Theoretical study on the molecular mechanism for the reaction of VO2+ with C2H4

The complex reaction between VO2+ ((1)A(1)/(3)A) and C2H4 (Ag-1(g)/(3)A(1)) to yield VO+ ((1)Delta/(3)Sigma) and CH3CHO ('A'/(3)A) has been studied by means of B3LYP/6-31G* and B3LYP/6-311G(2d,p) calculations. The structures of all reactants, products, intermediates, and transition structures of this reaction have been optimized and characterized at the fundamental singlet and first excited triplet electronic states. Crossing points are localized, and possible spin inversion processes are discussed by means of the intrinsic reaction coordinate approach. Relevant stationary points along the most favorable reaction pathways have been studied at the CCSD/6-311G(2d,p)//B3LYP/6-311G(2d,p) calculation level. The theoretical results allow the development of thermodynamic and kinetic arguments about the reaction pathways of the title process. In the singlet state, the first step is the barrierless obtention of a reactant complex associated with the formation of a V-C bond, while in the triplet state a three-membered ring addition complex with the V bonded to the two C atoms is obtained. Similar behavior is found in the exit channels: the product complexes can be formed from isolated products without barriers. The reactant and product complexes are the most stable stationary points in the singlet and triplet electronic states. From the singlet state reactant complex, two reaction pathways are posssible to reach the triplet state product complex. (i) A mechanism in which a hydrogen transfer process is the first and rate limiting step and the second step is an oxygen transfer between vanadium and carbon atoms with a concomitant change in the spin state. The crossing point between singlet and triplet spin states is not kinetically relevant because it takes place at a later stage occurring in the exit channel. (ii) A mechanism in which the first stage renders a four-membered ring between vanadyl cation and the ethylene fragment and an oxygencarbon bond is formed; on going from this minimum to the second transition structure, associated with a carbon-vanadium bond breaking process, the crossing point between singlet and triplet spin states is reached. The final step is the hydrogen transfer between both carbon atoms to yield the product complex. In this case the spin change opens a lower barrier pathway. The transition structures with larger values of relative energies for both reactive channels of VO2+ ((1)A(1)) + C2H4 (Ag-1) --> VO+ ((3)Sigma) + CH3CHO ((1)A') present similar energies, and the two reaction pathways can be considered as competitive.

Adequação da metodologia para o teste de germinação de sementes de pitaia vermelha

Hylocereus undatus (Haw.), popularmente conhecida como pitaia vermelha é uma cactácea para a qual se tem registrado um aumento de consumo nos últimos anos e, por ser ainda pouco explorada, vários aspectos referentes à sua propagação ainda são desconhecidos. Até o momento, não existem critérios para a execução de testes de germinação para sementes dessa espécie, publicados nas Regras para Análise de Sementes. Nesse sentido, objetivou-se com este trabalho adequar a metodologia quanto ao substrato, temperatura e tempo de contagem inicial e final para o teste de germinação. Foram testados quatro substratos (rolo de papel, areia, vermiculita e solo) e quatro temperaturas (20, 25, 30 e 20-30°C). O efeito dos substratos no desempenho germinativo das sementes foi avaliado pelo teste de germinação e de primeira contagem instalado com quatro subamostras de 50 sementes. Foram feitas contagens diárias do número de plântulas emergidas até atingirem a estabilidade e, no final do experimento, foram avaliados a porcentagem de germinação das sementes, considerando as plântulas normais, anormais e sementes mortas. Concluiu-se que o teste de germinação de sementes de pitaia vermelha deve ser realizado à temperatura constante de 25°C em rolo de papel, com contagens inicial e final aos cinco e dez dias após a semeadura, respectivamente.

Impacto do racionamento nos resultados das empresas concessionárias do serviço público de distribuição de energia elétrica: um estudo nas empresas privadas da Região Nordeste

This work verifies the impact caused by the Emergencial Program of Reduction of Consumption of Electric Energy (energy-rationing program) in the results of the concessionary private companies of the public service of electric energy distribution localized in the Northeast Area. As the rationing invigorated from June 2001 to February 2002, its effects are diluted in the results presented by these companies in the second semester of 2001 and first quarter of 2002, with prominence for the last quarter of 2001, when the revenue of extraordinary tariff restore was instituted by the National Agency of Electric Energy (ANEEL), consequence of the so-called General Agreement of the Electric Sector made between the federal government and the companies of the electric sector. The structure of a generic electric sector and a historical review of the Brazilian electric sector from the time it was controlled by the private enterprises, including the State control period, about 1960, and returning to the control of the private enterprises in 1990, under a new regulation structure are presented. An explanation of the models of economic regulation that Brazil used for the electric sector is made, with prominence for the price cap that is the actual effective model. The process of tariff revision foreseen in the concession contracts signed by the federal government and the concessionary companies is presented, highlighting its two stages: the tariff rebalancing that defines the new price cap and the calculation of the factor X that establishes the efficiency goals for the companies. There is made a presentation of the Emergencial Program of Reduction of Consumption of Electric Energy and of the consequent General Agreement of the Electric Sector, which created the revenue of extraordinary tariff restore. A conceptual revision on reviews is presented, regarding to concepts, accomplishment and recognition. A brief review of the six companies that made part of the worked sample is also presented. Analyzing the quarters historical review and of amount of sold energy, it was possible to conclude that the energy-rationing altered the results of the studied companies significantly and that alteration was masked by the accounting process of the revenue of extraordinary tariff restore

Rastreabilidade da farinha de carne e ossos bovinos em ovos de poedeiras comerciais pela técnica dos isótopos estáveis do carbono e nitrogênio

Objetivou-se com este estudo rastrear a inclusão de farinha de carne e ossos bovinos em dietas para poedeiras comerciais, por meio da análise dos ovos e de suas frações (gema e albúmen), pela técnica dos isótopos estáveis do carbono e nitrogênio e avaliar o índice analítico mínimo detectável. Foram utilizadas 240 galinhas poedeiras da linhagem Shaver White de 73 semanas de idade, distribuídas em delineamento inteiramente casualizado, com cinco tratamentos e seis repetições. Foram avaliados cinco níveis de inclusão (0; 1,5; 3,0; 4,5 e 6,0%) de farinha de carne e ossos bovinos em uma dieta à base de milho e farelo de soja. No 35º dia, foram tomados aleatoriamente 24 ovos por tratamento: 12 serviram para amostragem de gema e albúmen e os outros 12 para amostragem do ovo (gema + albúmen). Os resultados isotópicos foram submetidos à análise multivariada de variância e, a partir das matrizes de erro, com 95% de confiança, foram determinadas elipses para identificar as diferenças entre os resultados obtidos com o fornecimento das dietas experimentais e a dieta controle, sem farinha de carne e ossos bovinos. No ovo e na gema, a partir do par isotópico da dieta com 3,0% de farinha de carne e ossos, houve diferenciação do par do tratamento controle, enquanto, no albúmen, a diferenciação ocorreu a partir do nível de 1,5% de farinha de carne e ossos bovinos na dieta. Pela técnica dos isótopos estáveis, é possível rastrear o uso de farinha de carne e ossos bovinos na alimentação de poedeiras; no albúmen, o nível mínimo de inclusão detectável é de 1,5% e, no ovo e na gema, 3,0%.

Biologic width changes around loaded implants inserted in different levels in relation to crestal bone: histometric evaluation in canine mandible

Objectives: The aim of the present study was to evaluate histometric changes around dental implants inserted at different levels in relation to the crestal bone, under different loading conditions.Material and methods: Thirty-six implants were inserted in the edentulous mandible of six mongrel dogs. Each implant was assigned to an experimental group according to the distance from the top of the implant to the crestal bone: Bone Level (at the crestal bone level), Minus 1 (1 mm below the crestal bone) or Minus 2 group (2 mm below the crestal bone). Each hemimandible was submitted to a loading protocol: conventional or immediate restoration. After 90 days, the animals were killed. Specimens were processed, and measurements were performed concerning the length of soft and hard peri-implant tissues. Data were analyzed using ANOVA and Student's t test (alpha=5%).Results: Among conventionally restored sites, the distance from the most coronal position of soft tissue margin (PSTM) and first bone-implant contact (fBIC) was greater for Minus 2 than for Bone Level and Minus 1 sites (P=0.03), but significant differences were not observed among immediately restored sites. Differences among groups were not observed concerning the PSTM, and the distance from the implant-abutment junction to fBIC. Greater amounts of lateral bone loss were observed for conventionally than for immediately restored sites (P=0.006).Conclusions: These findings suggest that the apical positioning of the top of the implant may not jeopardize the position of soft peri-implant tissues, and that immediate restoration can be beneficial to minimize lateral bone loss. Further studies are suggested to evaluate the clinical significance of these results in longer healing periods.

What About the Actor's Formant in Actresses' Voices?

Spectrographic analysis of male actors' voices showed a cluster, the actor's formant (AF), which is related to the perception of good and projected voice quality. To date, similar phenomena have not been described in the voices of actresses. Therefore, the objective of the current investigation was to compare actresses' and nonactresses' voices through acoustic analysis to verify the existence of the AF cluster or the strategies used to produce the performing voice. Thirty actresses and 30 nonactresses volunteered as subjects in the present study. All subjects read a 40-second text at both habitual and loud levels. Praat (v.5.1) was then used to analyze equivalent sound pressure level (Leq), speaking fundamental frequency (SFF), and in the long-term average spectrum window, the difference between the amplitude level of the fundamental frequency and first formant (L1 - L0), the spectral tilt (alpha ratio), and the amplitude and frequency of the AF region. Significant differences between the groups, in both levels, were observed for SFF and L1 - L0, with actresses presenting lower values. There were no significant differences between groups for Leq or alpha ratio at either level. There was no evidence of an AF cluster in the actresses' voices. Voice projection for this group of actresses seemed to be mainly a result of a laryngeal setting instead of vocal tract resonances.

Effects of the hydromethanolic extract of Austroplenckia populnea (Celastraceae) on reproductive parameters of male rats

Austroplenckia populnea (Reiss.) Lundell. was selected for this study because it has been shown that some plants from the Celastraceae family have antifertility effects. Twelve adult male rats were treated with hydromethanolic extract made from the leaves, 500 mg/kg/day, orally, for 70 days. Distilled water was administered to the control animals (n = 10). At the end of the experiment, and before killing the rats, their sexual behavior was evaluated. The number of intromissions, latencies to first mount and ejaculation, and first intromission after ejaculation were significantly reduced in the treated group, but the total number of ejaculations did not differ from the control group. The weight and histology of the reproductive organs, sperm production, spermatogenesis, prostate fructose content, cauda epidydimides duct diameter, and sperm morphology were not affected. Sperm concentration in cauda epidydimides was significantly decreased. The results showed that A. populnea has effects on male rat reproduction, affecting the sexual behavior and epididymal sperm concentration. (C) 2002 Elsevier B.V. All rights reserved.

A new species of Hyphessobrycon (Characiformes : Characidae) from rio Portuguesa, rio Orinoco basin, Venezuela

A new species of Hyphessobrycon is described from tributaries of the rio Portuguesa, rio Orinoco Basin, Venezuela. The new species is diagnosed from congeners by the presence of two large hooks on each side of the anal fin in adult males ( processes of last unbranched and first branched anal-fin rays), distal third of caudal-fin black except for its distal tips ( which are hyaline), anal-fin rays v, 19-21, and dorsal-fin rays ii, 8. Comments on its generic status and putative relationships are provided.

Helminth component community of the paradoxal frog Pseudis platensis Gallardo, 1961 (Anura: Hylidae) from south-eastern Pantanal, Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Occurrence of gastrointestinal parasites in goat kids

Amostras fecais de cabritos machos e fêmeas, de diferentes raças e com até uma ano de idade, foram examinadas para determinação do número de ovos e oocistos por grama de fezes (OPG e OoPG, respectivamente) e coprocultura para identificação genérica dos nematódeos. Ovos de helmintos e oocistos de Eimeria spp. foram observados em 93,06% (188/202) e 77,22% (156/202) das amostras, respectivamente. Pelas coproculturas, foram identificados os gêneros Cooperia em 11,88% (24/202), Haemonchus em 51,98% (105/202), Oesophagostomum em 9,4% (19/202), Strongyloides em 5,94 (12/202) e Trichostrongylus em 20,79% (42/202) das amostras. As espécies de Eimeria encontradas foram E. alijevi em 25,24% (51/202), E. arloingi em 7,42% (15/202), E. caprina em 2,97% (6/202), E. caprovina em 10,39% (21/202), E. christenseni em 4,45% (9/202), E. joklchijevi em 11,38% (23/202), E. hirci em 9,4% (19/202) e E. ninakohlyakimovae em 28,71% (58/202) das amostras. Dentre os parasitas gastrintestinais, houve predominância do gênero Haemonchus e de duas espécies de Eimeria: E. ninakohlyakimovae e E. alijevi.

Gap solitons in a model of a superfluid fermion gas in optical lattices

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

Quasiprobability distribution functions for finite-dimensional discrete phase spaces: Spin-tunneling effects in a toy model

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Intense visible photoluminescence in Ba(Zr0.25Ti0.75)O-3 thin films

Photoluminescence at room temperature in Ba(Zr0.25Ti0.75)O-3 thin films was explained by the degree of structural order-disorder. Ultraviolet-visible absorption spectroscopy, photoluminescence, and first principles quantum mechanical measurements were performed. The film annealed at 400 degrees C for 4 h presents intense visible photoluminescence behavior at room temperature. The increase of temperature and annealing time creates [ZrO6]-[TiO6] clusters in the lattice leading to the trapping of electrons and holes. Thus, [ZrO5]-[TiO6]/[ZrO6]-[TiO6] clusters were the main reason for the photoluminescence behavior.

Quantum Mechanics Insight into the Microwave Nucleation of SrTiO3 Nanospheres

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Traceability of animal meals in Japanese quail eggs using the technique of 13C e 15N* stable isotopes

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