The photochemistry of dioxorhenium(V)

The excited-state properties of trans-ReO₂(py)₄⁺ (ReO₂⁺) in acetonitrile solution have been investigated. The excited-state absorption spectrum of ReO₂⁺ is dominated by bleaching of the ground state MLCT and d-d systems. The reduction potential of ReO₂^2+/+* is estimated from emission and electrochemical data to be -0.7 V (SSCE). The ReO₂⁺ excited state efficiently reduces methylviologen and other pyridinium and olefin acceptors. The resulting Re(VI) species oxidizes secondary alcohols and silanes. Acetophenone is the product of sec-phenethyl alcohol oxidation.

The emission properties of ReO₂⁺ in aqueous solutions of anionic and nonionic surfactants have been investigated. The emission and absorption maxima of ReO₂⁺ are dependent on the water content of its environment. Emission lifetimes vary over four orders of magnitude upon shifting from aqueous to nonaqueous environments. The emission lifetime has a large (8.6) isotope effect (k(H₂O)/k(D₂O)) that reflects its sensitivity towards the environment. These properties have been used to develop a model for the interactions of ReO₂⁺ with sodium dodecyl sulfate (SDS). A hydrophobic ReO₂⁺ derivative, ReO₂(3-Ph-py)₄⁺, has been used to probe micelles of nonionic surfactants, and these results are consistent with those obtained with SDS.

The emission properties of ReO₂⁺ in Nafion perfluorosulfonated membranes have been investigated. Absorption and emission spectroscopy indicate that the interior of the membrane is quite polar, similar to ethylene glycol. Two well-resolved emission components show different lifetimes and different isotope effects, indicative of varying degrees of solvent accessibility. These components are taken as evidence for chemically distinct regions in the polymer film, assigned as the interfacial region and the ion cluster region.

The unsubstituted pyridine complex shows monophasic, τ = 1.7 µs, emission decay when bound to calf thymus DNA. Switching to the 3-Ph-py complex yields a biphasic emission decay (τ₁ = 2.4 µs, τ₂ = 10 µs) indicative of an additional, solvent-inaccessible binding mode. Photoinduced electron transfer to methylviologen leads to oxidative cleavage of the DNA as detected by gel electrophoresis. Electrochemical and spectrophotometric techniques used with organic substrates also can be used to monitor the oxidation of DNA. Abstraction of the ribose 4' hydrogen by ReO₂²⁺ is a possible mechanism.

Travel time tomographic studies of seismic structures around subducted lithospheric slabs

The nature of the subducted lithospheric slab is investigated seismologically by tomographic inversions of ISC residual travel times. The slab, in which nearly all deep earthquakes occur, is fast in the seismic images because it is much cooler than the ambient mantle. High resolution three-dimensional P and S wave models in the NW Pacific are obtained using regional data, while inversion for the SW Pacific slabs includes teleseismic arrivals. Resolution and noise estimations show the models are generally well-resolved.

The slab anomalies in these models, as inferred from the seismicity, are generally coherent in the upper mantle and become contorted and decrease in amplitude with depth. Fast slabs are surrounded by slow regions shallower than 350 km depth. Slab fingering, including segmentation and spreading, is indicated near the bottom of the upper mantle. The fast anomalies associated with the Japan, Izu-Bonin, Mariana and Kermadec subduction zones tend to flatten to sub-horizontal at depth, while downward spreading may occur under parts of the Mariana and Kuril arcs. The Tonga slab appears to end around 550 km depth, but is underlain by a fast band at 750-1000 km depths.

The NW Pacific model combined with the Clayton-Comer mantle model predicts many observed residual sphere patterns. The predictions indicate that the near-source anomalies affect the residual spheres less than the teleseismic contributions. The teleseismic contributions may be removed either by using a mantle model, or using teleseismic station averages of residuals from only regional events. The slab-like fast bands in the corrected residual spheres are are consistent with seismicity trends under the Mariana Tzu-Bonin and Japan trenches, but are inconsistent for the Kuril events.

The comparison of the tomographic models with earthquake focal mechanisms shows that deep compression axes and fast velocity slab anomalies are in consistent alignment, even when the slab is contorted or flattened. Abnormal stress patterns are seen at major junctions of the arcs. The depth boundary between tension and compression in the central parts of these arcs appears to depend on the dip and topology of the slab.

Segurança na Organização dos Estados Americanos (OEA): uma análise crítica dos discursos sobre segurança cidadã e direitos humanos

A segurança cidadã é apresentada nos dias de hoje como um novo modelo de segurança, forjado a partir da necessidade de aliar direito à segurança e proteção de direitos humanos. A expressão segurança cidadã habita planos de segurança nacionais e estratégias hemisféricas sobre segurança de forma bastante consensual, representando um avanço na atuação estatal frente às ameaças do campo da segurança pública, refletida em uma atuação humanizada. No desdobramento do conteúdo em ações, bem como na legitimação e propagação da terminologia e estratégias associadas a este modelo de segurança, a OEA se destaca como um importante espaço jurídico-político de caráter interamericano. O modelo de segurança cidadã é a conformação mais recente do conceito de segurança, que, entretanto, teve início na OEA - ainda anos 80 - por meio do desenvolvimento de documentos estratégicos de combate às drogas. Neste sentido, este trabalho quer entender, concretamente, em que medida esta novo modelo de segurança realmente oferece novas abordagens e/ou outras condições que representem uma ampliação na garantia de direitos humanos. Para tanto, considerasse relevante à análise dos mais relevantes documentos sobre segurança, nos quais é possível identificar conceitos-chave e estratégias de ação e como estes foram atualizados ao longo do tempo. Esta análise é feita a partir de uma perspectiva da criminologia crítica, que com seus conceitos e categorias equaciona aspectos da realidade político-criminal, bem como fatores socioeconômicos e da realidade carcerária da região, que usualmente não integram os modelos de segurança, embora tenham relação direta com uma mais ampla garantia de direitos humanos.

O Centro Cultural Cartola e o Processo de Patrimonialização do Samba Carioca

O Centro Cultural Cartola, sediado no bairro da Mangueira, na cidade do Rio de Janeiro, foi criado a partir da observação de que os processos de preservação de memória, de transmissão da história e dos saberes do samba carioca se encontravam profundamente fragilizados pela engrenagem comercial e turística a que foram subvertidos, principalmente nos redutos tradicionais dessa expressão cultural. Reconhecido como Ponto de Cultura, em 2005, o Centro Cultural Cartola foi proponente da candidatura do samba do Rio de Janeiro a Patrimônio Cultural Imaterial Brasileiro e, desde então, vem trabalhando o protagonismo social de sambistas, visando a sua afirmação social e a salvaguarda desse patrimônio, com a implantação de uma política de resgate, valorização e difusão dos bens registrados: Partido- Alto, Samba de Terreiro e Samba-enredo. Desde 2009, passou a ser reconhecido como um Pontão de Cultura. Esta pesquisa de doutorado tem por hipótese central verificar o impacto da política de patrimônio junto aos agentes de cultura popular e como esse fato vem possibilitar- lhes sua elevação à condição de protagonistas sociais da própria história, a fim de garantir- lhes direitos e a valorização da identidade cultural que representam. Paralelamente, procurou- se conhecer a implantação de um museu de memória social, bem como levantar as principais conquistas e dificuldades do CCC no cumprimento de sua missão institucional, no que se refere à preservação do samba carioca e às interferências sociohistóricas a que é submetido, considerando-o como algo fluído e mutante. Parte essencial será também verificar se o discurso dos sambistas sobre sua arte e identidade mudou com a incorporação do conceito de patrimônio. Ressalta-se que a implantação do processo de salvaguarda das matrizes do samba do Rio de Janeiro que não está dissociada dos seus criadores e das práticas socioculturais na construção de ações de preservação, fomento e difusão de bens titulados

Hybrid LES - RANS of complex geometry jets

Large eddy simulation (LES) type studies are made of a realistic geometry coaxial nozzle with a pylon. For the LES, since the solver being used tends towards having dissipative qualities, the subgrid scale (SGS) model is omitted, giving Numerical LES (NLES). To overcome near wall streak resolution problems a near wall RANS (Reynolds averaged Navier Stokes) model is used giving a hybrid NLES-RANS approach.The pylon is shown to influence the flow development, having a significant impact on peak turbulence levels and spreading rates. The results show that real geometry effects are influential and should be taken into account when moving towards real engine simulations. If their effects are ignored then, based on the studies here, key turbulence parameters will have significant error.

The influence of geometry on jet plume development

Our recent efforts of using large-eddy simulation (LES) type methods to study complex and realistic geometry single stream and co-flow nozzle jets and acoustics are summarized in this paper. For the LES, since the solver being used tends towards having dissipative qualities, the subgrid scale (SGS) model is omitted, giving a numerical type LES (NLES). To overcome near wall streak resolution problems a near wall RANS (Reynolds averaged Navier-Stokes) model is smoothly blended in the LES making a hybrid RANS-NLES approach. Several complex nozzle geometries including the serrated (chevron) nozzle, realistic co-axial nozzles with eccentricity, pylon and wing-flap are discussed. The hybrid RANS-NLES simulations show encouraging predictions for the chevron jets. The chevrons are known to increase the high frequency noise at high polar angles, but decrease the low frequency noise at lower angles. The deflection effect of the potential core has an important mechanism of noise reduction. As for co-axial nozzles, the eccentricity, the pylon and the deployed wing-flap are shown to influence the flow development, especially the former to the length of potential core and the latter two having a significant impact on peak turbulence levels and spreading rates. The studies suggest that complex and real geometry effects are influential and should be taken into count when moving towards real engine simulations. © 2012 Elsevier Ltd. All rights reserved.

Doping during low-temperature growth of materials for n-p-n Si/SiGe/Si heterojuction bipolar transistor by gas source molecular beam epitaxy

In situ doping for growth of n-p-n Si/SiGe/Si heterojuction bipolar transistor (HBT) structural materials in Si gas source molecular beam epitaxy is investigated. We studied high n-type doping kinetics in Si growth using disilane and phosphine, and p-type doping in SiGe growth using disilane, soild-Ge, and diborane with an emphasis on the effect of Ge on B incorporation. Based on these results, in situ growth of n-p-n Si/SiGe/Si HBT device structure is demonstrated with designed structural and carrier profiles, as verified from characterizations by X-ray diffraction, and spreading resistance profiling analysis. (C) 2000 Elsevier Science B.V. All rights reserved.

Properties of proton-implanted p-type Si: supports for the models explaining a novel p-n junction in Si

Proton-implanted and annealed p-type Si wafers were investigated by using both transmission electron microscopy and spreading resistivity probe. The novel pn junction [Li et al., Mat. Res. Sec. Symp, Proc. 396 (1996) 745], as obtained by using n-type Si subjected to the process as this work, was not observed in the p-type Si wafers in this work. A drop of superficial resistivity in the sample was found and is explained by the proposed models interpreting the novel pn junction. (C) 2000 Elsevier Science B.V. All rights reserved.

Rapid thermal annealing of arsenic implanted Si1-xGex epilayers

Rapid thermal annealing of arsenic implanted Si1-xGex was studied by secondary ion-mass spectroscopy (SIMS) and spreading resistance probe (SRP) over a wide range of Ge fractions (0-43%). Redistribution of the implanted arsenic was followed as a function of Ge content and annealing temperature. Arsenic concentration profiles from SIMS indicated that the behavior of implanted arsenic in Si1-xGex after RTA was different from that in Si, and the Si1-xGex samples exhibited box-shaped, concentration-dependent diffusion profiles with increasing Ge content. The maximum concentrations of electrically active arsenic in Si1-xGex was found to decrease with increasing Ge content. Experimental results showed that the arsenic diffusion is enhanced with increasing temperature for certain Ge content and strongly dependent on Ge content, and the higher Ge content, the faster As diffusion.

Biodegradable electrospun fibers for drug delivery

The influences of surfactants and medical drugs on the diameter size and uniformity of electrospun poly(L-lactic acid) (PLLA) fibers were examined by adding various surfactants (cationic, anionic, and nonionic) and typical drugs into the PLLA solution. Significant diameter reduction and uniformity improvement were observed. It was shown that the drugs were capsulated inside of the fibers and the drug release in the presence of proteinase K followed nearly zero-order kinetics due to the degradation of the PLLA fibers. Such ultrafine fiber mats containing drugs may find clinical applications in the future.

Deoxyribonucleic acid sample preparation in scanning probe microscope

The process of deoxyribonucleio acid (DNA) sample preparation in scanning tunneling microscope (STM) and atomic force microscope (AFM) is reviewed. The main discussions are devoted to the methods, advantages or drawbacks and improvement of the DNA sample's immobilization and spreading.

手持通信设备的多通道文本输入研究

Recently，Handheld Communication Devices is developing very fast, extending in users and spreading in application fields, and has an promising future. This study investigated the acceptance of the multimodal text entry method and the behavioral characteristics when using it. Based on the general information process model of a bimodal system and the human factor studies about the multimodal map system, the present study mainly focused on the hand-speech bimodal text entry method. For acceptance, the study investigated the subjective perception of the accuracy of speech recognition by Wizard of Oz (WOz) experiment and a questionnaire. Results showed that there was a linear relationship between the speech recognition accuracy and the subjective accuracy. Furthermore, as the familiarity increasing, the difference between the acceptable accuracy and the subjective accuracy gradually decreased. In addition, the similarity of meaning between the outcome of speech recognition and the correct sentences was an important referential criterion. The second study investigated three aspects of the bimodal text entry method, including input, error recovery and modal shifts. The first experiment aimed to find the behavioral characteristics of user when doing error recovery task. Results indicated that participants preferred to correct the error by handwriting, which had no relationship with the input modality. The second experiment aimed to discover the behavioral characteristics of users when doing text entry in various types of text. Results showed that users preferred to speech input in both words and sentences conditions, which was highly consistent among individuals, while no significant difference was found between handwriting and speech input in the character condition. Participants used more direct strategy than jumping strategy to deal with mixed text, especially for the Chinese-English mixed type. The third experiment examined the cognitive load in the different modal shifts, results suggesting that there were significant differences between different shifts. Moreover, relevant little time was needed in the Shift from speech input to hand input. Based on the main findings, implications were discussed as follows: Firstly, when evaluating a speech recognition system, attention should be paid to the fact that the speech recognition accuracy was not equal to the subjective accuracy. Secondly, in order to make a speech input system more acceptable, a good method is to train and supply the feedback for the accuracy in training, which improving the familiarity and sensitivity to the system. Thirdly, both the universal and individual behavioral patterns were taken into consideration to improve the error recovery method. Fourthly, easing the study and the use of speech input, the operations of speech input should be simpler. Fifthly, more convenient text input method for non-Chinese text entry should be provided. Finally, the shifting time between hand input and speech input provides an important parameter for the design of automatic-evoked speech recognition system.