Estudo teórico QTAIM e DFT dos compostos de coordenação: efeito quelato, titanocenos e ligação química

This work is a study of coordination compounds by quantum theory of atoms in molecules (QTAIM), based on the topological analysis of the electron density of molecular systems, both theoretically and experimentally obtained. The coordination chemistry topics which were studied are the chelate effect, bent titanocene and chemical bond in coordination complexes. The chelate effect was investigated according to topological and thermodynamic parameters. The exchange of monodentate ligands on polydentate ligands from same transition metal increases the stability of the complex both from entropy and enthalpy contributions. In some cases, the latter had a higher contribution to the stability of the complex in comparison with entropy. This enthalpic contribution is explained according to topological analysis of the M-ligand bonds where polidentate complex had higher values of electron density of bond critical point, Laplacian of electron density of bond critical point and delocalization index (number of shared electrons between two atoms). In the second chapter, was studied bent titanocenes with bulky cyclopentadienyl derivative π-ligand. The topological study showed the presence of secondary interactions between the atoms of π-ligands or between atoms of π-ligand and -ligand. It was found that, in the case of titanocenes with small difference in point group symmetry and with bulky ligands, there was an nearly linear relationship between stability and delocalization index involving the ring carbon atoms (Cp) and the titanium. However, the titanocene stability is not only related to the interaction between Ti and C atoms of Cp ring, but secondary interactions also play important role on the stability of voluminous titanocenes. The third chapter deals with the chemical bond in coordination compounds by means of QTAIM. The quantum theory of atoms in molecules so far classifies bonds and chemical interactions in two categories: closed shell interaction (ionic bond, hydrogen bond, van der Waals interaction, etc) and shared interaction (covalent bond). Based on topological parameters such as electron density, Laplacian of electron density, delocalization index, among others, was classified the chemical bond in coordination compounds as an intermediate between closed shell and shared interactions

Clinical and microbiological studies of children and adolescents receiving orthodontic treatment

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Molibdênio via semente e nitrogênio em cobertura no feijoeiro irrigado em solo de cerrado

O nitrogênio é o nutriente mais exigido pelo feijoeiro e seu metabolismo pode ser seriamente prejudicado pela deficiência de molibdênio. Conduziu-se este trabalho, com o objetivo de avaliar o efeito da aplicação de molibdênio via semente e nitrogênio em cobertura nas características agronômicas e produtividade do feijoeiro 'BRS Pontal' irrigado, cultivado em Neossolo Quartzarênico, no município de Cassilândia, MS. O delineamento experimental utilizado foi o de blocos casualizados, no esquema fatorial 4x2, com quatro repetições. Os tratamentos foram constituídos pela aplicação ou não de Mo (80 g ha-1) via semente e quatro doses de N (0, 30, 60 e 120 kg ha-1), em cobertura aos 16 dias, após a emergência, na forma de uréia. A aplicação de Mo via semente aumentou o índice relativo de clorofila, o número de vagens por planta, a massa e a produtividade de grãos no feijoeiro, principalmente com o uso de altas doses de N em cobertura. O índice relativo de clorofila, o número de vagens por planta, a massa e a produtividade de grãos do feijoeiro foi aumentada linearmente pela aplicação de até 120 kg ha-1 de N em cobertura. O fornecimento de Mo via tratamento de semente aumentou a eficiência de utilização do N pelo feijoeiro.

Active planar waveguides based on sol-gel Er3+-doped SiO2-ZrO2 for photonic applications: Morphological, structural and optical properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Chemometric analysis of Hymenoptera toxins and defensins: A model for predicting the biological activity of novel peptides from venoms and hemolymph

When searching for prospective novel peptides, it is difficult to determine the biological activity of a peptide based only on its sequence. The trial and error approach is generally laborious, expensive and time consuming due to the large number of different experimental setups required to cover a reasonable number of biological assays. To simulate a virtual model for Hymenoptera insects, 166 peptides were selected from the venoms and hemolymphs of wasps, bees and ants and applied to a mathematical model of multivariate analysis, with nine different chemometric components: GRAVY, aliphaticity index, number of disulfide bonds, total residues, net charge, pI value, Boman index, percentage of alpha helix, and flexibility prediction. Principal component analysis (PCA) with non-linear iterative projections by alternating least-squares (NIPALS) algorithm was performed, without including any information about the biological activity of the peptides. This analysis permitted the grouping of peptides in a way that strongly correlated to the biological function of the peptides. Six different groupings were observed, which seemed to correspond to the following groups: chemotactic peptides, mastoparans, tachykinins, kinins, antibiotic peptides, and a group of long peptides with one or two disulfide bonds and with biological activities that are not yet clearly defined. The partial overlap between the mastoparans group and the chemotactic peptides, tachykinins, kinins and antibiotic peptides in the PCA score plot may be used to explain the frequent reports in the literature about the multifunctionality of some of these peptides. The mathematical model used in the present investigation can be used to predict the biological activities of novel peptides in this system, and it may also be easily applied to other biological systems. © 2011 Elsevier Inc.

Fontes potássicas na produção do pimenteiro em substrato fertirrigado

Pós-graduação em Agronomia (Horticultura) - FCA

Nutritional status and immune response in murine experimental Jorge Lobo's disease

There are no studies investigating the role of nutritional status and immunity associated with Jorge Lobo's disease. The objective of this study was to evaluate the effects of protein-calorie malnutrition on the immune response of BALB/c mice inoculated with Lacazia loboi. In this study,the animals were divided into four groups: G1: inoculated with restricted diet, G2: not inoculated with restricted diet, G3: inoculated with regular diet, G4: not inoculated with regular diet. The animals of groups G1 and G2 were submitted to malnutrition for 20 days and once installed the animals were inoculated intradermally into the footpad. After 4 months, they were euthanised for the isolation of peritoneal lavage cells and removal of the footpad. The production of IL-2, IL-4, IL-10, IL-12, IFN-γ, TNF-α, H2 O2 and nitric oxide (NO) was evaluated in the peritoneal lavage cells. The footpad was evaluated regarding the size of macroscopic lesions, number of fungi and viability index. The results showed that the infection did not exert great influence on the body weight of the mice and previous malnutrition was an unfavourable factor for viability index, number of fungi, macroscopic lesion size in the footpad and production of H2 O2 , NO, IL-12, IL-10 and IFN-γ, suggesting that malnutrition significantly altered fungal activity and peritoneal cells. The results suggest considerable interaction between nutrition and immunity in Jorge Lobo's disease.

Relationship between connectivity and academic productivity

A relevant factor in the growth of academic productivity in the second half of 20th century is the implementation of the internet, particularly in developing countries. One of the first networks in Brazil is the Academic Network at Sao Paulo (ANSP), a regional network implemented in the state of Sao Paulo, which contains the largest concentration of researchers in the country. This study presents a unique metric for analyzing the impact of ANSP in academic productivity in the state of Sao Paulo. We correlate academic production and available bandwidth using Fisher ideal price index with suitable variables to evaluate the impact of the internet on research centers and universities. We find that the members of ANSP show a steady growth in academic productivity compared with other institutions outside of the ANSP network. These results suggest that policies which increase available bandwidth can positively affect academic productivity.

Charakterisierung atherosklerotischer Plaques am Beispiel der A. carotis mittels Histologie, CT und semiautomatischer Farbcodierung

Auf der Suche nach dem „vulnerablen Plaque“, der ein besonders hohes Risiko für Schlaganfall und Herzinfarkt besitzt, findet momentan ein Paradigmenwechsel statt. Anstelle des klassischen Stenosegrades gewinnt die Darstellung der Plaquemorphologie zunehmend an Bedeutung. Fragestellung: Ziel dieser Arbeit ist es, die Fähigkeiten eines modernen 16-Kanal-CT hinsichtlich der Auflösung des Plaqueinneren bei Atherosklerose der Karotiden zu untersuchen und den Halo-Effekt in vivo zu erforschen. Methoden: Für die Studie wurden von 28 Patienten mit bekannter, symptomatischer Karotisstenose vor der gefäßchirurgischen Intervention CT-Bilder angefertigt, die nachfolgend mit der Histologie der Gefäßpräparate korreliert wurden. Auf diese Weise konnten die mikroskopisch identifizierten Lipidkerne im CT-Bild eingezeichnet und hinsichtlich ihrer Fläche und Dichtewerte evaluiert werden. In einem weiteren Schritt führten 2 Radiologen in Unkenntnis der histologischen Ergebnisse unabhängig voneinander eine Befundung durch und markierten mutmaßliche Lipidkerne. Zudem wurden sowohl in der verblindeten als auch in der histologiekontrollierten Auswertung die Plaquetypen anhand der AHA-Klassifikation bestimmt. Ein dritter Befundungsdurchgang geschah unter Zuhilfenahme einer von uns entwickelten Software, die CT-Bilder farbkodiert um die Detektion der Lipidkerne zu verbessern. Anhand der Farbkodierung wurde zudem ein Indexwert errechnet, der eine objektive Zuordnung zur AHA-Klassifikation ermöglichen sollte. Von 6 Patienten wurde zusätzlich noch eine native CT-Aufnahme angefertigt, die durch MPR exakt an die Kontrastmittelserie angeglichen wurde. Auf diese Weise konnte der Halo-Effekt, der die Plaqueanteile im lumennahen Bereich überstrahlt, quantifiziert und charakterisiert werden. Ergebnisse: Während die Einstufung in die AHA-Klassifikation sowohl durch den Befunder als auch durch den Softwarealgorithmus eine hohe Korrelation mit der Histologie aufweist (Typ IV/Va: 89 %, Typ Vb: 70 %, Typ Vc: 89 %, Typ VI: 55 %), ist die Detektion der Lipidkerne in beiden Fällen nicht ausreichend gut und die Befunderabhängigkeit zu groß (Cohens Kappa: 18 %). Eine Objektivierung der AHA-Klassifikation der Plaques durch Indexberechnung nach Farbkodierung scheint möglich, wenn auch dem Befunder nicht überlegen. Die fibröse Kappe kann nicht abgegrenzt werden, da Überstrahlungseffekte des Kontrastmittels dessen HU-Werte verfälschen. Dieser Halo-Effekt zeigte sich im Median 1,1 mm breit mit einer Standardabweichung von 0,38 mm. Eine Abhängigkeit von der Kontrastmitteldichte im Gefäßlumen konnte dabei nicht nachgewiesen werden. Der Halo-Effekt fiel im Median um -106 HU/mm ab, bei einer Standardabweichung von 33 HU/mm. Schlussfolgerung: Die CT-Technologie zeigt sich, was die Darstellung von einzelnen Plaquekomponenten angeht, den bekannten Fähigkeiten der MRT noch unterlegen, insbesondere in Bezug auf die fibröse Kappe. Ihre Fähigkeiten liegen bisher eher in der Einstufung von Plaques in eine grobe Klassifikation, angelehnt an die der AHA. Die klinische Relevanz dessen jedoch gilt es in Zukunft in größeren Studien weiter zu untersuchen. Auch lässt die Weiterentwicklung der Computertomographie auf eine zukünftig höhere Auflösung der Plaquemorphologie hoffen.

Interlaboratory variability of MIB1 staining in well-differentiated pancreatic neuroendocrine tumors

Neuroendocrine tumors (NET) are routinely graded and staged to judge prognosis. Proliferation index using MIB1 staining has been introduced to assess grading. There are vivid discussions on cutoff definitions, automated counting, and interobserver variability. However, no data exist regarding interlaboratory reproducibility for low proliferation indices which are of importance to discriminate between G1 and G2 NET. We performed MIB1 staining in three different university hospital-based pathology laboratories on a tissue micro array (TMA) of a well-characterized patient cohort, containing pancreatic NET of 61 patients. To calculate the proliferation index, number of positive tumor nuclei was divided by the total number of tumor nuclei. Labeling index was compared to mitotic counts in whole tissue sections and to clinical outcome. Linear regression analysis, intraclass comparison, and log-rank analysis were performed. Intraclass correlation showed moderate-to-fair agreement. Especially low proliferating tumors were affected by interlaboratory differences. Log-rank analysis was performed for each lab and resulted in three different cutoffs (5.0, 3.0, and 0.5 %). Every calculated cutoff stratified the patient cohort to a significant extent for the underlying stain (p < 0.001, <0.001, and <0.001) but showed no or lesser significance when applied to the other stains. Significant and relevant interlab differences for MIB1 exist. Since the MIB1 proliferation index influences grading, local cutoffs or external standardization should urgently be introduced to achieve reliability and reproducibility.

Cross-sectional study examining the role of acculturation in self-reported hypertension among Mexican Americans in Harris County, Texas

The objective of this secondary analysis was to examine the role of acculturation and self-reported hypertension in a Mexican-American cohort from Harris County, Texas. Specifically, we examined the acculturation measures of language-based Bidimensional Acculturation Scale (BAS), nativity, and length of United States (U.S) residency. Of 6,229 participants aged 40 and older, 38.0% self-reported hypertension at baseline. ^ Multiple logistic regression was used to estimate the prevalence odds ratios (pOR) for the association of each acculturation measure and hypertension while controlling for confounding. When adjusted for age, gender, body mass index, number of comorbidities, and family history of hypertension, U.S.-born participants were 1.37 times more likely to report having hypertension compared to Mexico-born participants (95% CI: 1.21, 1.55). Similarly, immigrants residing in the U.S. for more than 20 years had an adjusted pOR of 1.40 (95% CI: 1.16, 1.70) as compared to immigrants living in the U.S. for less than 10 years. ^ In conclusion, individuals who were born in the U.S. or emigrated to the U.S. over 20 years ago were more likely to report having hypertension compared to individuals born in Mexico or compared to those who emigrated more recently to the U.S. This study will contribute to the literature in demonstrating the need for more initiatives in prevention of cardiovascular disease, specifically hypertension, in the acculturating Mexican American population.^

Standardized rainfall indices for the West and Central Sahel, and the Guinea Coast

For years, various indices of seasonal West African precipitation have served as useful predictors of the overall tropical cyclone activity in the Atlantic Ocean. Since the mid-1990s, the correlation unexpectedly deteriorated. In the present study, statistical techniques are developed to describe the nonstationary nature of the correlations between annual measures of Atlantic tropical cyclone activity and three selected West African precipitation indices (namely, western Sahelian precipitation in June-September, central Sahelian precipitation in June-September, and Guinean coastal precipitation in the preceding year's August-November period). The correlations between these parameters are found to vary over the period from 1921 to 2007 on a range of time scales. Additionally, considerable year-to-year variability in the strength of these correlations is documented by selecting subsamples of years with respect to various meteorological factors. Broadly, in years when the environment in the main development region is generally favorable for enhanced tropical cyclogenesis (e.g., when sea surface temperatures are high, when there is relatively little wind shear through the depth of the troposphere, or when the relative vorticity in the midtroposphere is anomalously high), the correlations between indices of West African monsoon precipitation and Atlantic tropical cyclone activity are considerably weaker than in years when the overall conditions in the region are less conducive. Other more remote climate parameters, such as the phase of the Southern Oscillation, are less effective at modulating the nature of these interactions.