbO3+ stoichiometries. The net atomic charges suggest that oxygen donor molecules can interact more favorably on central niobium atoms of cluster cations, while the interaction with oxygen acceptor molecules is more favorable on the terminal oxygen atoms of neutral clusters. A topological analysis of the electron localization function gradient field indicates that the clusters may be described as having a strong ionic interaction between Nb and O atoms. Published by Elsevier B.V. B.V.

Duality of parity doublets of helicity +/- 2 in D=2+1 dimensions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Quadratic gravity in (2+1)D with a topological Chern-Simons term

Three-dimensional quadratic gravity, unlike general relativity in (2+1)D, is dynamically nontrivial and has a well behaved nonrelativistic potential. Here we analyse the changes that occur when a topological Chem-Simons term is added to this theory. It is found that the harmless massive scalar mode of the latter gives rise to a troublesome massive spin-0 ghost, while the massive spin-2 ghost is replaced by two massive physical particles both of spin 2. We also found that light deflection does not have the 'wrong sign' such as in the framework of three-dimensional quadratic gravity.

Mixing of d(x)(-y)(2)(2) and d(xy) superconducting states for different filling and temperature

We investigate the solution of the gap equation for mixed order parameter symmetry states as a function of filling using a two-dimensional tight-binding model incorporating second-neighbor hopping for tetragonal and orthorhombic lattice, the principal (major) component of the order parameter is taken to be of the d(x2-y2) type, As suggested in several investigations the minor component of the order parameter is taken to be of the d(xy) type. Both the permissible mixing angles 0 and pi/2 between the two components are considered. As a function of filling pronounced maxima of d(x2-y2) order parameter is accompanied by minima of the d(xy) order parameter. At fixed filling. The temperature dependence of the two components of the order parameter is also studied in all cases. The variation of critical temperature T, with filling is also studied and T-c is found to increase with second-neighbor hopping. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Eficácia do glyphosate e 2,4-D no controle de Commelina villosa

O objetivo do presente trabalho foi avaliar a eficácia de glyphosate e 2,4-D, isolados e em mistura, no controle de Commelina villosa. Foram estudadas duas metodologias de avaliação de absorção de herbicidas em oito intervalos de tempo para a lavagem (simulando chuva após a aplicação) e corte (simulando abortamento, como estratégia de defesa) das folhas: 2, 4, 6, 8, 12, 24 e 48 horas após a aplicação dos herbicidas, além de um tratamento sem lavagem ou corte das folhas, em delineamento experimental inteiramente casualizado com quatro repetições, dispostos em um esquema fatorial 3 x 7 + 1 (três herbicidas x sete períodos - horas após a aplicação). Os herbicidas e doses testados foram: glyphosate (1.440 g ha-1), 2,4-D (720 g ha-1) e a mistura glyphosate + 2,4-D (1.080 + 720 g ha-1). A simulação de chuva interferiu de forma negativa no controle das plantas com o herbicida glyphosate. O controle com o herbicida 2,4-D foi influenciado apenas no período de 2 horas. Os períodos de simulação de chuva não influenciaram no controle das plantas com a mistura de glyphosate + 2,4-D. Para o estudo com corte das folhas tratadas, todos os tratamentos independente do período para corte das folhas foram influenciados de forma negativa no controle, sendo que as plantas apresentaram rebrotas quando tratadas com o herbicida 2,4-D isolado.

Estudo da adsorção/dessorção de 2,4-D em solos usando técnica cromatográfica

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estudo anatômico comparativo entre formas normais e estruturas teratogênicas provocadas por 2,4 -D em cana-de-açúcar

A aplicação do herbicida 2,4-D amina, para controlar plantas daninhas em cultura de cana-de-açúcar, produziu estruturas anormais e afetou a própria cultura da cana. Foram estuda das as alterações anatômicas e organográfícas dessas formas teratogénicas e comparadas com as estruturas normais. Foram observadas deformações no colmo que apresentou curvatur as e entrenós mais finos e curtos; o sistema radicular apresentou-se pouco desenvolvido. Na região do anel meristemático e saída das raízes adventícias, observou-se um intumescimento com tumoração e posterior necrose. Anatomicamente, na região do anel meristemático, a epiderme e o parênquima cortical apresentaram células hipertrofíadas e crescimento desordenado; houve malformação de feixes fibrovasculares. Na região das raízes adventícias foi observada tumoração com acentuada hiperplasia e necrose na periferia.

Multivariate analysis of photo-Fenton degradation of the herbicides tebuthiuron, diuron and 2,4-D

The degradation of herbicides in aqueous solution by photo-Fenton process using ferrioxalate complex (FeOx) as source of Fe2+ was evaluated under blacklight irradiation. The commercial products of the herbicides tebuthiuron, diuron and 2,4-D were used. The multivariate analysis, more precisely, the response surface methodology was applied to evaluate the role of FeOx and hydrogen peroxide concentrations as variables in the degradation process, and in particular, to define the concentration ranges that result in the most efficient degradation of the herbicides. The degradation process was evaluated by the determination of the remaining total organic carbon content (TOC), by monitoring the decrease of the concentrations of the original compounds using HPLC and by the chloride ion release in the case of diuron and 2,4-D. Under optimized conditions, 20min were sufficient to mineralize 93% of TOC from 2,4-D and 90% of diuron, including oxalate. Complete dechlorination of these compounds was achieved after 10 min reaction. It was found that the most recalcitrant herbicide is tebuthiuron, while diuron shows the highest degradability. However, under optimized conditions the initial concentration of tebuthiuron was reduced to less than 15%, while diuron and 2,4-D were reduced to around 2% after only 1 min reaction. Furthermore, it was observed that the ferrioxalate complex plays a more important role than H2O2 in the photodegradation of these herbicides in the ranges of concentrations investigated. (C) 2004 Elsevier Ltd. All rights reserved.

Sorption and preconcentration of metal ions on silica gel modified with 2,5-dimercapto-1,3,4-thiadiazole

Silica gel, chemically modified with 2,5-dimercapto-1,3,4-thiadiazole [=Si(CH2)(3)-NC2HNS3], abbreviated as SiB, was used to adsorb metal ions from ethanol by both batch and column techniques. Elution of Cu(II) was done with a solvent mixture of acetone and hydrochloric acid (9:1 v/v). Zn(II), Cd(II), Ni(II), Pb(II), Co(II) and Fe(III) were eluted with 0.5 mol l(-1) HC1 in ethanol solution. The modified silica was applied in the preconcentration of metal ions from commercial ethanol, normally used as engine fuel. The method is suitable for quantifying these metals at low mu g l(-1) levels.

Fmoc-POAC: [(9-fluorenylmethyloxycarbonyl)-2,2,5,5-tetramethylpyrrolidine-N-oxyl-3-amino-4-carboxylic acid]: A novel protected spin labeled beta-amino acid for peptide and protein chemistry

The stable free radical 2,2,6,6-tetramethylpiperidine-N-oxyl-4-amino-4-carboxylic acid (TOAC) is the only spin labeled amino acid that has been used to date to successfully label peptide sequences for structural studies. However, severe difficulty in coupling the subsequent amino acid has been the most serious shortcoming of this paramagnetic marker. This problem stems from the low nucleophilicity of TOAC's amine group towards the acylation reaction during peptide chain elongation. The present report introduces the alternative beta -amino acid 2,2,5,5-tetramethylpyrrolidine-N-oxyl-3-amino-4-carboxylic acid (POAC), potentially useful in peptide and protein chemistry. Investigations aimed at addressing the stereochemistry of this cyclic molecule through X-ray diffraction measurements of crystalline and bulk samples revealed that it consists only of the trans conformer. The 9-fluorenylmethyloxyearbonyl group (Fmoc) was chosen for temporary protection of the POAC amine function, allowing insertion of the probe at any position in a peptide sequence. The vasoactive octapeptide angiotensin II (AII, DRVYIHPF) was synthesized by replacing Pro(7) with POAC. The reaction of Fmoc-POAC with the peptidyl-resin occurred smoothly, and the coupling of the subsequent amino acid showed a much faster reaction when compared with TOAC. POAC(7)-AII was obtained in good yield, demonstrating that, in addition to TOAC, POAC is a convenient amino acid for the synthesis of spin labeled peptide analogues. The present findings open the possibility of a wide range of chemical and biological applications for this novel beta -amino acid derivative, including structural investigations involving its differentiated bend-inducing characteristics.

REGULATION OF BOVINE ENDOMETRIAL SECRETION OF PROSTAGLANDINS AND SYNTHESIS OF 2',5'-OLIGOADENYLATE SYNTHETASE BY INTERFERON-ALPHA MOLECULES

Experiments were performed to (1) verify the inhibitory effect of bovine trophoblast protein-1 (bTP-1) on uterine prostaglandin synthesis, (2) evaluate whether other interferon-alpha (IFN-alpha) molecules also inhibit prostaglandin secretion, and (3) test whether the enzyme 2',5'-oligoadenylate synthetase (2-5A synthetase) can be induced in endometrium by interferon-alpha. In experiment 1, all interferon molecules (bTP-1, oTP-1, bIFN-alpha and hIFN-alpha) equally inhibited secretion of PGF and PGE2 from endometrial explant cultures obtained at day 17 of the estrous cycle. In experiment 2, endometrial explants obtained from day 17 of the cycle were cultured with and without bovine serum albumin (BSA; 50-mu-g/ml) and bIFN-alpha (0, 0.84, 4.2, and 42 nM). Addition of BSA to the culture medium greatly enhanced the accumulation of PGF into the medium. The bIFN-alpha inhibited accumulation of PGF and PGE2 in both the presence or absence of BSA by 12 h. All three concentrations of bIFN-alpha were equally effective in inhibiting prostaglandin accumulation. Additionally, all concentrations of bIFN-alpha increased the amounts of 2-5A synthetase in endometrium. In conclusion, these results confirm the inhibitory effect of bTP-1 on PGF release from endometrium and demonstrate that bTP-1 can also inhibit PGE2 secretion. Furthermore, other interferon-alpha molecules, including bIFN-alpha, hIFN-alpha, and oTP-1, also reduced PGF and PGE2 secretion in culture. It is likely, therefore, that conceptus and other interferon-alpha molecules exert similar effects on endometrium in vitro and that the antiluteolytic effects of bIFN-alpha in vivo are mediated in part by changes in endometrial prostaglandin synthesis.