Raman spectroscopy of a sulfur dioxide visual sensor: The origin of the two colors in the solid sample

The vibrational spectroscopic characterization of a sulfur dioxide visual sensor was carried out using a Raman microscope system. It was observed the formation of two distinct complexes, that were characterized by the position and relative intensities of the bands assigned to the symmetric stretching, nu(s)(SO(2)),of the linked SO(2) molecules. In fact, in the yellowish orange complex, that corresponds to the 1:1 stoichiometry, only one band is observed, assigned to nu(s)(SO(2)) at ca. 1080 cm-(1) and, in the deep red complex, that corresponds to the 1:2 complex, at ca. 1070 and 1090 cm(-)1 are observed. The variation of the relative intensities of the bands assigned to nu(s)(SO(2)) present in the Ni(II)center dot SO(2) complex, in different points of the sample, shows clearly the requirement of the Raman microscope in the vibrational characterization of this kind of molecular sensor. (C) 2008 Elsevier B.V. All rights reserved.

Chemical profile of rums as a function of their origin. The use of chemometric techniques for their identification

To identify chemical descriptors to distinguish Cuban from non-Cuban rums, analyses of 44 samples of rum from 15 different countries are described. To provide the chemical descriptors, analyses of the the mineral fraction, phenolic compounds, caramel, alcohols, acetic acid, ethyl acetate, ketones, and aldehydes were carried out. The analytical data were treated through the following chemometric methods: principal component analysis (PCA), partial least square-discriminate analysis (PLS-DA), and linear discriminate analysis (LDA). These analyses indicated 23 analytes as relevant chemical descriptors for the separation of rums into two distinct groups. The possibility of clustering the rum samples investigated through PCA analysis led to an accumulative percentage of 70.4% in the first three principal components, and isoamyl alcohol, n-propyl alcohol, copper, iron, 2-furfuraldehyde (furfuraldehyde), phenylmethanal (benzaldehyde), epicatechin, and vanillin were used as chemical descriptors. By applying the PLS-DA technique to the whole set of analytical data, the following analytes have been selected as descriptors: acetone, sec-butyl alcohol, isobutyl alcohol, ethyl acetate, methanol, isoamyl alcohol, magnesium, sodium, lead, iron, manganese, copper, zinc, 4-hydroxy3,5-dimethoxybenzaldehyde (syringaldehyde), methaldehyde (formaldehyde), 5-hydroxymethyl-2furfuraldehyde (5-HMF), acetalclehyde, 2-furfuraldehyde, 2-butenal (crotonaldehyde), n-pentanal (valeraldehyde), iso-pentanal (isovaleraldehyde), benzaldehyde, 2,3-butanodione monoxime, acetylacetone, epicatechin, and vanillin. By applying the LIDA technique, a model was developed, and the following analytes were selected as descriptors: ethyl acetate, sec-butyl alcohol, n-propyl alcohol, n-butyl alcohol, isoamyl alcohol, isobutyl alcohol, caramel, catechin, vanillin, epicatechin, manganese, acetalclehyde, 4-hydroxy-3-methoxybenzoic acid, 2-butenal, 4-hydroxy-3,5-dimethoxybenzoic acid, cyclopentanone, acetone, lead, zinc, calcium, barium, strontium, and sodium. This model allowed the discrimination of Cuban rums from the others with 88.2% accuracy.

The origin of the molecular interaction between amino acids and gold nanoparticles: A theoretical and experimental investigation

This study describes the synthesis of novel biological hybrid materials, where 3D structures were obtained using gold nanoparticles (AuNps) and methionine (Met) in a one-step procedure in aqueous media. The type of nanostructure can be controlled by tuning the intermolecular interactions between Met and AuNp, which strongly depends on the pH used for the synthesis. Computational simulation using the density-functional theory (DFT) showed that the AuNp - Met 3D structures are formed upon reorientation of Met molecules so that the backbone amine groups interact via H-bonds. These findings were experimentally confirmed using FTIR and UV-vis spectroscopy. Crown Copyright (C) 2008 Published by Elsevier B. V. All rights reserved.

The origin of the asymmetry in the irradiation distribution at high latitudes

The possibility of using solar energy during winter depends on the available solar radiation and on the geometry of the receiving surface. For high latitudes, the annual distribution of the available radiation is characterized by high asymmetry with a large amount of solar radiation from high altitude angles during the summer and a small amount of direct radiation from small altitude angles during the winter. This article deals with the origin of the difference between available solar radiation during summer and winter at high latitudes. Factors like the tilt of the earth’s axis, the eccentricity of the earth’s orbit, absorption and scattering of radiation in the atmosphere and seasonal changes in the weather conditions are discussed. Numerical examples of how these factors contribute to the reduction of the winter radiation compared to the summer radiation on surfaces with different orientation in Stockholm, latitude 59.4°N, are given. It is shown that the influence of the atmosphere and seasonal changes in the climate, and not pure earth-sun geometry, are the main reasons why it is hard to utilize solar energy at high latitudes during the winter.

Genetic Heteroscedasticity for Domestic Animal Traits

Animal traits differ not only in mean, but also in variation around the mean. For instance, one sire’s daughter group may be very homogeneous, while another sire’s daughters are much more heterogeneous in performance. The difference in residual variance can partially be explained by genetic differences. Models for such genetic heterogeneity of environmental variance include genetic effects for the mean and residual variance, and a correlation between the genetic effects for the mean and residual variance to measure how the residual variance might vary with the mean. The aim of this thesis was to develop a method based on double hierarchical generalized linear models for estimating genetic heteroscedasticity, and to apply it on four traits in two domestic animal species; teat count and litter size in pigs, and milk production and somatic cell count in dairy cows. The method developed is fast and has been implemented in software that is widely used in animal breeding, which makes it convenient to use. It is based on an approximation of double hierarchical generalized linear models by normal distributions. When having repeated observations on individuals or genetic groups, the estimates were found to be unbiased. For the traits studied, the estimated heritability values for the mean and the residual variance, and the genetic coefficients of variation, were found in the usual ranges reported. The genetic correlation between mean and residual variance was estimated for the pig traits only, and was found to be favorable for litter size, but unfavorable for teat count.

Avoiding the Fog of Crisis: A Protocol for the Proper Domestic Use of the Military

Failure to contemplate and define an appropriate role for the armed forces of the national government in domestic crises of this sort is a serious problem. It is all the more serious now as these potential crises seem to multiply in character and scope. This thesis will explore the history of this problem and its recent implications. It will argue the need for a comprehensive, operational framework, codified in law, which defines the various alternative uses of all emergency services, both civilian and military, and is applicable to “all hazards.” I will attempt to provide a blue-print for what such a framework should look like.

Sports administration: an examination of the competitive balance concept through european and brazilian domestic soccer leagues comparison

A questão do Equilíbrio Competitivo é um tema importante da economia dos esportes profissionais nos Estados Unidos e na Europa. Muitas pesquisas foram feitas para estabelecer os critérios mais relevantes para avaliar a competitividade das ligas profissionais de futebol. Esta pesquisa analisou a relevância do Equilíbrio Competitivo como determinante da competitividade comparando o Brasileirão Série A com as nove principais ligas na Europa (Bélgica, Inglaterra, Alemanha, Holanda, França, Itália, Portugal, Escócia e Espanha). A competitividade é a capacidade de uma empresa (um clube) ou de uma indústria de enfrentar a concorrência efetiva ou potencial. A medida da competitividade deve levar em consideração uma série de fatores importantes como a qualidade e a relação qualidade/preço, a gestão de recursos humanos e a organização empresarial. Esse trabalho visa demonstrar que, apesar da incerteza do resultado ter sido considerado por muito tempo como um fator positivo de atratividade/interesse dos fãs nos esportes, um campeonato equilibrado poderia ter um efeito insignificante, para não dizer desprezível sobre a competitividade das ligas de futebol a longo prazo. Os resultados mostraram que o aumento do Equilíbrio Competitivo pode ser relevante para os campeonatos mais fracos (Bélgica, Holanda, Portugal, Escócia), mas nao dos cincos melhores (Alemanha, Espanha, França, Inglaterra, Itália). Consequentemente, o Equilíbrio Competitivo deve ser contemplado como uma variável desprezível quanto à competitividade das ligas de futebol, apesar do interesse crescente pelo conceito na literatura. Baseado principalmente em pesquisas de Dell'Osso e Symanski (1991) e de Oughton e Michie (2004), o índice HHI (Herfindahl-Hirschman) tem sido utilizado para determinar o nível de concentração de 11 ligas de futebol estudadas. Uma revisão da literatura sobre administração de futebol e esportes foi realizada.

Crise de confiança e liquidez bancária: evidências empíricas no mercado bancário brasileiro

A reação da autoridade bancária frente a uma crise é de fundamental importância para a sua contenção. No Brasil, durante a crise do subprime, em 2008, observou-se a ocorrência de uma crise de liquidez em alguns bancos que levou o Banco Central a autorizar uma linha especial de captação de depósitos com limite muito superior ao habitual, denominado Depósito a Prazo com Garantia Especial (DPGE). Estes fatos propiciaram uma oportunidade de observar a reação dos depositantes frente a um choque exógeno ao sistema financeiro nacional para, em seguida, explorar a captação exógena de recursos devido à ampliação nos limites dos depósitos assegurados, com cobertura do Fundo Garantidor de Crédito (FGC). Além disso, analisou-se o efeito do DPGE sobre o crédito, considerando que depósitos assegurados e não-assegurados não são substitutos perfeitos e um aumento na oferta de depósitos assegurados deveria aumentar a oferta de crédito do mercado, como um todo. A estratégia empírica utilizada permitiu reconhecer os bancos emissores de DPGE, separando-os por outros fatores relacionados aos fundamentos bancários (tamanho, liquidez, qualidade dos ativos e retorno) e analisar os efeitos do DPGE nas taxas de juros praticadas na captação de depósitos a prazo, em geral. A base de dados utilizada também permitiu observar o comportamento desses bancos e a estratégia por eles utilizada na origem e destinação de tais recursos. Tomados em conjunto, os resultados encontrados são consistentes com a ideia de que depositantes migram seus recursos para a segurança durante a crise, na chamada “fuga para a qualidade” e retornam quando lhes dão a garantia necessária. Também é coerente com a teoria que diz que a substituição imperfeita entre depósitos assegurados e depósitos não-assegurados afeta a restrição de financiamentos dos bancos. O resultado deste estudo revela a importância da atuação da autoridade reguladora frente a situações críticas, bem como os efeitos no mercado causados pela permanência de um produto desenhado para uma situação específica.