Rates of electronic energy transfer in conformationally flexible bichromophoric macrocyclic complexes: a combined experimental and molecular modeling study

Electronic energy transfer (EET) rate constants between a naphthalene donor and anthracene acceptor in [ZnL4a](ClO4)(2) and [ZnL4b](ClO4)(2) were determined by time-resolved fluorescence where L-4a and L-4b are the trans and cis isomers of 6-((anthracen-9-yl-methyl)amino)-6,13-dimethyl-13-((naphthalen-1-yl-methyl)amino)-1,4,8,11-tetraazacyclotetradecane, respectively. These isomers differ in the relative disposition of the appended chromophores with respect to the macrocyclic plane. The trans isomer has an energy transfer rate constant (k(EET)) of 8.7 x 10(8) s(-1), whereas that of the cis isomer is significantly faster (2.3 x 10(9) s(-1)). Molecular modeling was used to determine the likely distribution of conformations in CH3CN solution for these complexes in an attempt to identify any distance or orientation dependency that may account for the differing rate constants observed. The calculated conformational distributions together with analysis by H-1 NMR for the [ZnL4a](2+) trans complex in the common trans-III N-based isomer gave a calculated Forster rate constant close to that observed experimentally. For the [ZnL4b](2+) cis complex, the experimentally determined rate constant may be attributed to a combination of trans-Ill and trans-I N-based isomeric forms of the complex in solution.

Structural variations and formation constants of first-row transition metal complexes of biologically active aroylhydrazones

Iron chelators of the 2-pyridinecarbaldehyde isonicotinoylhydrazone (HPCIH) class show high potential for the treatment of iron overload diseases. In the present study, selected first-row transition metal (from Mn to Zn) complexes with HPCIH and 2-pyridinecarbaldehyde (4'-aminobenzoyl)hydrazone (HPCAH) were synthesised and characterised. Crystallography reveals that HPCAH exclusively forms bis complexes with divalent transition metals, with each ligand coordinating meridionally through its pyridine-N, imine-N and carbonyl-O atoms, forming distorted octahedral cis-MN4O2 complexes. Complexes of HPCIH were more varied and unpredictable, with metal/ligand ratios of 1:1, 1:2, 2:2 and 3:2 obtained with different metal ions. The isonicotinoyl ring N-atom in HPCIH was found to be an effective ligand, and this resulted in the varied metal/ligand ratios observed. The formation constants of divalent metal complexes with HPCIH were determined by potentiometric titrations and the values obtained were consistent with similar tridentate ligands and with the Irving-Williams order. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

Isomers of 1,4,8,11-tetraazacyclotetradecane-6,13-dicarboxylate characterized as cobalt(III) complexes

The major trans (1) and minor cis (2) isomers of 1,4,8,11-tetraazacyclotetradecane-6,13-dicarboxylate have been characterized as the complexes [Co(1)](ClO4) and [Co(H-2)(OH2)]Cl(ClO4).H2O. The former crystallized in the C-2/c space group and the latter in the P2(1)/c space group, with cell parameters a 16.258(7), b 9.050(3), c 15.413(6) Angstrom, beta133.29(3)degrees, and a 9.694(4), b 16.135(1), c 12.973(5) Angstrom, beta 93.00(2)degrees, respectively. Their characterization completes identification of the respective trans and cis isomers for the series of C-pendant macrocycles also including 1,4,8,11-tetraazacyclotetradecane-6-amine-13-carboxylate ((3), (4)) and 1,4,8,11-tetraazacyclotetradecane-6,13-diamine ((5), (6)). The complexes show limited distortion from octahedral geometry with the strain in the presence of the coordinated C-pendant carboxylate significantly reduced compared with that for the C-pendant amine in analogues, a consequence mainly of six-membered as opposed to five-membered chelate rings involving the pendant donor. A comparison of the physical properties for the trans isomers of the octahedral complexes of (1), (3), and (5), which reflect progressively increasing strain, is presented.

Dietary influences on survival after ovarian cancer

We evaluated the effects of various food groups and micronutrients in the diet on survival among women who originally participated in a population-based case-control study of ovarian cancer conducted across 3 Australian states between 1990 and 1993. This analysis included 609 women with invasive epithelial ovarian cancer, primarily because there was negligible mortality in women with borderline tumors. The women's usual diet was assessed using a validated food frequency questionnaire. Deaths in the cohort were identified using state-based cancer registries and the Australian National Death Index (NDI). Crude 5-year survival probabilities were estimated using the Kaplan-Meier technique, and adjusted hazard ratios (HRs) and 95% confidence intervals (CIs) were obtained from Cox regression models. After adjusting for important confounding factors, a survival advantage was observed for those who reported higher intake of vegetables in general (HR = 0.75, 95% CI = 0.57-0.99, p-value trend 0.01 for the highest third, compared to the lowest third), and cruciferous vegetables in particular (HR = 0.75, 95% CI = 0.57-0.98, p-value trend 0.03), and among women in the upper third of intake of vitamin E (HR = 0.76, 95% CI = 0.58-1.01, p-value trend 0.04). Inverse associations were also seen with protein (p-value trend 0.09), red meat (p-value trend 0.06) and white meat (p-value trend 0.07), and modest positive trends (maximum 30% excess) with lactose (p-value trend 0.04), calcium and dairy products. Although much remains to be learned about the influence of nutritional factors after a diagnosis of ovarian cancer, our study suggests the possibility that a diet high in vegetable intake may help improve survival. (C) 2003 Wiley-Liss, Inc.

Influência da idade da planta na produção de óleo essencial de alevante

O teor de óleo essencial e a sua composição química são características genéticas e podem ser influenciados pelo ambiente e pelo estádio de desenvolvimento ou idade da planta. Dessa forma, objetivou-se, com este trabalho, avaliar a influência da idade da planta sobre a produção e a qualidade do óleo essencial de alevante. O experimento foi conduzido em Ilhéus, BA, no período de maio a dezembro de 2009. Os tratamentos foram constituídos da colheita, em seis idades da planta (60, 90, 120, 150, 180 e 210 dias após o transplante), utilizando-se o delineamento inteiramente casualizado, com quatro repetições. O óleo essencial foi obtido por hidrodestilação, em aparelho de Clevenger modificado. A identificação dos constituintes químicos foi realizada por cromatografia gasosa acoplada ao espectrômetro de massas (CG-EM). O maior teor do óleo essencial (1%) ocorreu aos 120 dias e o maior teor dos compostos majoritários α-fenchol (49,92%) e cis-mirtanol (30,03%), aos 120 e 150 dias após o transplante, respectivamente.

Relação metionina + cistina / lisina digestível para frangos de corte cobb

Em vista da constante evolução do melhoramento genético de frangos de corte, torna-se necessária a determinação das exigências nutricionais dessas aves, para assegurar seu desempenho. Assim sendo, dois experimentos foram realizados, com o objetivo de avaliar diferentes relações de metionina + cistina / lisina digestível sobre o desempenho de frangos de corte, nas fases de 11 a 21 e 22 a 35 dias de idade. O delineamento experimental nas duas fases avaliadas foi o de blocos casualizados, em arranjo fatorial 2x5+2, (2 sexos e 5 diferentes relações met+cis/lis digestível e um tratamento controle para cada sexo), com oito repetições de 23 e 20 aves (COBB 500) por unidade experimental, nas fases descritas. As dietas atenderam às exigências, exceto para metionina + cistina e lisina. Para evitar o excesso de lisina digestível, seu nível foi calculado para 97% do recomendado para todas as fases. O tratamento controle foi adequado em lisina e metionina + cistina. As relações metionina + cistina/lisina digestível, para máximo desempenho de frangos de corte, machos e fêmeas, respectivamente, são de 75,53 e 78,23%, na fase de 11 a 21 dias, e 78,83 e 79,82%, na fase de 22 a 35 dias.

A promoção da cooperação nos consórcios intermunicipais de saúde do estado do Paraná

Os consórcios intermunicipais de saúde (CIS) são hoje instituições públicas disseminadas. A descentralização promovida na área de saúde nos anos 1990 estimulou a aglutinação de municípios, em especial os menores, para enfrentar uma dificuldade comum - a prestação de serviços especializados. São vinculados a algum CIS 41% dos municípios do país. Se considerarmos apenas os municípios com até 20 mil habitantes, 76% deles têm tal vínculo. Os CIS tentam fortalecer a cooperação entre os municípios e assim viabilizar parte de suas políticas públicas na área de saúde. O objetivo desta pesquisa é verificar, através de um survey com seus diretores, como se lida com conflitos e se promove a cooperação nos CIS paranaenses. Os resultados indicam que há atratividade financeira para participação nos CIS; valoriza-se o consenso entre os membros; há grande tolerância ao comportamento desviante; e a retaliação não cooperativa é rara e menos intensa do que a ação inicial.

Detection of psychiatric morbidity in the primary medical care setting in Brazil

The aims of this study were a) to assess the ability of primary care doctors to make accurate ratings of psychiatric disturbance and b) to evaluate the use of a case-finding questionnaire in the detection of psychiatric morbidity. The estudy took place in three primary care clinics in the city of São Paulo, Brazil, during a six-month survey. A time sample of consecutive adult attenders were asked to complete a case-finding questionnaire for psychiatric disorders (the Self Report Questionnaire - SRQ) and a subsample were selected for a semi-structured psychiatric interview (the Clinical Interview Schedule - CIS). At the end of the consultation the primary care doctors were asked to assess, in a standardized way, the presence or absence of psychiatric disorder; these assessments were then compared with that ratings obtained in the psychiatric interview. A considerable proportion of minor psychiatric morbidity remained undetected by the three primary care doctors: the hidden morbidity ranged from 22% to 79%. When these were compared to those of the case-finding questionnaire, they were consistently lower, indicating that the use of these instruments can enhance the recognition of psychiatric disorders in primary care settings. Four strategies for adopting the questionnaire are described, and some of the clinical consequences of its use are discussed.

Synthesis and Coordination Chemistry of a New N-4-Polydentate Class of Pyridyl-Functionalized Scorpionate Ligands: Complexes of Fe-II, Zn-II, V-IV, Pd-II and Use for Heterobimetallic Systems

The new potentially N-4-multidentate pyridyl-functionalized scorpionates 4-((tris-2,2,2-(pyrazol-1-ypethoxy)methyl)pyridine (TpmPy, (1)) and 4-((tris-2,2,2-(3-phenylpyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy(Ph), (2)) have been synthesized and their coordination behavior toward Fe-II, Ni-II, Zn-II, Cu-II, Pd-II, and V-III centers has been studied. Reaction of (1) with Fe(BF4)(2)center dot 6H(2)O yields [Fe(TpmPy)(2)](BF4)(2) (3), that, in the solid state, shows the sandwich structure with trihapto ligand coordination via the pyrazolyl arms, and is completely low spin (LS) until 400 K. Reactions of 2 equiv of (1) or (2) with Zn-II or Ni-II chlorides give the corresponding metal complexes with general formula [MCl2(TpmPy*)(2)] (M = Zn, Ni; TpmPy* = TpmPy, TpmPy(Ph)) (4-7) where the ligand is able to coordinate through either the pyrazolyl rings (in case of [Ni(TpmPy)(2)Cl-2 (5)) or the pyridyl-side (for [ZnCl2(TpmPy)(2)] (4), [ZnCl2(TpmPy(Ph))(2)] (6) and [NiCl2(TpmPy(Ph))(2)] (7)). The reaction of (1) with VCl3 gives [VOCl2(TpmPy)] (8) that shows the N-3-pyrazolyl coordination-mode. Moreover, (1) and react with cis-[PdCl2(CH3CN)(2)] to give the disubstituted complexes [PdCl2(TprnPy)(2)] (9) and [PdCl2(TpmPy(Ph))(2)] (10), respectively, bearing the scorpionate coordinated via the pyridyl group. Compounds (9) and (10) react with Fe(BF4)(2) to give the heterobimetallic Pd/Fe systems [PdCl2(mu-TpmPy)(2)-Fe](BF4)(2) (11) and [PdCl2(mu-TpmPy(Ph))(2)Fe-2(H2O)(6)]BF4)(4) (13), respectively. Compound (11) can also be formed from reaction of (3) with cis-[PdCl2(CH3CN)(2)], while reaction of (3) with Cu(NO3)(2).2.5H(2)O generates [Fe(mu-TpmPy)(2)-Cu(NO3)(2)](BF4)(2) (12), confirming the multidentate ability of the new chelating ligands. The X-ray diffraction analyses of compounds (1), (3), (4), (5), and (9) are also reported.

Gerenciamento do setor saúde na década de 80, no Estado de São Paulo, Brasil

Foi analisado o processo de gerenciamento colegiado implementado pelas Ações Integradas de Saúde (AIS), no Estado de São Paulo, na década de 80. A base de dados foi constituída por informações coletadas junto à Comissão Interinstitucional de Saúde (CIS-SP). Foram também investigadas a participação dos diversos representantes, as decisões e as resoluções originadas nessa instância de gerenciamento do sistema de saúde. A análise conjunta das informações coletadas mostrou que houve mudança substancial no papel de gerenciamento do setor saúde no Estado, principalmente a partir de 1987. O processo de gestão colegiada, iniciada com as AIS, foi sendo substituído paulatinamente pela gestão única, com a separação nítida das responsabilidades entre os níveis de governo municipal, estadual e federal. Esta mudança dificultou o processo de negociação e de definição de objetivos comuns entre os responsáveis pela política de saúde, que vinham sendo constituídos no Estado desde as AIS.

Transtornos do humor em enfermaria de clínica médica e validação de escala de medida (HAD) de ansiedade e depressão

Para estimar a prevalência de transtornos do humor, foram utilizadas a entrevista estruturada, "Clinical Interview Schedule" (CIS-R), e a escala "Hospital Anxiety and Depression" (HAD) em 78 pacientes internados em uma enfermaria geral de adultos (43 homens e 35 mulheres, média de idade = 43,2 anos). Foi encontrada prevalência instantânea de 39% de transtornos do humor. Dezesseis (20,5%) pacientes preencheram critérios para ansiedade, a maioria dos casos sendo de gravidade leve. Vinte e seis (33%) casos de depressão foram detectados, 7 dos quais de gravidade moderada. Observou-se uma combinação de sintomas de preocupação, depressão, ansiedade e insônia. A HAD mostrou-se de fácil compreensão pelos pacientes. As subescalas de ansiedade e de depressão tiveram consistência interna de 0,68 e 0,77, respectivamente. A correlação dos itens com as respectivas subescalas sugere que essas possuem validades convergentes, não discriminantes. Com ponto de corte 8/9, a sensibilidade e a especificidade foram 93,7% e 72,6%, para ansiedade, e 84,6% e 90,3%, para depressão. Na prática clínica, a utilização da HAD poderia auxiliar na detecção de casos de transtornos do humor que necessitam de tratamento.

Syntheses, Molecular Structures, Electrochemical Behavior, Theoretical Study, and Antitumor Activities of Organotin(IV) Complexes Containing 1-(4-Chlorophenyl)-1-cyclopentanecarboxylato Ligands

The organotin(IV) compounds [Me2Sn(L)(2)] (1), [Et(2)sn(L)(2)] (2), [(Bu2Sn)-Bu-n(L)(2)] (3), [(n)Oct(2)Sn(L)(2)] (4), [Ph2Sn(L)(2)] (5), and [PhOSnL](6) (6) have been synthesized from the reactions of 1-(4-chlorophenyl)-1-cyclopentanecarboxylic acid (HL) with the corresponding diorganotin(IV) oxide or dichloride. They were characterized by IR and multinuclear NMR spectroscopies, elemental analysis, cyclic voltammetry, and, for 2, 3, 4 and 6, single crystal X-ray diffraction analysis. While 1-5 are mononuclear diorganotin (IV) compounds, the X-ray diffraction of 6 discloses a hexameric drumlike structure with a prismatic Sn6O6 core. All these complexes undergo irreversible reductions and were screened for their in vitro antitumor activities toward HL-60, BGC-823, Bel-7402, and KB human cancer cell lines. Within the mononuclear compounds, the most active ones (3, 5) are easiest to reduce (least cathodic reduction potentials), while the least active ones (1, 4) are the most difficult to reduce. Structural rearrangements (i.e., Sn-O bond cleavages and trans-to-cis isomerization) induced by reduction, which eventually can favor the bioactivity, are disclosed by theoretical/electrochemical studies.

A qualidade das salas de berçários nos concelhos de Setubal e de Palmela

Tendo por principal objetivo contribuir para o estudo da qualidade das creches dos Concelhos de Setúbal e de Palmela, com este trabalho pretende-se (1) avaliar e descrever a qualidade de 30 salas de berçário através da aplicação da Escala de Avaliação do Ambiente de Creche – Edição Revista (Infant/Toddler Environment Rating Scale – Revised Edition [ITERS-R], Harms, Cryer, & Clifford, 2006), (2) avaliar e descrever as práticas de socialização dos prestadores de cuidados responsáveis pelas 30 salas de berçário através da aplicação da Escala de Interação do Prestador de Cuidados (Caregiver Interaction Scale [CIS], Arnett, 1989), (3) estudar a associação entre as práticas de socialização dos profissionais e a qualidade das salas de berçário, (4) estudar associações entre a qualidade das salas de berçário e as práticas de socialização dos profissionais e algumas variáveis de estrutura (rácio adulto/criança, tamanho do grupo, educação, formação e experiência dos prestadores de cuidados). Tendo em conta que os estudos efetuados em Portugal revelam qualidade inadequada e mínima nas salas de creche, os resultados obtidos no presente estudo sugerem que as salas observadas possuem qualidade entre o mínimo e o bom. Embora o presente estudo apresente resultados superiores, verificou-se que os itens que apresentam maiores fragilidades (áreas deficitárias), assim como os itens que expressam maior qualidade (áreas fortes) parecem convergir com os resultados das investigações já efetuadas, com efeito os itens relacionados com as subescalas Atividades e Rotinas de cuidados pessoais são os que apresentam os resultados mais preocupantes. A subescala Interação foi a que apresentou resultados superiores e as práticas de socialização dos prestadores de cuidados revelaram ser excelentes. Verificou-se, igualmente, que as salas orientadas por educadores de infância, assim como, as salas em que o principal prestador de cuidados era educador de infância revelaram qualidade superior do que salas orientadas por assistentes operacionais (auxiliares de ação educativa). Este efeito chama a atenção para a importância da formação e qualificação dos profissionais de educação, assim como, para a necessidade de se alterarem as políticas educativas, nomeadamente no que diz respeito à obrigatoriedade de existirem educadores de infância nas salas de berçário. - ABSTRACT With the main objective of contributing to the study of quality of infant/toddler center-based child care in the Counties of Setúbal and Palmela, this work aims to (1) assess and describe the quality of 30 infant classrooms by applying the Infant/Toddler Environment Rating Scale-Revised Edition ([ITERS-R], Harms, Cryer, & Clifford, 2006), (2) assess and describe the socialization practices of caregivers responsible for 30 infant classrooms by applying the Caregiver Interaction Scale ([CIS], Arnett, 1989), (3) study the association between the socialization practices of professionals and the quality of infant classrooms, (4) to study associations between the quality of infant classrooms and the socialization practices of professionals and some structure variables (ratio adult/child group size, education, training, and experience of carers). Considering that the studies carried out in Portugal reveal minimum or inadequate quality in infant/toddler center-based child care, the results of this study suggest that, in accordance with ITERS-R, the quality of the infant classrooms observed varies between minimum and good. Although the present study reports higher quality scores, it was found that items which present the biggest weaknesses (deficit areas) as well as the items which express higher quality (strengths) appear to converge with the results of the investigations already carried out, since the items related with subscales Activities and Personal Care Routines are those with the most worrisome results. The Interaction subscale from ITERS-R proved to be the one with higher scores, and socialization practices of caregivers proved to be excellent. It was also found that the rooms oriented by early childhood teachers, as well as the rooms in which the primary care provider was also guided by childhood teachers showed higher quality than when guided by operational assistants (educational activities assistants). This effect draws attention to the importance of the education professionals training and qualification, as well as the need for altering the educational policies, in particular as regards the obligation to ensure the existence of early childhood teachers in infant classrooms.

Self-organization for scheduling in agile manufacturing

Agility refers to the manufacturing system ability to rapidly adapt to market and environmental changes in efficient and cost-effective ways. This paper addresses the development of self-organization methods to enhance the operations of a scheduling system, by integrating scheduling system, configuration and optimization into a single autonomic process requiring minimal manual intervention to increase productivity and effectiveness while minimizing complexity for users. We intend to conceptualize real manufacturing systems as interacting autonomous entities in order to build future Decision Support Systems (DSS) for Scheduling in agile manufacturing environments.

Innovation and the performance of Portuguese businesses: a ‘SURE’ approach

There is a general consensus that in a competitive business environment, firms’ performance will depend on their capacity to innovate. To clarifying how, when and to what extent innovation affects the market and financial performance of firms, the authors deploy seemingly unrelated regression equation model to examine innovation in over 500 Portuguese firms from 1998 to 2004. The results confirm, as theorists have frequently assumed, that innovation positively affects firms’ performance; but they also suggest that the reverse is true, a result that is less intuitively obvious, given the complexity of the innovation process and local, national and global competitive environments.