Synthesis and properties of new trinuclear Mo(II) complexes containing imidazole and benzimidazole ferrocene units

The reaction of FcCOC1 (Fc = (C5H5) Fe(C5H4)) with benzimidazole or imidazole in 1: 1 ratio gives the ferrocenyl derivatives FcCO(benzim) (L1) or FcCO(im) (L2), respectively. Two molecules of L1 or L2 can replace two nitrile ligands in [Mo(eta(3)-C3H5)( CO)(2)(CH3CN)(2)Br] or [Mo(eta(3)-C5H5O)(CO)(2)(CH3CN)(2)Br] leading to the new trinuclear complexes [Mo(eta(3)-C3H5)(CO)(2)(L)(2)Br] (C1 for L = L1; C3 for L = L2) and [Mo(eta(3)-C5H5O)(CO)(2)(L)(2)Br] (C-2 for L = L1; C4 for L = L2) with L1 and L2 acting as N-monodentade ligands. L1, L2 and C2 were characterized by X-ray diffraction studies. [Mo(eta(3)-C5H5O)(CO) 2(L1)(2)Br] was shown to be a trinuclear species, with the two L1 molecules occupying one equatorial and one axial position in the coordination sphere of Mo(II). Cyclic voltammetric studies were performed for the two ligands L1 and L2, as well as for their molybdenum complexes, and kinetic and thermodynamic data for the corresponding redox processes obtained. In agreement with the nature of the frontier orbitals obtained from DFT calculations, L1 and L2 exhibit one oxidation process at the Fe(II) center, while C1, C3, and C4 display another oxidation wave at lower potentials, associated with the oxidation of Mo(II). (C) 2007 Elsevier B. V. All rights reserved.

Nitrogen donor ligands bearing N-H groups: Effect on catalytic and cytotoxic activity of molybdenum eta(3)-allyldicarbonyl complexes

Reactions of [Mo(eta(3)-C3H5)Br(CO)(2)(NCMe)(2)] with the bidentate nitrogen ligands 2-(2'-pyridyl)imidazole (L1), 2-(2'-pyridyl)benzimidazole (L2), N,N'-bis(2'-pyridinecarboxamido)-1,2-ethane (L3), and 2,2'-bisimidazole (L4) led to the new complexes [Mo(eta(3)-C3H5)Br(CO)(2)(L)] (L = L1, 1; L2, 2; L4, 4) and [{Mo(eta(3)-C3H5) Br(CO)(2)}(2)(mu-L-3)] (3). The reaction of complexes 2 and 3 with Tl[CF3SO3] afforded [Mo(eta(3)-C3H5)(CF3SO3)(CO)(2)(L2)] (2T) and [{Mo(eta(3)-C3H5)(CF3SO3)(CO)(2)}(2)(mu-L-3)] (3T). Complexes 3 and 2T were structurally characterized by single crystal X-ray diffraction, showing the facial allyl/carbonyls arrangement and the formation of the axial isomer. In 2T, two molecules are assembled in a hydrogen bond dimer. The four complexes 1-4 were tested as precursors in the catalytic epoxidation of cyclooctene and styrene, in the presence of t-butylhydroperoxide (TBHP), with moderate conversions and turnover frequencies for complexes 1-3 and very low ones for 4. The increasing number of N-H groups in the complexes seems to be responsible for the loss of catalytic activity, compared with other related systems. The cytotoxic activities of all the complexes were evaluated against HeLa cells. The results showed that compounds 1,2,4, and 2T exhibited significant activity, complexes 2 and 2T being particularly promising. (C) 2008 Elsevier B.V. All rights reserved.

Standardized evaluation of algorithms for computer-aided diagnosis of dementia based on structural MRI: The CADDementia challenge

Algorithms for computer-aided diagnosis of dementia based on structural MRI have demonstrated high performance in the literature, but are difficult to compare as different data sets and methodology were used for evaluation. In addition, it is unclear how the algorithms would perform on previously unseen data, and thus, how they would perform in clinical practice when there is no real opportunity to adapt the algorithm to the data at hand. To address these comparability, generalizability and clinical applicability issues, we organized a grand challenge that aimed to objectively compare algorithms based on a clinically representative multi-center data set. Using clinical practice as the starting point, the goal was to reproduce the clinical diagnosis. Therefore, we evaluated algorithms for multi-class classification of three diagnostic groups: patients with probable Alzheimer's disease, patients with mild cognitive impairment and healthy controls. The diagnosis based on clinical criteria was used as reference standard, as it was the best available reference despite its known limitations. For evaluation, a previously unseen test set was used consisting of 354 T1-weighted MRI scans with the diagnoses blinded. Fifteen research teams participated with a total of 29 algorithms. The algorithms were trained on a small training set (n = 30) and optionally on data from other sources (e.g., the Alzheimer's Disease Neuroimaging Initiative, the Australian Imaging Biomarkers and Lifestyle flagship study of aging). The best performing algorithm yielded an accuracy of 63.0% and an area under the receiver-operating-characteristic curve (AUC) of 78.8%. In general, the best performances were achieved using feature extraction based on voxel-based morphometry or a combination of features that included volume, cortical thickness, shape and intensity. The challenge is open for new submissions via the web-based framework: http://caddementia.grand-challenge.org.

Supercritical CO(2) extraction of carotenoids from pitanga fruits (Eugenia uniflora L.)

Supercritical carbon dioxide (SC-CO(2)) extraction was employed to extract carotenoids from the freeze-dried pulp of pitanga fruits (Eugenia uniflora L.), an exotic fruit, rich in carotenoids and still little explored commercially. The SC-CO(2) extraction was carried out at two temperatures, 40 and 60 degrees C, and seven pressures, 100, 150, 200, 250, 300, 350 and 400 bar. The carotenoids were determined by high-performance liquid chromatography connected to photodiode array and mass spectrometry detectors. Lycopene, rubixanthin and P-cryptoxanthin were the main carotenoids present in the freeze-dried pitanga pulp, whereas beta-cryptoxanthin concentration was negligible in the SC-CO(2) extracts, for all the investigated state conditions. The maximum recovery of carotenoids was obtained at 60 degrees C and 250 bar, extracting 55% of the total carotenoid content, 74% of the rubixanthin and 78% of the lycopene from the pulp. Under these state conditions, the total carotenoid concentration in the extract was 5474 mu g/g, represented by 66% lycopene and 32% rubixanthin. The experimental state conditions produced different SC-CO(2) extracts with respect to the extraction yield and concentration of different carotenoids, indicating that the supercritical carbon dioxide was selective in the extraction of the pitanga carotenoids as a function of temperature and pressure. (C) 2008 Elsevier B.V. All rights reserved.

Cavernous sinus thrombosis in a patient with facial myiasis

Cavernous sinus thrombosis is a severe encephalic complication of the cervicofacial infections that can lead to death if not treated in adequate time. Among the several etiologies related to the development of this infection, myiasis has not been reported, enforcing the importance of the report of a case of thrombosis of the cavernous sinus developed from a facial myiasis. (Quintessence Int 2010;41:e72-e74)

A new dwarf shrubby species of Baccharis subg. Baccharis (Asteraceae, Astereae) from southeastern Brazil

Baccharis dichotoma, a new dwarf shrubby species, with small leaves and few heads, of high-altitude grasslands from southeastern Brazil, is described, illustrated, and assigned to subgenus Baccharis.

Genotoxic effects of X-rays on keratinized mucosa cells during panoramic dental radiography

Objectives: The aim of this study was to evaluate the genotoxic effects of X-rays on epithelial gingival cells during panoramic dental radiography using a differentiated protocol for the micronucleus test. Methods: 40 healthy individuals who underwent this procedure for diagnostic purposes on request from their dentists agreed to participate in this study. All of them answered a questionnaire before the examination. Epithelial gingival cells were obtained from the keratinized mucosa of the upper dental arcade by gentle scraping with a cervical brush immediately before exposure and 10 days later. Cytological preparations were stained according to the Feulgen-Rossenbeck reaction, counterstained with fast green 1% for 1 min and analysed under a light microscope. Micronuclei, nuclear projections (broken eggs) and degenerative nuclear alterations (pyknosis, karyolysis, karyorrhexis and condensed chromatin) were scored. Results: The frequency of micronuclei was significantly higher after exposure (P < 0.05), as were frequencies of nuclear alterations indicate of apoptosis (P < 0.001). Conclusions: These results indicate that X-ray radiation emitted during panoramic dental radiography induces a genotoxic effect on epithelial gingival cells that increases the frequency of chromosomal damage and nuclear alterations indicative of apoptosis.

Early Changes in Gene Expression Induced by Tobacco Smoke: Evidence for the Importance of Estrogen within Lung Tissue

Lung cancer is the leading cause of cancer deaths in the United States, surpassing breast cancer as the primary cause of cancer-related mortality in women. The goal of the present study was to identify early molecular changes in the lung induced by exposure to tobacco smoke and thus identify potential targets for chemoprevention. Female A/J mice were exposed to either tobacco smoke or HEPA-filtered air via a whole-body exposure chamber (6 h/d, 5 d/wk for 3, 8, and 20 weeks). Gene expression profiles of lung tissue from control and smoke-exposed animals were established using a 15K cDNA microarray. Cytochrome P450 1b1, a phase I enzyme involved in both the metabolism of xenobiotics and the 4-hydroxylation of 17 beta-estradiol (E(2)), was modulated to the greatest extent following smoke exposure. A panel of 10 genes were found to be differentially expressed in control and smoke-exposed lung tissues at 3, 8, and 20 weeks (P < 0.001). The interaction network of these differentially expressed genes revealed new pathways modulated by short-term smoke exposure, including estrogen metabolism. In addition, E(2) was detected within murine lung tissue by gas chromatography-coupled mass spectrometry and immunohistochemistry. Identification of the early molecular events that contribute to lung tumor formation is anticipated to lead to the development of promising targeted chemopreventive therapies. In conclusion, the presence of E2 within lung tissue when combined with the modulation of cytochrome P450 1b1 and other estrogen metabolism genes by tobacco smoke provides novel insight into a possible role for estrogens in lung cancer. Cancer Prev Res; 3(6); 707-17. (C) 2010 AACR.

Avaliação do desempenho empresarial: o passo seguinte à implementação do sistema de gestão

This study aimed to verify the steps involved in the deployment of Balanced Score Card as a system of strategic management at a Brazilian public company. It also had intended to verify if company can be considered a Strategy Focused Organization, by comparing the results of the management system implementation with the items listed in the literature, which also highlights the ability to obtain maximizing the financial and human resources through the strategic alignment. The results demonstrated that the company has implemented the management system according to the method indicated in the literature and after implementation presented evidence that, although has optimizing points on the alignment process, it can be considered a Strategy Focused Organization.

Luiz Cosme e suas manchas : um recorte musicológico

Este artigo é um estudo sobre os três grupos de peças denominados Três Manchas, do compositor brasileiro Luiz Cosme (1908-1965): Três Manchas para piano (1930), Três Manchas Gaúchas para canto e piano (1931) e Três Manchas de Cecília Meireles (1947). Este trabalho envolveu a busca pelas partituras das três séries de Manchas, a descrição deste material, bem como a comparação entre edições diferentes e fontes primárias. Além disso, foi feita uma descrição comentada sobre o conteúdo musical de cada uma das peças.

The certification role of venture capitalists, top underwriters and big-n auditors in ipos

Esta tese avalia o impacto dos principais atores recorrentes durante o processo de IPO, em particular, o venture capitalist, o underwriter, e o auditor, sobre as condições de comercialização das ações da empresa, capturado pelo bid-ask spread, a fração de investidores institucionais que investem na empresa, a dispersão de capital, entre outros. Além disso, este estudo também analisa alguns benefícios que os fundos de Venture Capital (VCs) fornecem às empresas que eles investem. Ele investiga o papel dos VCs em dificultar o gerenciamento de resultados em IPOs e quantifica o papel desempenhado por eles no desempenho operacional das empresas após sua oferta inicial de ações. No primeiro capítulo, os resultados indicam que as empresas inflam seus resultados principalmente nos períodos pré-IPO e do IPO. Quando nós controlamos para os quatro períodos diferentes do IPO, observamos que IPOs de empresas investidas por VCs apresentam significativamente menos gerenciamento de resultados no IPO e em períodos seguintes à orfeta inicial das ações, exatamente quando as empresas tendem a inflar mais seus lucros. Este resultado é robusto a diferentes métodos estatísticos e diferentes metodologias usadas para avaliar o gerenciamento de resultados. Além disso, ao dividir a amostra entre IPOs de empresas investidas e não investidas por VCs, observa-se que ambos os grupos apresentam gerenciamento de resultados. Ambas as subamostras apresentam níveis de gerenciamento de resultados de forma mais intensa em diferentes fases ao redor do IPO. Finalmente, observamos também que top underwriters apresentam menores níveis de gerenciamento de resultados na subamostra das empresas investidas por VCs. No segundo capítulo, verificou-se que a escolha do auditor, dos VCs, e underwriter pode indicar escolhas de longo prazo da empresa. Nós apresentamos evidências que as características do underwriter, auditor, e VC têm um impacto sobre as características das empresas e seu desempenho no mercado. Além disso, estes efeitos são persistentes por quase uma década. As empresas que têm um top underwriter e um auditor big-N no momento do IPO têm características de mercado que permanecem ao longo dos próximos 8 anos. Essas características são representadas por um número maior de analistas seguindo a empresa, uma grande dispersão da propriedade através de investidores institucionais, e maior liquidez através um bid-ask spread menor. Elas também são menos propensas a saírem do mercado, bem como mais propensas à emissão de uma orferta secundária. Finalmente, empresas investidas por VCs são positivamente afetadas, quando consideramos todas as medidas de liquidez de mercado, desde a abertura de capital até quase uma década depois. Tais efeitos não são devido ao viés de sobrevivência. Estes resultados não dependem da bolha dot-com, ou seja, os nossos resultados são qualitativamente similares, uma vez que excluímos o período da bolha de 1999-2000. No último capítulo foi evidenciado que empresas investidas por VCs incorrem em um nível mais elevado de saldo em tesouraria do que as empresas não investidas. Este efeito é persistente por pelo menos 8 anos após o IPO. Mostramos também que empresas investidas por VCs estão associadas a um nível menor de alavancagem e cobertura de juros ao longo dos primeiros oito anos após o IPO. Finalmente, não temos evidências estatisticamente significantes entre VCs e a razão dividendo lucro. Estes resultados também são robustos a diversos métodos estatísticos e diferentes metodologias.

Análise sobre a influência da personalidade e dos vieses comportamentais nos hábitos de investimento dos indivíduos

Com base nos estudos sobre finanças comportamentais, esta dissertação tem como objetivo verificar se o estilo cognitivo do indivíduo e seus respectivos vieses comportamentais exercem influência em seus hábitos de investimento como, por exemplo, sua decisão em investir em renda fixa ou renda variável. Uma survey foi realizada com os alunos de pós-graduação de 5 faculdades da cidade de São Paulo. O método foi escolhido por melhor se ajustar ao objetivo do trabalho. Foram analisados quatro tipos de perfis psicológicos, que se diferenciam, entre outras características, por possuírem maior ou menor tolerância ao risco. Foram examinados também dezoito vieses comportamentais entre eles: excesso de confiança, representatividade, aversão à perda e conta mental. Os resultados mostram evidências de que a personalidade pode exercer influência sobre a decisão do indivíduo em investir em renda fixa ou renda variável. Verificou-se também que os vieses confirmação e otimismo sinalizam uma possível influência na decisão dos indivíduos em investir em renda variável.

Aspectos Econômicos para a Comercialização do Açúcar e Etanol: Uma análise da competitividade.

Este material faz parte de um grupo de palestras realizadas durante o Encontro do Curso Superior de Tecnologia Sucroalcooleira UFSCar.