Simple finite field method for calculation of static and dynamic vibrational hyperpolarizabilities: curvature contributions

In the static field limit, the vibrational hyperpolarizability consists of two contributions due to: (1) the shift in the equilibrium geometry (known as nuclear relaxation), and (2) the change in the shape of the potential energy surface (known as curvature). Simple finite field methods have previously been developed for evaluating these static field contributions and also for determining the effect of nuclear relaxation on dynamic vibrational hyperpolarizabilities in the infinite frequency approximation. In this paper the finite field approach is extended to include, within the infinite frequency approximation, the effect of curvature on the major dynamic nonlinear optical processes

Variational calculation of static and dynamic vibrational nonlinear optical properties

The vibrational configuration interaction method used to obtain static vibrational (hyper)polarizabilities is extended to dynamic nonlinear optical properties in the infinite optical frequency approximation. Illustrative calculations are carried out on H2 O and N H3. The former molecule is weakly anharmonic while the latter contains a strongly anharmonic umbrella mode. The effect on vibrational (hyper)polarizabilities due to various truncations of the potential energy and property surfaces involved in the calculation are examined

Calculation of Franck-Condon factors including anharmonicity: simulation of the C2 H4+ X̃2B 3u←C2 H4X̃1 Ag band in the photoelectron spectrum of ethylene

Our new simple method for calculating accurate Franck-Condon factors including nondiagonal (i.e., mode-mode) anharmonic coupling is used to simulate the C2H4+X2B 3u←C2H4X̃1 Ag band in the photoelectron spectrum. An improved vibrational basis set truncation algorithm, which permits very efficient computations, is employed. Because the torsional mode is highly anharmonic it is separated from the other modes and treated exactly. All other modes are treated through the second-order perturbation theory. The perturbation-theory corrections are significant and lead to a good agreement with experiment, although the separability assumption for torsion causes the C2 D4 results to be not as good as those for C2 H4. A variational formulation to overcome this circumstance, and deal with large anharmonicities in general, is suggested

A comparative analysis of two methods for the calculation of electric-field-induced perturbations to molecular vibration

Two common methods of accounting for electric-field-induced perturbations to molecular vibration are analyzed and compared. The first method is based on a perturbation-theoretic treatment and the second on a finite-field treatment. The relationship between the two, which is not immediately apparent, is made by developing an algebraic formalism for the latter. Some of the higher-order terms in this development are documented here for the first time. As well as considering vibrational dipole polarizabilities and hyperpolarizabilities, we also make mention of the vibrational Stark effec

Variational calculation of vibrational linear and nonlinear optical properties

A variational approach for reliably calculating vibrational linear and nonlinear optical properties of molecules with large electrical and/or mechanical anharmonicity is introduced. This approach utilizes a self-consistent solution of the vibrational Schrödinger equation for the complete field-dependent potential-energy surface and, then, adds higher-level vibrational correlation corrections as desired. An initial application is made to static properties for three molecules of widely varying anharmonicity using the lowest-level vibrational correlation treatment (i.e., vibrational Møller-Plesset perturbation theory). Our results indicate when the conventional Bishop-Kirtman perturbation method can be expected to break down and when high-level vibrational correlation methods are likely to be required. Future improvements and extensions are discussed

Avaliação dos padrões de dose em radiologia pediátrica : comparação entre sistemas convencionais de películas e sistemas de digitalização de imagem em crianças dos 0-5 anos de idade, na radiografia do tórax em incidência antero-posterior

As evidências indicam que os sistemas de digitalização de imagem deveriam possibilitar uma redução da dose de radiação utilizada na execução de um determinado exame radiológico mas, na prática, nem sempre a dose utilizada é menor que em sistemas convencionais, por um lado, devido às características inerentes dos detectores utilizados e, por outro, ao papel preponderante da intervenção do Técnico de Radiologia. Pretendeu-se comparar a dose à entrada da pele (DEP) em crianças dos 0-5 anos, submetidas a radiografia do tórax, em Incidência Antero-Posterior (AP), em dois hospitais com diferentes sistemas de aquisição de imagem, comparando, também, os valores obtidos, com os níveis de referência de diagnóstico regulamentados pela ICRP. A média da dose à entrada da pele, no hospital que utiliza sistema de digitalização de imagem é de 26,64 Gy, enquanto que no hospital que utiliza sistema convencionail de películas é de 6,85 Gy. Observou-se que a média da dose à entrada da pele, nos sistemas de digitalização de imagem foram superiores à média das doses à entrada da pele nos sistemas convencionais de películas. Em ambos os hospitais a média da dose para as respectivas faixas etárias dos pacientes, não ultrapassou os limites estipulados por lei.

Contribuição para o conceito dose-resposta em exposições a infrasons e ruído de baixa frequência

O espectro acústico é normalmente dividido em dois segmentos distintos: um referente às frequências audíveis e outro às não audíveis. É também costume presumir que o fenómeno acústico só terá um efeito nocivo quando percepcionado pelo aparelho auditivo. Em comparação, no espectro electromagnético (EM) existe também um segmento passivel de ser percepcionado pelos sentidos humanos – a radiação visível (luz). No entanto, ao contrário do espectro acústico, o espectro EM não é dicotomizado em frequências visíveis e não-visíveis, nem é feita a suposição que apenas os fenómenos EM percepcionados pelo sistema ocular é que são nocivos. É esta a razão pela qual foi possível estabelecerem-se relações de dose-resposta entre os diferentes tipos de radiação e os respectivos efeitos biológicos. Uma abordagem semelhante deverá ser aplicada ao espectro acústico, para adequadamente estudar as relações de dose-resposta para exposições aos infrasons e ruído de baixa frequência (IRBF, <500 Hz). Este trabalho está fundamentado em informação recolhida ao longo de 28 anos de investigação biomédica dedicada aos efeitos biológicos da exposição aos IRBF.O objectivo é o de contribuir para o estabelecimento das relações de dose resposta para este agente de doença, propondo uma segmentação mais detalhada do espectro acústico.

Avaliação de dose em radiologia pediátrica numa unidade de cuidados intensivos neonatal

A radiossenssibilidade em crianças é superior à dos adultos, pelo que a avaliação dos parâmetros de dose utilizados em pediatria, principalmente em recém-nascidos, assume particular importância. Também importante é a avaliação da quantidade de dose de radiação a que os pacientes, pelo simples facto de estarem perto, ou na vizinhança, de outros que vão realizar exames radiológicos, estão sujeitos. Neste estudo, efectuado no Hospital D. Estefânia em Lisboa, avaliou-se a dose de radiação ionizante com dosímetros (ATOMTEX 3509B) no paciente examinado e no paciente adjacente. Foram calculadas as doses à entrada da pele (DEP) utilizando os parâmetros físicos empregados. Nos 28 exames efectuados por 8 técnicos diferentes, as leituras obtidas com os dosímetros eram praticamente insignificantes, quer para o paciente examinado (énero feminino e 0.04 énero masculino) quer para o adjacente (0 ). Os valores de DEP calculados estavam abaixo do limite recomendado internacionalmente para recém-nascidos, de 80 μGy. Apesar de haver uma diferença estatisticamente significativa entre os pesos das crianças do género masculino e feminino, não se verificou uma diferença semelhante para as DEP calculadas. Este estudo demonstrou que a DEP calculada com os parâmetros físicos utilizados ficava abaixo da DEP recomendada internacionalmente, e que as leituras obtidas nos pacientes examinados, bem como no paciente adjacente, atingiram níveis insignificantes.

Avaliação dos padrões de dose em radiologia pediátrica na radiografia simples do abdómen

A radiossensibilidade de crianças, muito superior à dos adultos, aliada à elevada utilização de exames radiológicos, justifica a preocupação com as doses à entrada da pele (DEP) e doses efectivas (DEF) durante exames radiológicos pediátricos. Neste trabalho quantificou-se a DEP e a DEF em sistemas convencionais e digitais em exames abdominais em crianças dos 0-15 anos, comparando os parâmetros físicos utilizados com os estipulados pelos critérios de boas práticas. Em 35 exames, verificou-se uma diferença estatisticamente significativa (p=0.025) entre DEP convencional (522.78 μGy) e digital (35.29 μGy), o que não ocorreu com a DEF (48.89 vs. 41.35 μGy). Os valores de DEP em sistema convencional ultrapassavam os de referência para os grupos etários de 1-4 (477.5 vs. 400 μGy) e 15 anos (2260 vs. 1200 μGy).A maior parte dos critérios de boas práticas estavam em conformidade com os critérios internacionais, excepto a utilização de filtragem (superior ao recomendado), a utilização inadequada de grelha e a utilização (não recomendada) de controlo automático de exposição em crianças com idade inferior a 5 anos.

Optimal dose of Kanamycin for protection from noise induced hearing loss

Young CBA/J mice were injected with kanamycin under varying schedules then exposed to noise in order to determine the boundary conditions for cochlear protection against noise.

Genetic influences on early cochlear vulnerability to noise and protection from noise by low-dose kanamycin in hybrid mice

Experiments evaluated both noise vulnerability and the extent of protection from noise by sub-chronic low-dose kanamycin in young F1 hybrids resulting from a cross between C57BL/6J and CBA/J inbred mice.

Chronic pesticide poisoning from persistent low-dose exposures in Ecuadorean floriculture workers: toward validating a low-cost test battery

Chronic pesticide poisoning is difficult to detect. We sought to develop a low-cost test battery for settings such as Ecuador’s floriculture industry. First we had to develop a case definition; as with all occupational diseases a case had to have both sufficient effective dose and associated health effects. For the former, using canonical discriminant analysis, we found that adding measures of protection and overall environmental stressors to occupational category and duration of exposure was useful. For the latter, factor analysis suggested three distinct manifestations of pesticide poisoning. We then determined sensitivity and specificity of various combinations of symptoms and simple neurotoxicity tests from the Pentox questionnaire, and found that doing so increased sensitivity and specificity compared to use of acethylcholinesterase alone – the current screening standard. While sensitivity and specificity varied with different case definitions, our results support the development of a low-cost test battery for screening in such settings.

An X-ray micro-tomography system optimised for the low-dose study of living organisms

An X-ray micro-tomography system has been designed that is dedicated to the low-dose imaging of radiation sensitive living organisms and has been used to image the early development of the first few days of plant development immediately after germination. The system is based on third-generation X-ray micro-tomography system and consists of an X-ray tube, two-dimensional X-ray detector and a mechanical sample manipulation stage. The X-ray source is a 50 kVp X-ray tube with a silver target with a filter to centre the X-ray spectrum on 22 keV.A 100 mm diameter X-ray image intensifier (XRII) is used to collect the two-dimensional projection images. The rotation tomography table incorporates a linear translation mechanism to eliminate ring artefact that is commonly associated with third-generation tomography systems' Developing maize seeds (Triticum aestivum) have been imaged using the system with a cubic voxel linear dimension of 100 mum, over a diameter of 25 mm and the root lengths and volumes measured. The X-ray dose to the plants was also assessed and found to have no effect on the plant root development. (C) 2003 Elsevier Science Ltd. All rights reserved.

Effect of high dose selenium enriched yeast diets on the distribution of total selenium and selenium species within lamb tissues

The objective of this study was to determine the distribution of total selenium (Se) and of the proportion of total Se comprised as the selenized amino acids selenomethionine (SeMet) and selenocysteine (SeCys) within the post mortem tissues of lambs that were fed high dose selenized enriched yeast (SY), derived from a specific strain of Saccharomyces cerevisae CNCM (Collection Nationale de Culture de Micro-organism) I-3060. Thirty two Texel X Suffolk lambs (6.87 ± 0.23 kg BW) were offered both reconstituted milk replacer and a pelleted diet, both of which had been either supplemented with high SY (6.30 ± 0.18 mg Se/kg DM) or unsupplemented (0.13 ± 0.01 mg Se/kg of DM), depending on treatment designation, for a continuous period of 91 d. At enrollment and 28, 56 and 91 d following enrollment lambs were blood sampled. At the completion of the treatment period, five lambs from each treatment group were euthanased and samples of heart, liver, kidney and skeletal muscle (Longissimus Dorsi and Psoas Major) were retained for Se analysis. The inclusion of high SY increased (P < 0.001) whole blood Se concentration, reaching a maximum mean value of 815.2 ± 19.1 ng Se/mL compared with 217.8 ± 9.1 ng Se/mL in control animals. Tissue total Se concentrations were significantly (P < 0.001) higher in SY supplemented animals than in controls irrespective of tissue type; values were 26, 16, 8 and 3 times higher in skeletal muscle, liver, heart and kidney tissue of HSY lambs when compared to controls. however, the distribution of total Se and the proportions of total Se comprised as either SeMet or SeCys differed between tissue types. Selenocysteine was the predominant selenized amino acid in glandular tissues, such the liver and kidney. irrespective of treatment, although absolute values were markedly higher in HSY lambs. Conversely selenomethionine was the predominat selenized amino acid in cardiac and skeletal muscle (Longissimus Dorsi, and Psoas Major) tissues in HSY animals, although the same trend was not apparent for control lambs in which SeCys was the predominant selenized amino acid. It was concluded that there were increases in both whole blood and tissue total Se concentrations as a result of dietary supplementation with high dose of SY. Furthermore, distribution of total Se and Se species differed between both treatment designation and tissue type.

Selenium persistency and speciation in the tissues of lambs following the withdrawal of dietary high-dose selenium-enriched yeast

The objective was to determine the concentration of total selenium (Se) and the proportion of total Se comprised as selenomethionine (SeMet) and selenocysteine (SeCys) in post mortem tissues of lambs in the six weeks period following the withdrawal of a diet containing high dose selenized yeast (SY), derived from a specific strain of Saccharomyces cerevisae CNCM (Collection Nationale de Culture de Micro-organism) I-3060. Thirty Texel x Suffolk lambs used in this study had previously received diets (91 days) containing either high dose SY (HSY; 6.30 mg Se/kg DM) or an unsupplemented control (C; 0.13 mg Se/kg DM). Following the period of supplementation all lambs were then offered a complete pelleted diet, without additional Se (0.15 mg Se/kg DM), for 42 days. At enrollment and 21 and 42 days later, five lambs from each treatment were blood sampled, euthanased and samples of heart, liver, kidney and skeletal muscle (Longissimus Dorsi and Psoas Major) tissue were retained. Total Se concentration in whole blood and tissues was significantly (P < 0.001) higher in HSY lambs at all time points that had previously received long term exposure to high dietary concentrations of SY. The distribution of total Se and the proportions of total Se comprised as SeMet and SeCys differed between tissues, treatment and time points. Total Se was greatest in HSY liver and kidney (22.64 and 18.96 mg Se/kg DM, respectively) and SeCys comprised the greatest proportion of total Se. Conversely, cardiac and skeletal muscle (Longissimus Dorsi and Psoas Major) tissues had lower total Se concentration (10.80, 7.02 and 7.82 mg Se/kg DM, respectively) and SeMet was the predominant selenized amino acid. Rates of Se clearance in HSY liver (307 µg Se/day) and kidney (238 µg Se/day) were higher compared with HSY cardiac tissue (120 µg Se/day) and skeletal muscle (20 µg Se/day). In conclusion differences in Se clearance rates were different between tissue types, reflecting the relative metabolic activity of each tissue, and appear to be dependant upon the proportions of total Se comprised as either SeMet or SeCys.