Chemical and thermal influence of the [4Fe-4S](2+) cluster of A/G-specific adenine glycosylase from Corynebacterium pseudotuberculosis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Reference Cluster Normalization Improves Detection of Frontotemporal Lobar Degeneration by Means of FDG-PET.

Positron emission tomography with [18F] fluorodeoxyglucose (FDG-PET) plays a well-established role in assisting early detection of frontotemporal lobar degeneration (FTLD). Here, we examined the impact of intensity normalization to different reference areas on accuracy of FDG-PET to discriminate between patients with mild FTLD and healthy elderly subjects. FDG-PET was conducted at two centers using different acquisition protocols: 41 FTLD patients and 42 controls were studied at center 1, 11 FTLD patients and 13 controls were studied at center 2. All PET images were intensity normalized to the cerebellum, primary sensorimotor cortex (SMC), cerebral global mean (CGM), and a reference cluster with most preserved FDG uptake in the aforementioned patients group of center 1. Metabolic deficits in the patient group at center 1 appeared 1.5, 3.6, and 4.6 times greater in spatial extent, when tracer uptake was normalized to the reference cluster rather than to the cerebellum, SMC, and CGM, respectively. Logistic regression analyses based on normalized values from FTLD-typical regions showed that at center 1, cerebellar, SMC, CGM, and cluster normalizations differentiated patients from controls with accuracies of 86%, 76%, 75% and 90%, respectively. A similar order of effects was found at center 2. Cluster normalization leads to a significant increase of statistical power in detecting early FTLD-associated metabolic deficits. The established FTLD-specific cluster can be used to improve detection of FTLD on a single case basis at independent centers - a decisive step towards early diagnosis and prediction of FTLD syndromes enabling specific therapies in the future.

Core derived downhole logs for holes CRP-2 and CRP-2A

In the northern McMurdo Sound (Ross Sea, Antarctica), the CRP-2/2A drillhole targeted the western margin of the Victoria Land Basin to investigate Neogene to Palaeogene climatic and tectonic history by obtaining continuous core and downhole logs. Well logging of CRP-2/2A has provided a complete and comprehensive dataset of in situ geophysical measurements. This paper describes the evaluation and interpretation of the downhole logging data using multivariate statistical methods. Two major types of multivariate statistical methods were each yielding a different perspective: (1) Factor analysis was used as an objective tool for classification of the drilled sequence based on physical and chemical properties. The factor logs are mirroring the basic geological controls (i.e., grain size, porosity, clay mineralogy) behind the measured geophysical properties, thereby making them easier to interpret geologically. (2) Cluster analysis of the logs groups similar downhole geophysical properties into one cluster, delineating individual logging or sedimentological units. These objectively and independently defined units, or statistical electrofacies, are helpful in differentiating lithological and sedimentological characterisations (e.g. grain size, provenance). The multivariate statistical methods of factor and cluster analysis proved to be powerful tools for fast, reliable, and objective characterisation of downhole geophysical properties at CRP-2/2A, resulting in interpretations which are consistent with sedimentological findings.

Sintesi e studio dell'attività catalitica, in reazioni di idrogenazione e trasferimento di idrogeno, di cluster carbonilici idrurici di rutenio e iridio

Il presente elaborato finale è incentrato sulla sintesi, caratterizzazione e studio della reattività di nuovi cluster idrurici carbonilici di rutenio e iridio a bassa nuclearità; inoltre, l’attività catalitica di suddetti cluster è stata valutata in modo preliminare in reazioni di idrogenazione e trasferimento di idrogeno. In particolare è stata ottimizzata la sintesi del composto [NEt4][H2Ru3Ir(CO)12] (2), cluster principale dello studio catalitico, e sono stati sintetizzati altri cinque cluster bimetallici Ru-Ir di cui non risulta nota la struttura in letteratura: [H3Ru3Ir(CO)12] (3), [PPN]2[H2Ru3Ir(CO)12] (4a) ([PPN]+= [N(PPh3)2]+), [NEt4][HRu3Ir2(CO)12(COD)] (5) (COD = C8H12) e [H2Ru3Ir2(CO)10(COD)2]-[HRu2Ir3(CO)12(COD)2] (miscela 1:1) (6). Tutte le specie ottenute sono state caratterizzate mediante diffrazione a raggi X su cristallo singolo (SC-XRD), spettrometria di massa ESI-MS, spettroscopia IR e 1H-NMR. Il cluster 2 è risultato attivo nella reazione di idrogenazione di doppi legami polari mediante meccanismo di H transfer, utilizzando iPrOH come fonte di idrogeno, e 4-fluoro acetofenone come substrato modello; inoltre, con l'utilizzo di un'autoclave, si sono condotte prove di idrogenazione sotto pressione di idrogeno molecolare H2 utilizzando come substrato trans-cinnamaldeide, al fine di valutare l'effetto del catalizzatore sia in presenza di gruppi C=O che di un doppio legame C=C (aldeide α,β insatura).

Copper-organic frameworks assembled from in situ generated 5-(4-pyridyl) tetrazole building blocks: synthesis, structural features, topological analysis and catalytic oxidation of alcohols

Two new metal- organic compounds {[Cu-3(mu(3)-4-(p)tz)(4)(mu(2)-N-3)(2)(DMF)(2)](DMF)(2)}(n) (1) and {[Cu(4ptz) (2)(H2O)(2)]}(n) (2) {4-ptz = 5-(4-pyridyl)tetrazolate} with 3D and 2D coordination networks, respectively, have been synthesized while studying the effect of reaction conditions on the coordination modes of 4-pytz by employing the [2 + 3] cycloaddition as a tool for generating in situ the 5-substituted tetrazole ligands from 4-pyridinecarbonitrile and NaN3 in the presence of a copper(II) salt. The obtained compounds have been structurally characterized and the topological analysis of 1 discloses a topologically unique trinodal 3,5,6-connected 3D network which, upon further simplification, results in a uninodal 8-connected underlying net with the bcu (body centred cubic) topology driven by the [Cu-3(mu(2)-N-3)(2)] cluster nodes and mu(3)-4-ptz linkers. In contrast, the 2D metal-organic network in 2 has been classified as a uninodal 4-connected underlying net with the sql [Shubnikov tetragonal plane net] topology assembled from the Cu nodes and mu(2)-4-ptz linkers. The catalytic investigations disclosed that 1 and 2 act as active catalyst precursors towards the microwave-assisted homogeneous oxidation of secondary alcohols (1-phenylethanol, cyclohexanol, 2-hexanol, 3-hexanol, 2-octanol and 3-octanol) with tert-butylhydroperoxide, leading to the yields of the corresponding ketones up to 86% (TOF = 430 h(-1)) and 58% (TOF = 290 h(-1)) in the oxidation of 1-phenylethanol and cyclohexanol, respectively, after 1 h under low power ( 10 W) microwave irradiation, and in the absence of any added solvent or additive.

Identification of case complexity and increased health care utilization in patients with rheumatoid arthritis.

OBJECTIVES: To document biopsychosocial profiles of patients with rheumatoid arthritis (RA) by means of the INTERMED and to correlate the results with conventional methods of disease assessment and health care utilization. METHODS: Patients with RA (n = 75) were evaluated with the INTERMED, an instrument for assessing case complexity and care needs. Based on their INTERMED scores, patients were compared with regard to severity of illness, functional status, and health care utilization. RESULTS: In cluster analysis, a 2-cluster solution emerged, with about half of the patients characterized as complex. Complex patients scoring especially high in the psychosocial domain of the INTERMED were disabled significantly more often and took more psychotropic drugs. Although the 2 patient groups did not differ in severity of illness and functional status, complex patients rated their illness as more severe on subjective measures and on most items of the Medical Outcomes Study Short Form 36. Complex patients showed increased health care utilization despite a similar biologic profile. CONCLUSIONS: The INTERMED identified complex patients with increased health care utilization, provided meaningful and comprehensive patient information, and proved to be easy to implement and advantageous compared with conventional methods of disease assessment. Intervention studies will have to demonstrate whether management strategies based on INTERMED profiles can improve treatment response and outcome of complex patients.

RESONANCES EXCITED BY THE (9)Be((6)Li,d) (13)C REACTION

Alpha resonant states in (13)C tu to 15MeV were excited by the (9)Be ((6)Li,d) (13)C reaction, The data were taken at a bombarding energy of 25.5 MeV employing the sao Paulo-Pelletron-Enge Split Pole facility and the nuclear emulsion technique. The resolution of 50 keV allowed for the separation of the resonant contributions to the known 7/2(-) and (5/2(-)) states near the (9)Be + alpha threshold both associated with an L = 4 transfer. Several narrow alpha resonant states not previously measured were detected, in particular the one at the 3 alpha + n threshold populated by an L = 2 transfer, revealing a (9)Be + alpha component for the 1/2(-) cluster state candidate at this threshold.

Proposta de avaliação estratégica de clusters turísticos: o caso de Paranapiacaba – SP

O artigo tem como objetivo utilizar a contribuição do conceito de cluster para avaliação estratégica e apresentar uma proposta de análise das oportunidades do setor turístico, considerando todos os agentes envolvidos na criação,comercialização e divulgação dos serviços/produtos turísticos, que possibilitem atender as necessidades exigidas pela demanda e o desenvolvimento sustentável da população receptora. Utilizando como foco o distrito de Paranapiacaba, na cidade de Santo André/SP, foi feita uma pesquisa descritiva, em que inicialmente foram utilizados dados secundários e, em seguida, foi realizada a coleta de dados primários por meio de entrevistas programadas e observação direta em campo dos agentes envolvidos. Os resultados obtidos indicam a necessidade da consolidação de uma entidade supra-empresarial que exerça a governança e que seja capaz de agregar os interesses dos diversos setores, além de garantir a implantação de uma série de ações que venham contribuir para a criação de vantagens competitivas.

Impacto dos investimentos em tecnologia de informação no desempenho financeiro das indústrias brasileiras

Os resultados obtidos possibilitam afirmar que as indústrias que mais investiram em Tecnologia de Informação (TI), no período de 2001 a 2011, obtiveram maior crescimento da sua receita operacional e resultados operacionais mais eficazes, comparadas com as indústrias que investiram menos no período. De acordo com o modelo proposto, para as empresas estudadas foi possível encontrar, no prazo de dois anos, um crescimento de 7% no resultado operacional para cada 1% a mais de investimentos em TI. Destaca-se o objetivo da pesquisa de identificar e analisar os impactos dos gastos e investimentos em tecnologia de informação no desempenho financeiro das indústrias brasileiras, para alcançá-lo, adotou-se um modelo de pesquisa que utilizou métricas contábeis-financeiras e indicadores de uso TI, bem como a combinação de técnicas estatísticas para as análises. O trabalho aprofunda e amplia as discussões existentes sobre a avaliação dos investimentos em TI e como aferir o impacto desta sobre o desempenho organizacional. O universo do estudo foi composto pelas companhias brasileiras, de capital aberto, do ramo industrial, com ações ativas na BOVESPA, totalizando 119 companhias. Por meio de uma survey obteve-se os dados complementares referentes aos gastos e investimentos em TI; os questionários semiestruturados foram encaminhados diretamente ao Gerente de TI (Chief Information Officer). Estes esforços na coleta de dados primários possibilitaram a obtenção de uma amostra bastante significativa, com 63 indústrias, ou seja, 53% da população estudada. Após coleta, a análise dos dados foi desenvolvida em três etapas: (1) Análise Fatorial (AF) para seleção de fatores de desempenho que resultou no final do processo em doze variáveis para o modelo da pesquisa; (2) Análise de Cluster (AC) que evidenciou três agrupamentos distintos de indústrias por suas características e desempenho e (3) Regressão Múltipla que adotou um modelo econométrico dinâmico, estimado pelo Método dos Momentos Generalizado (GMM), satisfazendo as condições do modelo de Arellano-Bond (1991). Salienta-se que o modelo proposto permitiu tratar de forma adequada metodologicamente as correlações espúrias, possibilitando identificar que os gastos e investimentos em TI, (IGTI t-2), de dois períodos anteriores impactaram no Resultado Operacional Atual, (ROPt), evidenciando o efeito tardio, ou lag effect. Além disso, foi constatado que outras variáveis de rentabilidade e liquidez impactam neste resultado, também adotando defasagem das variáveis. A principal variável de TI da pesquisa, o IGTI, é calculada pela soma de gastos e investimentos em TI anuais (OPEX/CAPEX), dividida pela Receita Operacional Líquida anual. Para pesquisas futuras, há a possibilidade de buscar medidas de avaliação por tipos (categorias) de investimento em TI, visando ao aprofundamento da análise destes impactos no desempenho setorizado (ligado a cada investimento) e da análise de clusters, adotando o modelo de análise da pesquisa.

Das GAF-Domänen-Protein NreA : ein neuartiger Nitratrezeptor aus Staphylococcus carnosus

Staphylococcus carnosus ist ein fakultativ anaerobes Bakterium, das aerobe Atmung, anaerobe Nitratatmung und Gärungsstoffwechsel betreiben kann. Die Expression des Nitratstoffwechsels wird durch das Dreikomponentensystem NreABC reguliert.rnUnter anaeroben Bedingungen besitzt die Sensorhistidinkinase NreB in ihrer PAS-Domäne ein [Fe4S4]2+-Cluster. Das aktive (anaerobe) [Fe4S4]2+-NreB überträgt nach Autophosphorylierung die Phosphorylgruppe auf den Antwortregulator NreC, welcher dann die Expression der Gene der Nitratatmung aktiviert. Nitrat wirkt mit Hilfe des NreA-Proteins auf diese Gene induzierend. Im Rahmen der vorliegenden Arbeit wurde gezeigt, dass NreA ein GAF-Domänen-Protein und ein neuartiger Nitratrezeptor ist.rnDie Natur von NreA als GAF-Domänen-Protein bestätigte sich beim Vergleich der Kristallstruktur mit denen anderer GAF-Domänen. GAF-Domänen sind weit verbreitet und binden typischer Weise kleine Moleküle. Als physiologischer Ligand von NreA zeigte sich Nitrat, das innerhalb einer definierten Bindetasche gebunden wird. NreA bindet vermutlich in dimerer Form an dimeres NreB und inhibiert dadurch die Phosphorylierung der Sensorhistidinkinase NreB. Die Interaktion von NreA mit NreB wurde in vivo durch BACTH-Messungen und sowohl in vivo als auch in vitro durch Cross-Linking Experimente gezeigt. Nitrat reduziert den Ergebnissen nach die Interaktion von NreA mit NreB.rnDurch Sequenzvergleiche von NreA mit Homologen wurden konservierte Aminosäuren identifiziert. Über gerichtete Mutagenese wurden 25 NreA-Varianten hergestellt und bezüglich ihres Verhaltens in Abhängigkeit von Nitrat in narG-lip-Reportergenstudien getestet. Anhand ihres Phänotyps wurden sie als Wildtyp, NreA- und NreABC-Mutanten klassifiziert. Die Nitratbindetasche war in sechs Fällen betroffen. Die Phänotypen der Mutationen in der Peripherie lassen sich mit Auswirkungen auf die vermutete Konformationsänderung oder auf die Interaktion mit NreB erklären. Mutationen von konservierten, oberflächenexponierten Resten führten vermehrt zu NreA/ON-Varianten. Es ließen sich Bereiche auf der Proteinoberfläche identifizieren, die für NreA/NreA- oder NreA/NreB-Interaktionen wichtig sein könnten.rnDie Untersuchungen zeigten, dass NreA mit NreB interagiert und dass dadurch ein NreA/NreB-Sensorkomplex für die gemeinsame Erkennung von Nitrat und Sauerstoff gebildet wird.

The NreABC system of Staphylococcus carnosus combines nitrate and oxygen sensing by an NreA,NreB sensor complex

Staphylococcus carnosus is a facultative anaerobic bacterium which features the cytoplasmic NreABC system. It is necessary for regulation of nitrate respiration and the nitrate reductase gene narG in response to oxygen and nitrate availability. NreB is a sensor kinase of a two-component system and represents the oxygen sensor of the system. It binds an oxygen labile [4Fe-4S]2+ cluster under anaerobic conditions. NreB autophosphorylates and phosphoryl transfer activates the response regulator NreC which induces narG expression. The third component of the Nre system is the nitrate receptor NreA. In this study the role of the nitrate receptor protein NreA in nitrate regulation and its functional and physiological effect on oxygen regulation and interaction with the NreBC two-component system were detected. In vivo, a reporter gene assay for measuring expression of the NreABC regulated nitrate reductase gene narG was used for quantitative evaluation of NreA function. Maximal narG expression in wild type S. carnosus required anaerobic conditions and the presence of nitrate. Deletion of nreA allowed expression of narG under aerobic conditions, and under anaerobic conditions nitrate was no longer required for maximal induction. This indicates that NreA is a nitrate regulated inhibitor of narG expression. Purified NreA and variant NreA(Y95A) inhibited the autophosphorylation of anaerobic NreB in part and completely, respectively. Neither NreA nor NreA(Y95A) stimulated dephosphorylation of NreB-phosphate, however. Inhibition of phosphorylation was relieved completely when NreA with bound nitrate (NreA•[NO3-]) was used. The same effects of NreA were monitored with aerobically isolated Fe-S-less NreB, which indicates that NreA does not have an influence on the iron-sulfur cluster of NreB. In summary, the data of this study show that NreA interacts with the oxygen sensor NreB and controls its phosphorylation level in a nitrate dependent manner. This modulation of NreB-function by NreA and nitrate results in nitrate/oxygen co-sensing by an NreA/NreB sensory unit. It transmits the regulatory signal from oxygen and nitrate in a joint signal to target promoters. Therefore, nitrate and oxygen regulation of nitrate dissimilation follows a new mode of regulation not present in other facultative anaerobic bacteria.

Marital stability, satisfaction and well-being in old age: Variability and continuity in long-term continuously married older persons

Objectives: Recent research shows that the well-documented positive effects of marital stability on well-being and health outcomes are conditional upon the quality of marriage. To date, few studies have explored the relationship between marital satisfaction, well-being and health among very long-term married individuals. This study aims at identifying groups of long-term married persons with respect to marital satisfaction and comparing them longitudinally concerning their well-being outcomes, marital stressors, personality and socio-demographic variables. Method: Data are derived from a survey (data collection 2012 and 2014) with 374 continuously married individuals at wave 1 (mean age: 74.2 years, length of marriage: 49.2 years) and 252 at wave 2. Cluster analyses were performed comparing the clusters with regard to various well-being outcomes. The predictive power of cluster affiliation and various predictors at wave 1 on well-being outcomes at wave 2 was tested using regression analyses. Results: Two groups were identified, one happily the other unhappily married, with the happily married scoring higher on all well-being and health outcomes. Regression analyses revealed that group affiliation at wave 1 was not any longer predictive of health, emotional loneliness and hopelessness two years later, when taking into account socio-demographic variables, psychological resilience and marital strain, whereas it remained an important predictor of life satisfaction and social loneliness. Conclusion: Marital satisfaction is associated with health and well-being in older couples over time, whereas psychological resilience and marital strain are major predictors explaining the variance of these outcomes.

Results of bulk sediment X-ray diffraction analysis and quantification of mineral phases based on the RockJock and on the QUAX quantitative analysis

We have performed quantitative X-ray diffraction (qXRD) analysis of 157 grab or core-top samples from the western Nordic Seas between (WNS) ~57°-75°N and 5° to 45° W. The RockJock Vs6 analysis includes non-clay (20) and clay (10) mineral species in the <2 mm size fraction that sum to 100 weight %. The data matrix was reduced to 9 and 6 variables respectively by excluding minerals with low weight% and by grouping into larger groups, such as the alkali and plagioclase feldspars. Because of its potential dual origins calcite was placed outside of the sum. We initially hypothesized that a combination of regional bedrock outcrops and transport associated with drift-ice, meltwater plumes, and bottom currents would result in 6 clusters defined by "similar" mineral compositions. The hypothesis was tested by use of a fuzzy k-mean clustering algorithm and key minerals were identified by step-wise Discriminant Function Analysis. Key minerals in defining the clusters include quartz, pyroxene, muscovite, and amphibole. With 5 clusters, 87.5% of the observations are correctly classified. The geographic distributions of the five k-mean clusters compares reasonably well with the original hypothesis. The close spatial relationship between bedrock geology and discrete cluster membership stresses the importance of this variable at both the WNS-scale and at a more local scale in NE Greenland.