Fracionamento bioguiado para selação de substâncias antioxidante, antimalárica e antibiótica potenciais nas espécies Kielmeyera variabilis (Clusiaceae) e Brosimum Glaziovii (Moraceae)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Síntese, caracterização e estudo da atividade antitumoral de complexos de paládio(II) com ligantes sulfurados e trifenilfosfina

Pós-graduação em Química - IQ

Effect of gamma irradiation on the nutritional quality of Agaricus bisporus strains cultivated in different composts

The effect of irradiation doses (0, 125, 250 and 500 Gy) on the nutritional quality of A. bisporus mushrooms (strains ABI-07/06, ABI-05/03 and PB-1) cultivated in composts based on oat straw (Avena sativa) and brachiaria (Brachiaria sp.) was evaluated. The experimental design was 4 x 3 x 2 factorial scheme (irradiation doses x strains x composts), with 24 treatments, consisting of two repetitions each, totaling 48 experimental units (samples of mushrooms). The samples were irradiated in Cobalt-60 irradiator, model Gammacell 220 kGy, with dose rate of 0.740 kGy h(-1), according to the treatments proposed. Subsequently, the control (unirradiated) and the other treatments were maintained at 4 +/- 1 degrees C and 90% RH in a climatic chamber for carrying out the chemical analysis of the mushrooms on the 1st and 14th day of storage. It was found that all A. bisporus strains evaluated were food with excellent nutritional value, because they presented high protein and fiber contents and low ethereal extract content; the chemical characterization of the mushrooms was influenced by the compost type in which they were cultivated; gamma irradiation influenced the chemical composition of mushrooms.

Dihydrocinnamic acid derivatives from Hortia species and their chemotaxonomic value in the Rutaceae

Phytochemical studies of Hortia brasiliana and Hortia oreadica (Rutaceae) have led to the identification of three novel dihydrocinnamic acids: 5-methoxy-2,2-dimethyl-2H-1-benzopyran-8-propanoic acid, 5,6-dimethoxy-2,2-dimethyl-2H-1-benzopyran-8-propanoic acid and erythro-2-hydroxy-4-methoxy-3-(1,2,3-trihydroxy-3-methylbutyl) benzenepropanoic acid from H. brasiliana and the second compound and six known dihydrocinnamic acids from H. oreadica. Engler included Hortia as the single Neotropical genus in the Toddalioideae subtribe Toddaliinae. However, the range of dihydrocinnamic acid derivatives found in H. brasiliana and H. oreadica show that they contain similar compounds to other species of Hortia and clearly point to their phytochemical affinities with other Rutoideae species. (C) 2012 Elsevier Ltd. All rights reserved.

Multivariate analyses of UV-Vis absorption spectral data from cachaca wood extracts: a model to classify aged Brazilian cachacas according to the wood species used

Multivariate analyses of UV-Vis spectral data from cachaca wood extracts provide a simple and robust model to classify aged Brazilian cachacas according to the wood species used in the maturation barrels. The model is based on inspection of 93 extracts of oak and different Brazilian wood species by a non-aged cachaca used as an extraction solvent. Application of PCA (Principal Components Analysis) and HCA (Hierarchical Cluster Analysis) leads to identification of 6 clusters of cachaca wood extracts (amburana, amendoim, balsamo, castanheira, jatoba, and oak). LDA (Linear Discriminant Analysis) affords classification of 10 different wood species used in the cachaca extracts (amburana, amendoim, balsamo, cabreuva-parda, canela-sassafras, castanheira, jatoba, jequitiba-rosa, louro-canela, and oak) with an accuracy ranging from 80% (amendoim and castanheira) to 100% (balsamo and jequitiba-rosa). The methodology provides a low-cost alternative to methods based on liquid chromatography and mass spectrometry to classify cachacas aged in barrels that are composed of different wood species.

Design of a Dinuclear Nickel(II) Bioinspired Hydrolase to Bind Covalently to Silica Surfaces: Synthesis, Magnetism, and Reactivity Studies

Presented herein is the design of a dinuclear Ni-II synthetic hydrolase [Ni-2(HBPPAMFF)(mu-OAc)(2)(H2O)]-BPh4 (1) (H(2)BPPAMFF = 2-[(N-benzyl-N-2-pyridylmethylamine)]-4-methyl-6-[N-(2-pyridylmethyl)aminomethyl)])-4- methyl-6-formylphenol) to be covalently attached to silica surfaces, while maintaining its catalytic activity. An aldehyde-containing ligand (H(2)BPPAMFF) provides a reactive functional group that can serve as a cross-linking group to bind the complex to an organoalkoxysilane and later to the silica surfaces or directly to amino-modified surfaces. The dinuclear Ni-II complex covalently attached to the silica surfaces was fully characterized by different techniques. The catalytic turnover number (k(cat)) of the immobilized (NiNiII)-Ni-II catalyst in the hydrolysis of 2,4-bis(dinitrophenyl)phosphate is comparable to the homogeneous reaction; however, the catalyst interaction with the support enhanced the substrate to complex association constant, and consequently, the catalytic efficiency (E - k(cat)/K-M) and the supported catalyst can be reused for subsequent diester hydrolysis reactions.

Rarely selected distractors in high stakes medical multiple-choice examinations and their recognition by item authors: A simulation and survey

Background Many medical exams use 5 options for multiple choice questions (MCQs), although the literature suggests that 3 options are optimal. Previous studies on this topic have often been based on non-medical examinations, so we sought to analyse rarely selected, 'non-functional' distractors (NF-D) in high stakes medical examinations, and their detection by item authors as well as psychometric changes resulting from a reduction in the number of options. Methods Based on Swiss Federal MCQ examinations from 2005-2007, the frequency of NF-D (selected by <1% or <5% of the candidates) was calculated. Distractors that were chosen the least or second least were identified and candidates who chose them were allocated to the remaining options using two extreme assumptions about their hypothetical behaviour: In case rarely selected distractors were eliminated, candidates could randomly choose another option - or purposively choose the correct answer, from which they had originally been distracted. In a second step, 37 experts were asked to mark the least plausible options. The consequences of a reduction from 4 to 3 or 2 distractors - based on item statistics or on the experts' ratings - with respect to difficulty, discrimination and reliability were modelled. Results About 70% of the 5-option-items had at least 1 NF-D selected by <1% of the candidates (97% for NF-Ds selected by <5%). Only a reduction to 2 distractors and assuming that candidates would switch to the correct answer in the absence of a 'non-functional' distractor led to relevant differences in reliability and difficulty (and to a lesser degree discrimination). The experts' ratings resulted in slightly greater changes compared to the statistical approach. Conclusions Based on item statistics and/or an expert panel's recommendation, the choice of a varying number of 3-4 (or partly 2) plausible distractors could be performed without marked deteriorations in psychometric characteristics.

Comparison of Student Versus Employee Test Populations for Warning Sign Research Based on Severity Ratings for Signal Words

Most studies of warning signs involve undergraduate students as subjects. This paper reports a direct comparison of findings from an undergraduate population and an employed population. The 48 employed subjects from this study were compared with 59 undergraduate subjects from a companion study. Subjects from both populations were shown the same signs and asked to rate the severity level connoted by each sign. The signs differed only in signal word. Results for each population indicated that signal word had a highly significant effect on severity ratings. When the two populations were compared for ratings of each signal word, the only significant difference was for Caution. Median ratings of each population were the same: Deadly (4), Danger (3), Warning (2), Caution (1), and Notice (0).

Octreotide treatment of patients with hepatocellular carcinoma--a retrospective single centre controlled study

BACKGROUND: Studies of treatment with octreotide of patients with hepatocellular carcinoma (HCC) gave conflicting results. We analyzed retrospectively the survival of our patients treated with octreotide monotherapy and compared it to stage-matched patients who received either TACE, multimodal therapy or palliative care. METHODS: 95 patients seen at the department of Gastroenterology and Hepatology, Medical University of Vienna with HCC in BCLC stage A or B, who received either TACE, multimodal therapy, long-acting octreotide or palliative care were reviewed for this retrospective study. RESULTS: Survival rates of patients with BCLC stage B and any "active" treatment (long-acting octreotide, TACE or multimodal therapy) were significantly higher (22.4, 22.0, 35.5 months) compared to patients who received palliative care only (2.9 months). Survival rates of patients with BCLC stage A and "active" treatment (31.4, 37.3, 40.2 months) compared to patients who received only palliative care (15.1 months) did not show statistically significant differences. Octreotide monotherapy showed a similar outcome compared to patients who received TACE or multimodal therapy. CONCLUSION: Survival under octreotide treatment was not different compared to TACE or multimodal therapy and might be a therapeutic option for patients with HCC.

Thorium and radiocarbon measurements on sediment cores from the Northseast Atlantic

Radiocarbon and 230Thexcess data from six NE Atlantic box cores are considered. The cores form a transect from the Porcupine Abyssal Plain over the East Thulean Rise to the southern end of Feni Drift. The chronology for the cores is established from bulk sediment carbonate radiocarbon data and reveals that sections exhibiting constant accumulation rates can be identified in all the cores, with rates of 3.0-3.5 cm/kyr on the plain through the Holocene and late Holocene rates of 4.3-6.6 cm/kyr elsewhere. Five out of the six cores show accumulations of more 230Thexcess than is produced in the overlying water column, with the greatest inventories (up to 225% of production) in the cores from the rise and drift. A size fraction comparison between two cores from the plain and rise reveals that the higher overall accumulation rates and 230Thexcess inventories in the off-plain cores are due to an increased fine (<5 µm) component fraction, whereas the flux of coarser material is similar to that received on the plain. This suggests that the higher fluxes of materials observed are physically (rather than biogeochemically) driven and also that drift formation has been continuously active in the late Holocene. Sections of all the cores where regular accumulation is defined by the radiocarbon data are modeled first by a linear radiocarbon age/depth model and second by a constant rain (230Thexcess)0 model prorated for the observed core inventories. These modeling approaches yield historical mass accumulation rate estimates which are generally in reasonable agreement (±30%), but the differences observed appear to be well organized in time rather than random.

Major element and cadmium contents in phosphorites from Pacific seamounts

Cadmium contents in studied rocks from Pacific seamounts usually lower than both in biogenic-diagenetic shelf phosphorites and in pelagic sedimentatary-diagenetic Fe-Mn nodules. In general, the behavior of Cd in phosphorites, phosphatized rocks and iron-manganese-phosphate crusts from the seamounts shows that phosphorus, iron, and manganese are apparently of normal sedimentary origin.

Dinoflagellate cysts and pollen distribution of marine surface sediments off West Africa

An organic-walled dinoflagellate cyst analysis was carried out on 53 surface sediment samples from West Africa (17-6°N) to obtain insight in the relationship between their spatial distribution and hydrological conditions in the upper water column as well as marine productivity in the study area. Multivariate analysis of the dinoflagellate cyst relative abundances and environmental parameters of the water column shows that sea-surface temperature, salinity, marine productivity and bottom water oxygen are the factors that relate significantly to the distribution patterns of individual species in the region. The composition of cyst assemblages and dinoflagellate cyst concentrations allows the identification of four hydrographic regimes; 1) the northern regime between 17 and 14°N characterized by high productivity associated with seasonal coastal upwelling, 2) the southern regime between 12 and 6°N associated with high-nutrient waters influenced by river discharge 3) the intermediate regime between 14 and 12°N influenced mainly by seasonal coastal upwelling additionally associated with fluvial input of terrestrial nutrients and 4) the offshore regime characterized by low chlorophyll-a concentrations in upper waters and high bottom water oxygen concentrations. Our data show that cysts of Polykrikos kofoidii, Selenopemphix quanta, Dubridinium spp., Echinidinium species, cysts of Protoperidinium monospinum and Spiniferites pachydermus are the best proxies to reconstruct the boundary between the NE trade winds and the monsoon winds in the subtropical eastern Atlantic Ocean. The association of Bitectatodinium spongium, Lejeunecysta oliva, Quinquecuspis concreta, Selenopemphix nephroides, Trinovantedinium applanatum can be used to reconstruct past river outflow variations within this region.

Distribution of benthic foraminifera in surface sediments on the continental margin off North-West Africa

The benthic foraminiferal populations along three traverses across the Northwest African continental margin were analyzed on the base of ca. 60 surface sediment samples. Depth ranges of 213 species were established and the main trends of vertical distribution are compared with those known from adjacent regions. Main faunal breaks occure at 100/200 m and 1000/1500 m depth of water. Some species show latitudinal distribution boundaries and the same applies to population density (standing stock), reflecting the regional distribution of nutrients supply by river discharge and upwelling processes. - High proportions of Bolivina test at the lower slope indicate extended downslope transport.