Dinuclear Azide-Bridged Copper(II) Complex as Building Block for the Assembly of a 2D-Supramolecular Array

A novel Schiff base-copper(II) complex [Cu(2)L(2)(N(3))(2)](ClO(4))(2) 1, where L = (4-imidazolyl)ethylene-2-amino-1-ethylpyridine (apyhist), containing azide-bridges between adjacent copper ions in a dinuclear arrangement was isolated and characterized both in the solid state and in solution by X-ray crystallography and different spectroscopic techniques. Azide binding constants were estimated from titrations of the precursor [CuL(H(2)O)(2)](2+) solutions with sodium azide, giving rise to the azido-bridged species, [Cu(2)L(2)(N(3))(2)](2+). Raman spectra showed asymmetric stretching band at 2060 cm(-1), indicating the presence of azido ligands with a symmetric mu(1,) (1) binding geometry. EPA spectra, in frozen methanol/water solutions at 77 K, exhibited characteristic features of copper centers in tetragonal pyramidal coordination geometry, exhibiting magnetic interactions between them. Further, in solid state, two different values for magnetic coupling in this species were obtained, J/k = -(5.14 +/- 0.02) cm(-1) attributed to the mu(1, 1) azide-bridge mode, and J`z`/k = -(2.94 +/- 0.11) cm(-1) for the interaction between dinuclear moieties via water/perchorate bridges. Finally, an attempt was made to correlate structure and magnetic data for this dinuclear asymmetric end-on azido bridged-copper(II) 1 complex with those of another correlated dinuclear system, complex [Cu(2)L(2)Cl(2)](ClO(4))(2) 2, containing the same tridentate diimine ligand, but with chloro-bridged groups between the copper centres.

Fast batch injection analysis of H(2)O(2) using an array of Pt-modified gold microelectrodes obtained from split electronic chips

A fast and robust analytical method for amperometric determination of hydrogen peroxide (H(2)O(2)) based on batch injection analysis (BIA) on an array of gold microelectrodes modified with platinum is proposed. The gold microelectrode array (n = 14) was obtained from electronic chips developed for surface mounted device technology (SMD), whose size offers advantages to adapt them in batch cells. The effect of the dispensing rate, volume injected, distance between the platinum microelectrodes and the pipette tip, as well as the volume of solution in the cell on the analytical response were evaluated. The method allows the H(2)O(2) amperometric determination in the concentration range from 0.8 mu mol L(-1) to 100 mu mol L(-1). The analytical frequency can attain 300 determinations per hour and the detection limit was estimated in 0.34 mu mol L(-1) (3 sigma). The anodic current peaks obtained after a series of 23 successive injections of 50 mu L of 25 mu mol L(-1) H(2)O(2) showed an RSD < 0.9%. To ensure the good selectivity to detect H(2)O(2), its determination was performed in a differential mode, with selective destruction of the H(2)O(2) with catalase in 10 mmol L(-1) phosphate buffer solution. Practical application of the analytical procedure involved H(2)O(2) determination in rainwater of Sao Paulo City. A comparison of the results obtained by the proposed ampermetric method with another one which combines flow injection analysis (FIA) with spectrophotometric detection showed good agreement. (C) 2011 Elsevier B.V. All rights reserved.

On the interaction of bovine serum albumin with ionic surfactants: Temperature induced EPR changes of a maleimide nitroxide reflect local protein dynamics and probe solvent accessibility

The interaction of bovine serum albumin (BSA) with the ionic surfactants sodium dodecylsulfate (SDS, anionic), cetyltrimethylammonium chloride (CTAC, cationic) and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS, zwitterionic) was studied by electron paramagnetic resonance (EPR) spectroscopy of spin label covalently bound to the single free thiol group of the protein. EPR spectra simulation allows to monitor the protein dynamics at the labeling site and to estimate the changes in standard Gibbs free energy, enthalpy and entropy for transferring the nitroxide side chain from the more motionally restricted to the less restricted component. Whereas SDS and CTAC showed similar increases in the dynamics of the protein backbone for all measured concentrations. HPS presented a smaller effect at concentrations above 1.5 mM. At 10 mM of surfactants and 0.15 mM BSA, the standard Gibbs free energy change was consistent with protein backbone conformations more expanded and exposed to the solvent as compared to the native protein, but with a less pronounced effect for HPS. In the presence of the surfactants, the enthalpy change, related to the energy required to dissociate the nitroxide side chain from the protein, was greater, suggesting a lower water activity. The nitroxide side chain also detected a higher viscosity environment in the vicinity of the paramagnetic probe induced by the addition of the surfactants. The results suggest that the surfactant-BSA interaction, at higher surfactant concentration, is affected by the affinities of the surfactant to its own micelles and micelle-like aggregates. Complementary DLS data suggests that the temperature induced changes monitored by the nitroxide probe reflects local changes in the vicinity of the single thiol group of Cys-34 BSA residue. (C) 2011 Elsevier B.V. All rights reserved.

Inflammation markers in healthy and periodontitis patients: a preliminary data screening

Advances in diagnostic research are moving towards methods whereby the periodontal risk can be identified and quantified by objective measures using biomarkers. Patients with periodontitis may have elevated circulating levels of specific inflammatory markers that can be correlated to the severity of the disease. The purpose of this study was to evaluate whether differences in the serum levels of inflammatory biomarkers are differentially expressed in healthy and periodontitis patients. Twenty-five patients (8 healthy patients and 17 chronic periodontitis patients) were enrolled in the study. A 15 mL blood sample was used for identification of the inflammatory markers, with a human inflammatory flow cytometry multiplex assay. Among 24 assessed cytokines, only 3 (RANTES, MIG and Eotaxin) were statistically different between groups (p<0.05). In conclusion, some of the selected markers of inflammation are differentially expressed in healthy and periodontitis patients. Cytokine profile analysis may be further explored to distinguish the periodontitis patients from the ones free of disease and also to be used as a measure of risk. The present data, however, are limited and larger sample size studies are required to validate the findings of the specific biomarkers.

Innovation and entrepreneurship in scientific research

This research wants to lay emphasis on topics that historicize and rescue concepts, in addition, shows the relation between innovation and socioeconomic development resulted; reviews the legal framework to stimulate new innovation into Brazilian society; considers the definition and the entrepreneur university's new paradigm; and finally, this research highlights the importance of teaching entrepreneur at universities, with straight society benefits. The results suggests that innovation is directly enrolled with a successful development of certain society, as well, is actually the biggest business competitive differential into corporative universe. In one way of getting results of social advancement to inform entrepreneur research practice, it appears that entrepreneurs concepts, necessarily, must be incorporated into the array of Science/Technology/Innovation for the effective development of supported formula. This article develops a thought about actual scientific researches paradigm, the way that is built on today, and if it's sufficient to effectively get the results that society expects from main bodies to create human resource and researches, especially those with innovation aspects, at Brazilian economic improvement.

Correlação entre padrão facial e relação sagital entre os arcos dentários no estágio de dentadura decídua: considerações epidemiológicas

OBJETIVO: A inter-relação oclusão e morfologia facial é fundamental para o diagnóstico e planejamento em ortodontia, bem como para determinação do prognóstico de tratamento. De um modo geral, a relação sagital entre os arcos dentários (Classe) tende a refletir o comportamento sagital do esqueleto facial (Padrão). O presente trabalho avalia a correlação entre as características morfológicas sagitais da face (Padrão) e da oclusão (Classe) no estágio de dentadura decídua. METODOLOGIA: A amostra foi composta por 2009 crianças, entre 03 e 06 anos de idade, no período de dentadura decídua completa, de 20 pré-escolas do Município de Bauru - SP. Os resultados demonstraram uma correlação estreita entre o Padrão facial e a Classe. No Padrão I predominou a Classe I (62,99%), seguida pela Classe II (35,82%) e Classe III (1,18%). No Padrão II, a Classe II foi predominante (81,35%) acompanhada de uma incidência baixa de Classe I (18,64%). No Padrão III, a Classe III estava presente em 50% das crianças, seguida pela Classe I, em 48,64%, e Classe II, em 1,35%. RESULTADOS: A expectativa se comprovou. Há uma tendência da Classe acompanhar o Padrão, desde o estágio de dentadura decídua. Isso foi mais explícito no Padrão II. Os resultados também esclarecem que a oclusão guarda alguma independência em relação ao Padrão. CONCLUSÃO: A maior heterogeneidade na distribuição das Classes ficou para os Padrões I e III. No Padrão II, as Classes se comportaram de forma mais homogênea, com mais de 80% das crianças exibindo Classe II.

Benign focal seizures of adolescence and neuropsychological findings in patients from community

RATIONALE: Benign focal seizures of adolescence (BFSA) described by Loiseau et al in 1972, is considered a rare entity, but maybe underdiagnosed. Although mild neuropsychological deficits have been reported in patients with benign epilepsies of childhood, these evaluations have not so far been described in BFSA. The aim of this study is to evaluate neuropsychological functions in BFSA with new onset seizures (<12 months). METHODS: Eight patients with BFSA (according to Loiseau et al, 1972, focal or secondarily tonic clonic generalized seizures between the ages of 10-18 yrs., normal neurologic examination, normal EEG or with mild focal abnormalities) initiated in the last 12 months were studied between July 2008 to May 2009. They were referred from the Pediatric Emergency Section of the Hospital Universitário of the University of Sao Paulo, a secondary care regionalized facility located in a district of middle-low income in Sao Paulo city, Brazil. The study was approved by the Ethics Committee of the Institution. All patients performed neurological, EEG, brain CT and neuropsychological evaluation which consisted of Raven's Special Progressive Matrices - General and Special Scale (according to different ages), Wechsler Children Intelligence Scale-WISC III with ACID Profile, Trail Making Test A/B, Stroop Test, Bender Visuo-Motor Test, Rey Complex Figure, Rey Auditory Verbal Learning Test-RAVLT, Boston Naming Test, Fluency Verbal for phonological and also conceptual patterns - FAS/Animals and Hooper Visual Organization Test. For academic achievement, we used a Brazilian test for named "Teste do Desempenho Escolar", which evaluates abilities to read, write and calculate according to school grade. RESULTS: There were 2 boys and 6 girls, with ages ranging from 10 yrs. 9 m to 14 yrs. 3 m. Most (7/8) of the patients presented one to two seizures and only three of them received antiepileptic drugs (AEDs). Six had mild EEG focal abnormalities and all had normal brain CT. All were literate, attended regular public schools and scored in a median range for IQ, and seven showed discrete higher scores for the verbal subtests. There were low scores for attention in different modalities in six patients, mainly in alternated attention as well as inhibitory subtests (Stroop test and Trail Making Test part B). Four of the latter cases who showed impairment both in alternated and inhibitory attention were not taking AEDs. Visual memory was impaired in five patients (Rey Complex Figure). Executive functions analysis showed deficits in working memory in five, mostly observed in Digits Indirect Order and Arithmetic tests (WISC III). Reading and writing skills were below the expected average for school grade in six patients according to the achievement scholar performance test utilized. One patient of this series who had the best scores in all tests was taking phenobarbital. CONCLUSIONS: Neuropsychological imbalance between normal IQ and mild dysfunctions such as in attention domain and in some executive abilities like working memory and planning, as well as difficulties in visual memory and in reading and writing, were described in this group of patients with BFSA from community. This may reflect mild higher level neurological dysfunctions in adolescence idiopathic focal seizures probably caused by an underlying dysmaturative epileptogenic process. Although academic problems often have multiple causes, a specific educational approach may be necessary in these adolescents, in order to improve their scholastic achievements, helping in this way, to decrease the stigma associated to epileptic seizures in the community.

Detecção de contaminação de solo por vinhaça através de análise de dados de eletrorresistividade

The vinasse, awaste produced in the proportion of 13 liters for each liter of alcohol. It has a high potential of polluting groundwater and superficial water resources, changes the soil behaviour and can also develop sanilization problems. This work aims to evaluate the efficiency of the DC-resistivity method in detecting and mapping anomalies caused by inappropriate disposal of vinasse in an inactive infiltration tank located at Sepé-Tiarajú settlement of landless agricultural laborers in the Ribeirão Preto region. Besides, as secondary goals, this work aims to characterize the type of anomaly residue as well as to diagnose its influence inside and outside of the limits of the tank. Eleven electrical resistivity tomography profiles were carried out with the dipole-dipole array, 10m of dipoles length and 5 leveis of investigation The geophysical survey enabled us to conclude that the DC-resistivity method is appropriate for mapping the contamination plume caused by intense vinasse disposal and its influence. It enabled also to conclude that the contamination exceeds the tank limits. The vinasse influence can be characterized by low resistivity values between 10 Ohm.m and 90 Ohm.m and its behavior can be compared with the one of the chorume, which is also conductive.

O uso de sondagens dipolo-dipolo em estudos hidrogeológicos e de depósitos de resíduos

Ensaios de sondagem e caminhamento elétrico têm sido realizados globalmente na avaliação de uma grande variedade de problemas em exploração mineral e hidrogeologia, bem como na caracterização de locais com risco de contaminação. A despeito da utilidade de ensaios geoelétricos em estudos hidrogeológicos e na caracterização de depósitos de resíduos desativados, um problema na utilização de sondagens elétricas ocorre em conseqüência da falta de espaço para aquisição de dados nessas áreas. Em áreas urbanas, isto constitui uma limitação importante devido à existência de construções, o que muitas vezes interrompe o desenvolvimento de ensaios de campo com arranjos de comprimentos adequados. Embora investigações rasas tendam a ser eficazes em caracterização geoambiental, a estimativa de parâmetros-chave pode depender da investigação de porções mais profundas. Entretanto, uma profundidade de investigação ligeiramente maior é obtida pelo arranjo dipolo-dipolo em comparação aos arranjos Schlumberger e Wenner de mesmo comprimento. Essa característica do arranjo dipolo-dipolo pode ser observada em vários estudos, mas provavelmente devido à tradição e à relação sinal-ruído, a grande maioria das sondagens elétricas é feita com os arranjos Schlumberger e Wenner.O arranjo dipolo-dipolo é mais utilizado em ensaios 2D. Até onde se sabe, essa maior capacidade de investigação em profundidade do arranjo dipolo-dipolo 1D não foi explorada em estudos geoambientais e nem em estudos hidrogeológicos em áreas urbanas. Este trabalho apresenta resultados de ensaios de campo que ressaltam a utilidade de sondagens dipolo-dipolo na investigação de tais áreas.

Anomalous somatic embryos in Acca sellowiana (O. Berg) Burret (Myrtaceae)

Somatic embryogenesis represents a valuable tool for the studies on the basic aspects of plant embryo development. Today this process is used as a potencial technique for large-scale plant micropropagation although, so far, it has been applied to only a small number of species. However, when somatic embryos are malformed they are considered economically useless. In Acca sellowiana (O. Berg) Burret, an important fruit-producing crop, large amounts of anomalous somatic embryos (76.3%) were found just after 40 days of culture of explants in a 2,4-D containing medium. Among the anomalous forms found in the cotiledonary stage, 12.2% consisted of fused embryos, 40.4% displayed fused cotyledons, 13.0% presented supernumerary cotyledons, and 10.7% showed absence or poorly developed cotyledons, including those without the shoot apical meristem. Histological analyses indicated that the altered embryos were formed either directly from cotyledons, hypocotyl and radicle of the zygotic embryos used as explants, or indirectly from calli formed from these tissue parts. It is suggested that the formation of anomalous somatic embryos, as well as a low frequency of conversion into emblings reflect physiological and/or genetic disturbances triggered by the presence of 2,4-D in the medium. In vitro experimental alternative approaches are discussed in order to lessen the occurrence of malformed somatic embryos.

Engagement of multifocal neural circuits during recall of autobiographical happy events

Happy emotional states have not been extensively explored in functional magnetic resonance imaging studies using autobiographic recall paradigms. We investigated the brain circuitry engaged during induction of happiness by standardized script-driven autobiographical recall in 11 healthy subjects (6 males), aged 32.4 ± 7.2 years, without physical or psychiatric disorders, selected according to their ability to vividly recall personal experiences. Blood oxygen level-dependent (BOLD) changes were recorded during auditory presentation of personal scripts of happiness, neutral content and negative emotional content (irritability). The same uniform structure was used for the cueing narratives of both emotionally salient and neutral conditions, in order to decrease the variability of findings. In the happiness relative to the neutral condition, there was an increased BOLD signal in the left dorsal prefrontal cortex and anterior insula, thalamus bilaterally, left hypothalamus, left anterior cingulate gyrus, and midportions of the left middle temporal gyrus (P < 0.05, corrected for multiple comparisons). Relative to the irritability condition, the happiness condition showed increased activity in the left insula, thalamus and hypothalamus, and in anterior and midportions of the inferior and middle temporal gyri bilaterally (P < 0.05, corrected), varying in size between 13 and 64 voxels. Findings of happiness-related increased activity in prefrontal and subcortical regions extend the results of previous functional imaging studies of autobiographical recall. The BOLD signal changes identified reflect general aspects of emotional processing, emotional control, and the processing of sensory and bodily signals associated with internally generated feelings of happiness. These results reinforce the notion that happiness induction engages a wide network of brain regions.

Ensino de astronomia em um espaço não formal: observação do Sol e de manchas solares

O presente artigo analisa os resultados obtidos num minicurso sobre o Sol e sua dinâmica realizado no Observatório Astronômico do Centro de Divulgação Científica e Cultural (CDCC) pertencente à Universidade de São Paulo (USP) na cidade de São Carlos para alunos do ensino fundamental. As atividades foram desenvolvidas na recente inaugurada, Sala Solar. Ela é dedicada ao estudo do Sol, enfatizando a observação de manchas solares e do espectro do Sol. A metodologia adotada no minicurso consistiu em pequenos experimentos, observações e diálogos expositivos. Isto incentivou os estudantes a tomarem decisões, fazerem questionamentos e refletirem gerando pensamentos mais críticos e produzindo um maior número de conexões entre o real e o abstrato que contribuiu para níveis de maior complexidade conceitual verificados durante entrevistas semiestruturadas e nas respostas ao questionário final.

Transmissão psíquica transgeracional e construção de subjetividade: relato de uma psicoterapia psicanalítica vincular

O presente artigo tem como objetivo refletir acerca do conceito de transmissão psíquica entre gerações, especificamente de uma modalidade - a transmissão psíquica transgeracional - e sua influência na construção das subjetividades individuais e dos vínculos familiares, enfatizando-se aqui o vínculo mãe-filha como gerador de sintomas na criança e conflitos no âmbito familiar, através de um relato clínico de uma psicoterapia psicanalítica vincular, segundo os referenciais de Eiguer (2006) e Berenstein e Puget (1997, 2005). A apresentação do caso clínico permite discutir, ainda, a relação entre a transmissão psíquica transgeracional e o estabelecimento da “maternagem”, bem como os resultados obtidos ao longo de todo o processo psicoterápico. A finalidade desse espaço terapêutico familiar é a de propiciar transformações frente ao legado geracional, promovendo o surgimento de uma subjetividade nova, impulsionadora de vida.

Um estudo de follow up em psicoterapia psicanalítica de casais

Por 11 anos desenvolvemos uma pesquisa envolvendo uma proposta interventiva com famílias que buscam atendimento em um serviço-escola, com demanda localizada na criança. Por meio da psicoterapia psicanalítica com o casal procuramos atingir a remissão dos sintomas do(s) filho(s). O objetivo deste estudo é refletir sobre a manutenção das mudanças psíquicas ocorridas nesse tipo de clínica, que abrange a esfera conjugal e familiar, ao longo do tempo. Com base na metodologia de estudo de caso e no referencial psicanalítico, foram analisados dois casos clínicos enfatizando-se as sessões de follow up: dois casais que estiveram em processo terapêutico, respectivamente, por três anos e por dois anos e meio, sendo realizadas duas sessões de acompanhamento após o término da terapia. Esse tipo de intervenção mostrou-se efetiva para a elucidação de conflitos conjugais latentes e como promovedora de um ambiente saudável e favorecedor do desenvolvimento emocional da criança.

Behavioral alarm treatment for nocturnal enuresis

PURPOSES: To investigate the efficacy of alarm treatment in a sample of Brazilian children and adolescents with nocturnal enuresis and relate treatment success to age and type of clinical support. MATERIALS AND METHODS: During 32 weeks, 84 children and adolescents received alarm treatment together with weekly psychological support sessions for individual families or groups of 5 to 10 families. RESULTS: 71% of the participants achieved success, defined as 14 consecutive dry nights. The result was similar for children and adolescents and for individual or group support. The time until success was shorter for participants missing fewer support sessions. CONCLUSIONS: Alarm treatment was effective for the present sample, regardless of age or type of support. Missing a higher number of support sessions, which may reflect low motivation for treatment, increased the risk of failure.