The influence of cis/trans isomerism on the physical properties of a cyano-bridged dinuclear mixed valence complex

The cyano-bridged complexes cis-[L14CoIIINCFeII(CN)5]– and cis-[L14CoIIINCFeIII(CN)5] (L14= 6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine) are prepared and characterised spectroscopically, electrochemically and structurally: Na{cis-[L14CoIIINCFeII(CN)5]}·9H2O, monoclinic space group P21/c, a= 14.758(3), b= 10.496(1), c= 19.359(3) , = 92.00(2)°, Z= 4; cis-[L14CoIIINCFeIII(CN)5]·4H2O, orthorhombic space group P212121, a= 9.492(1), b= 14.709(2), c= 18.760(3) , Z= 4. In both complexes, the pendant amine is cis to the bridging cyanide ligand. An analysis of the metal-to-metal charge transfer (MMCT) transition in these systems with Hush theory has been carried out. This has revealed that the change in the configuration of the macrocycle both decreases the redox isomer energy difference (E1/2) and increases the reorganisational energy () of the cis-[L14CoIIINCFeII(CN)5]– complex with respect to the trans-[L14CoIIINCFeII(CN)5]– complex, the result being that both isomers display an MMCT transition of similar energy. The variation in redox isomer energy differences of the configurational isomers has been related to strain energy differences by molecular mechanics analysis of the [CoL14Cl]2+/+ precursor complexes.

Randomisation in clinical trials

Randomisation is the process of assigning clinical trial participants to treatment groups. Randomisation gives each participant a known (usually equal) chance of being assigned to any of the groups. Successful randomisation requires that group assignment cannot be predicted in advance.

Solution Structures of the cis- and trans-Pro30 Isomers of a Novel 38-Residue Toxin from the Venom of Hadronyche Infensa sp. that Contains a Cystine-Knot Motif within Its Four Disulfide Bonds

The primary sequence and three-dimensional structure of a novel peptide toxin isolated from the Australian funnel-web spider Hadronyche infensa sp. is reported. ACTX-HI:OB4219 contains 38 amino acids, including eight-cysteine residues that form four disulfide bonds. The connectivities of these disulfide bonds were previously unknown but have been unambiguously determined in this study. Three of these disulfide bonds are arranged in an inhibitor cystine-knot (ICK) motif, which is observed in a range of other disulfide-rich peptide toxins. The motif incorporates an embedded ring in the structure formed by two of the disulfides and their connecting backbone segments penetrated by a third disulfide bond. Using NMR spectroscopy, we determined that despite the isolation of a single native homologous product by RP-HPLC, ACTX-HI:OB4219 possesses two equally populated conformers in solution. These two conformers were determined to arise from cis/trans isomerization of the bond preceding Pro30. Full assignment of the NMR spectra for both conformers allowed for the calculation of their structures, revealing, the presence of a triple-stranded antiparallel sheet consistent with the inhibitor cystine-knot (ICK) motif.

James W. Gerard: His image of imperial Germany, 1913-1918

The subject of this study was a typical, if in some respects well qualified, U.S. ambassadorial appointee for his time, the early twentieth century: an attorney, judge, and politician who served competently in his one diplomatic assignment, in Berlin, before returning to private life.—Ed.

Mouse proteome analysis

A general overview of the protein sequence set for the mouse transcriptome produced during the FANTOM2 sequencing project is presented here. We applied different algorithms to characterize protein sequences derived from a nonredundant representative protein set (RPS) and a variant protein set (VPS) of the mouse transcriptome. The functional characterization and assignment of Gene Ontology terms was done by analysis of the proteome using InterPro. The Superfamily database analyses gave a detailed structural classification according to SCOP and provide additional evidence for the functional characterization of the proteome data. The MDS database analysis revealed new domains which are not presented in existing protein domain databases. Thus the transcriptome gives us a unique source of data for the detection of new functional groups. The data obtained for the RPS and VPS sets facilitated the comparison of different patterns of protein expression. A comparison of other existing mouse and human protein sequence sets (e.g., the International Protein Index) demonstrates the common patterns in mammalian proteornes. The analysis of the membrane organization within the transcriptome of multiple eukaryotes provides valuable statistics about the distribution of secretory and transmembrane proteins

Zygosity Diagnosis in the Absence of Genotypic Data: An Approach Using Latent Class Analysis

For zygosity diagnosis in the absence of genotypic data, or in the recruitment phase of a twin study where only single twins from same-sex pairs are being screened, or to provide a test for sample duplication leading to the false identification of a dizygotic pair as monozygotic, the appropriate analysis of respondents' answers to questions about zygosity is critical. Using data from a young adult Australian twin cohort (N = 2094 complete pairs and 519 singleton twins from same-sex pairs with complete responses to all zygosity items), we show that application of latent class analysis (LCA), fitting a 2-class model, yields results that show good concordance with traditional methods of zygosity diagnosis, but with certain important advantages. These include the ability, in many cases, to assign zygosity with specified probability on the basis of responses of a single informant (advantageous when one zygosity type is being oversampled); and the ability to quantify the probability of misassignment of zygosity, allowing prioritization of cases for genotyping as well as identification of cases of probable laboratory error. Out of 242 twins (from 121 like-sex pairs) where genotypic data were available for zygosity confirmation, only a single case was identified of incorrect zygosity assignment by the latent class algorithm. Zygosity assignment for that single case was identified by the LCA as uncertain (probability of being a monozygotic twin only 76%), and the co-twin's responses clearly identified the pair as dizygotic (probability of being dizygotic 100%). In the absence of genotypic data, or as a safeguard against sample duplication, application of LCA for zygosity assignment or confirmation is strongly recommended.

Calculation of bound and resonance states of HO2 for nonzero total angular momentum

Bound and resonance states of HO2 have been calculated quantum mechanically by the Lanczos homogeneous filter diagonalization method [Zhang and Smith, Phys. Chem. Chem. Phys. 3, 2282 (2001); J. Chem. Phys. 115, 5751 (2001)] for nonzero total angular momentum J = 1,2,3. For lower bound states, agreement between the results in this paper and previous work is quite satisfactory; while for high lying bound states and resonances these are the first reported results. A helicity quantum number V assignment (within the helicity conserving approximation) is performed and the results indicate that for lower bound states it is possible to assign the V quantum numbers unambiguously, but for resonances it is impossible to assign the V helicity quantum numbers due to strong mixing. In fact, for the high-lying bound states, the mixing has already appeared. These results indicate that the helicity conserving approximation is not good for the resonance state calculations and exact quantum calculations are needed to accurately describe the reaction dynamics for HO2 system. Analysis of the resonance widths shows that most of the resonances are overlapping and the interferences between them lead to large fluctuations from one resonance to another. In accord with the conclusions from earlier J = 0 calculations, this indicates that the dissociation of HO2 is essentially irregular. (C) 2003 American Institute of Physics.

NMR analysis of covalent intermediates in thiamin diphosphate enzymes

Enzymic catalysis proceeds via intermediates formed in the course of substrate conversion. Here, we directly detect key intermediates in thiamin diphosphate (ThDP)-dependent enzymes during catalysis using H-1 NMR spectroscopy. The quantitative analysis of the relative intermediate concentrations allows the determination of the microscopic rate constants of individual catalytic steps. As demonstrated for pyruvate decarboxylase (PDC), this method, in combination with site-directed mutagenesis, enables the assignment of individual side chains to single steps in catalysis. In PDC, two independent proton relay systems and the stereochemical control of the enzymic environment account for proficient catalysis proceeding via intermediates at carbon 2 of the enzyme-bound cofactor. The application of this method to other ThDP-dependent enzymes provides insight into their specific chemical pathways.

Solution structure of CnErg1 (Ergtoxin), a HERG specific scorpion toxin

The three-dimensional structure of chemically synthesized CnErg1 (Ergtoxin), which specifically blocks HERG (human ether-a-go-go-related gene) K+ channels, was determined by nuclear magnetic resonance spectroscopy. CnErg1 consists of a triple-stranded beta-sheet and an a-helix, as is typical of K+ channel scorpion toxins. The peptide structure differs from the canonical structures in that the first beta-strand is shorter and is nearer to the second beta-strand rather than to the third beta-strand on the C-terminus. There is also a large hydrophobic patch on the surface of the toxin, surrounding a central lysine residue, Lys13. We postulate that this hydrophobic patch is likely to form part of the binding surface of the toxin. (C) 2003 Published by Elsevier Science B.V. on behalf of the Federation of European Biochemical Societies.

Consignação em folha de pagamento : estudo sobre o papel da instituição nas implicações do uso da margem de consignação pelos servidores público

A utilização da margem de consignação é um fator indicativo de endividamento do servidor público, pois compromete parte de sua renda futura, diminuindo seu poder aquisitivo. A partir do ano de 2003 o governo brasileiro estimulou a oferta de crédito consignado, com taxas de juros mais atrativas, acarretando e um aumento do saldo de operações contratadas de 1.340,20% de 2004 a 2011. Devido as características do vínculo empregatício os servidores públicos se tornaram os principais tomadores de empréstimo consignado. Entretanto, o não entendimento da margem de consignação e a falta de educação financeira pode fazer com que o servidor entre em situação de dificuldade financeira, principalmente como sobreendividamento, que é a impossibilidade de pagar suas dívidas de créditos, podendo ter reflexo no desenvolvimento do trabalho. A fim de atingir o objetivo de identificar a atuação da instituição sobre as implicações do uso da margem de consignação pelos servidores públicos, foi realizado uma pesquisa de levantamento com abordagem quanti-qualitativa por meio de aplicação de questionário, obtendo um retorno de 210 respostas válidas. Os dados foram tabulados e analisados utilizando técnicas estatísticas como análise descritiva e tabelas de contingência observando os valores dos testes de qui-quadrado e V de Cramer. As conclusões indicam que a orientação financeira do servidor pode contribuir para utilização da margem de consignação de forma mais consciente evitando problemas financeiros e melhorando sua atuação no trabalho e que a instituição estudada poderia atuar de forma mais ativa sobre as implicações da margem de consignação. Por fim, foi recomendado como plano de intervenção da instituição a formulação de cursos sobre a educação financeira e sobre a margem de consignação, apresentado conceitos e casos cotidianos para melhor assimilação dos servidores, por meio do programa de capacitação dos servidores já existente na instituição

Percursos e identidades. A (re)construção da identidade profissional do docente de enfermagem: o olhar dos docentes

RESUMO: Considerando a identidade como um processo dinâmico de interacção social, afastando-nos da ideia de identidades pré-estabelecidas, ancoradas numa visão essencialista e, aproximando-nos de uma identidade profissional que se constrói através de sucessivas interacções, procurámos conhecer a identidade profissional do docente de enfermagem. Convictos de que o estudo da identidade pode oscilar entre um pólo individual e um estrutural, optámos pela dimensão biográfica como eixo estruturante deste trabalho. Efectuaram-se oito biografias a docentes integrados no conceito de perito com uma profissionalidade reflectida. Utilizámos ainda o focus group como método complementar. Constatámos que os actores deste estudo se sentem enfermeiros, embora a sua área de actuação seja a docência. Destacam a integração do ensino de enfermagem no ensino superior como determinante na mudança da sua representação social. Todos estes docentes se incluem nos grupos que apresentam um estatuto da identidade realizado ou outorgado. Das competências que devem estar presentes no docente de enfermagem, salientam-se a comunicação, actualização científica e relação, capazes de promover um ambiente que propicie as aprendizagens significativas, de internacionalização, de investigação, como um modelo de conduta a seguir, que participe na vida da organização e seja capaz de motivar o outro, mas sobretudo que seja um bom enfermeiro. ABSTRACT: Considering identity as a social dynamic integration process, departing from the concept of pre-established identities anchored in an essentialist vision, and approaching a professional identity built trough successive interaction, we aimed to know the professional identity of the nursing teacher. Believing that the identity study may oscillate between an individual and a structural pole, we have chosen the biographic dimension as the structural axis for this assignment. Eight biographies from teachers integrated in the expert with a reflective professional identity have been made. We have also used the focus group as a complementary method. We have seen that the actors of this study feel themselves as nurses although their working area is teaching. They point out the higher teaching of Nursing as a determinant in the change of their social representation. All of these teachers are included in the groups that present an identity status that has been fulfilled or attributed. From the skills that should be present in the nursing teacher, communication, scientific knowledge and relationship are indicated when these are able to provide significant learning, internationalization and research as a behaviour model to be followed regarding the life of the organization and that might incentive others, but above as a way to be a good nurse.

Planeamento e optimização em redes celulares móveis auto-geridas assentes em LTE

O objectivo deste trabalho consiste em avaliar os benefícios das Self Organizing Networks (SON), no que concerne ao planeamento e optimização de redes Long Term Evolution (LTE), não só através do seu estudo, como também através do desenvolvimento e teste de algoritmos, que permitem avaliar o funcionamento de algumas das suas principais funções. O estudo efectuado sobre as SON permitiu identificar um conjunto de funções, tais como a atribuição automática de Physical Cell Id (PCI), o Automatic Neighbour Relation (ANR) e a optimização automática de parâmetros de handover, que permitem facilitar ou mesmo substituir algumas das tarefas mais comuns em planeamento e optimização de redes móveis celulares, em particular, redes LTE. Recorrendo a um simulador LTE destinado à investigação académica, em código aberto e desenvolvido em Matlab®, foi desenvolvido um conjunto de algoritmos que permitiram a implementação das funções em questão. Para além das funções implementadas, foram também introduzidas alterações que conferem a este simulador a capacidade de representar e simular redes reais, permitindo uma análise mais coerente dos algoritmos desenvolvidos. Os resultados obtidos, para além de evidenciarem claramente o benefício dos algoritmos desenvolvidos, foram ainda comparados com os obtidos pela ferramenta profissional de planeamento e optimização Atoll®, tendo-se verificado a franca proximidade de desempenho em algumas das funções. Finalmente, foi desenvolvida uma interface gráfica que permite o desenho, configuração e simulação de cenários, bem como a análise de resultados.

Comparative evaluation of underlying causes of death processed by the Automated Classification of Medical Entities and the Underlying Cause of Death Selection Systems

INTRODUCTION: The correct identification of the underlying cause of death and its precise assignment to a code from the International Classification of Diseases are important issues to achieve accurate and universally comparable mortality statistics These factors, among other ones, led to the development of computer software programs in order to automatically identify the underlying cause of death. OBJECTIVE: This work was conceived to compare the underlying causes of death processed respectively by the Automated Classification of Medical Entities (ACME) and the "Sistema de Seleção de Causa Básica de Morte" (SCB) programs. MATERIAL AND METHOD: The comparative evaluation of the underlying causes of death processed respectively by ACME and SCB systems was performed using the input data file for the ACME system that included deaths which occurred in the State of S. Paulo from June to December 1993, totalling 129,104 records of the corresponding death certificates. The differences between underlying causes selected by ACME and SCB systems verified in the month of June, when considered as SCB errors, were used to correct and improve SCB processing logic and its decision tables. RESULTS: The processing of the underlying causes of death by the ACME and SCB systems resulted in 3,278 differences, that were analysed and ascribed to lack of answer to dialogue boxes during processing, to deaths due to human immunodeficiency virus [HIV] disease for which there was no specific provision in any of the systems, to coding and/or keying errors and to actual problems. The detailed analysis of these latter disclosed that the majority of the underlying causes of death processed by the SCB system were correct and that different interpretations were given to the mortality coding rules by each system, that some particular problems could not be explained with the available documentation and that a smaller proportion of problems were identified as SCB errors. CONCLUSION: These results, disclosing a very low and insignificant number of actual problems, guarantees the use of the version of the SCB system for the Ninth Revision of the International Classification of Diseases and assures the continuity of the work which is being undertaken for the Tenth Revision version.

Stabilization constraints from different-average public debt levels in a Monetary Union with country-size asymmetry

In the sequence of the recent financial and economic crisis, the recent public debt accumulation is expected to hamper considerably business cycle stabilization, by enlarging the budgetary consequences of the shocks. This paper analyses how the average level of public debt in a monetary union shapes optimal discretionary fiscal and monetary stabilization policies and affects stabilization welfare. We use a two-country micro-founded New-Keynesian model, where a benevolent central bank and the fiscal authorities play discretionary policy games under different union-average debt-constrained scenarios. We find that high debt levels shift monetary policy assignment from inflation to debt stabilization, making cooperation welfare superior to noncooperation. Moreover, when average debt is too high, welfare moves directly (inversely) with debt-to-output ratios for the union and the large country (small country) under cooperation. However, under non-cooperation, higher average debt levels benefit only the large country.

Conceções dos professores do ensino regular e dos professores de educação especial face à inclusão de alunos com multideficiência

Dissertação apresentada à Escola Superior de Educação de Lisboa para obtenção do grau de Mestre em Ciências da Educação - Especialização em Educação Especial, Domínio Cognição e Multideficiência