Integrated X-ray crystallography, optical and computational methods in studies of structure and luminescence of new synthesized complexes of lanthanides with ligands derived from 2,6-diformylpyridine

The reaction of 2,6-diformylpyridine-bis(benzoylhydrazone) [dfpbbh] and 2,6-diformylpyridine-bis(4-phenylsemicarbazone) [dfpbpsc] with lanthanides salts yielded the new chelates complexes [Eu(dfpbpsc-H +) 2]NO 3 (1), [Dy(fbhmp) 2][Dy(dfpbbh-2H +) 2]·2EtOH·2H 2O (fbhmp = 2-formylbenzoylhydrazone-6-methoxide-pyridine; Ph = phenyl; Py = pyridine; Et = ethyl) and [Er 2(dfpbbh-2H +) 2(μ-NO 3)(H 2O) 2(OH)]·H 2O. X-ray diffraction analysis was employed for the structural characterization of the three chelate complexes. In the case of complex 1, optical, synthetic and computational methods were also exploited for ground state structure determinations and triplet energy level of the ligand and HOMO-LUMO calculations, as well as for a detailed study of its luminescence properties. © 2010 Elsevier Ltd. All rights reserved.

Use of mathematical and numerical methods in the Latin American Demographic Centre CELADE. Santiago, Chile

Includes bibliography

Improving methods in gap ecology: Revisiting size and shape distributions using a model selection approach

Questions: We assess gap size and shape distributions, two important descriptors of the forest disturbance regime, by asking: which statistical model best describes gap size distribution; can simple geometric forms adequately describe gap shape; does gap size or shape vary with forest type, gap age or the method used for gap delimitation; and how similar are the studied forests and other tropical and temperate forests? Location: Southeastern Atlantic Forest, Brazil. Methods: Analysing over 150 gaps in two distinct forest types (seasonal and rain forests), a model selection framework was used to select appropriate probability distributions and functions to describe gap size and gap shape. The first was described using univariate probability distributions, whereas the latter was assessed based on the gap area-perimeter relationship. Comparisons of gap size and shape between sites, as well as size and age classes were then made based on the likelihood of models having different assumptions for the values of their parameters. Results: The log-normal distribution was the best descriptor of gap size distribution, independently of the forest type or gap delimitation method. Because gaps became more irregular as they increased in size, all geometric forms (triangle, rectangle and ellipse) were poor descriptors of gap shape. Only when small and large gaps (> 100 or 400m2 depending on the delimitation method) were treated separately did the rectangle and isosceles triangle become accurate predictors of gap shape. Ellipsoidal shapes were poor descriptors. At both sites, gaps were at least 50% longer than they were wide, a finding with important implications for gap microclimate (e.g. light entrance regime) and, consequently, for gap regeneration. Conclusions: In addition to more appropriate descriptions of gap size and shape, the model selection framework used here efficiently provided a means by which to compare the patterns of two different types of forest. With this framework we were able to recommend the log-normal parameters μ and σ for future comparisons of gap size distribution, and to propose possible mechanisms related to random rates of gap expansion and closure. We also showed that gap shape varied highly and that no single geometric form was able to predict the shape of all gaps, the ellipse in particular should no longer be used as a standard gap shape. © 2012 International Association for Vegetation Science.

Comparison of methods in oral health education from the perspective of adolescents.

To investigate whether teenagers' knowledge about oral health is influenced by educational methods and to verify the most effective method according to their perception. The study was performed in Araçatuba, São Paulo State, Brazil, with 127 teenagers from a vocational school. It was realised in 3 steps: 1. An evaluation of knowledge about oral health using a self-applied questionnaire. 2. An application of educational methods, where the students were divided into two groups (A and B). Group A participated in three educational activities that involved lectures, individual demonstration, and participatory activity. Group B was divided into three subgroups (B1, B2, B3) and each of them participated in only one of the methods. 3. The acquired knowledge was evaluated. Group A created a focus group to give their opinion about strategies. With regards to knowledge after the application of the different methods in all groups, there was a statistically significant difference concerning periodontitis, gingivitis and herpes. In group A, after the three activities, and in group B2 after the individual demonstration, an association was found between 'healthy teeth' and 'general health' (P = 0.004 and P = 0.022, respectively). After the individual demonstration, an association was shown between variables of acquired knowledge about 'harmful diet' and 'dental caries' (P = 0.002) as well as 'good diet' and 'prevention of oral diseases' (P = 0.032). The favourite method was individual demonstration, due to the contact with educational materials, followed by participatory activity because it encouraged learning in a more dynamic way. Educational methods influenced knowledge about oral health, with individual demonstration proving to be the most effective method for acquiring knowledge. In the adolescents' view, the participatory activity was the preferred method.

MHV tree amplitudes in super-Yang-Mills and in superstring theory

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Geostatistics and remote sensing methods in the classification of images of areas cultivated with citrus

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A simpler prescription for MHV graviton tree amplitudes in superstring theory

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

Validation of mechanical, electrical and thermal nociceptive stimulation methods in horses

To validate a model for investigating the effects of analgesic drugs on mechanical, thermal and electrical stimulation testing. To investigate repeatability, sensitivity and specificity of nociceptive tests. Randomised experiment with 2 observers in 2 phases. Mechanical (M), thermal (TL) and electrical (E) stimuli were applied to the dorsal metacarpus (M-left and TL-right) and coronary band of the left thoracic limb (E) and a thoracic thermal stimulus (TT) was applied caudal to the withers in 8 horses (405 ± 43 kg). Stimuli intensities were increased until a clear avoidance response was detected without exceeding 20 N (M), 60°C (TL and TT) and 15 V (E). For each set of tests, 3 real stimuli and one sham stimulus were applied (32 per animal) using a blinded, randomised, crossover design repeated after 6 months. A distribution frequency and, for each stimulus, Chi-square and McNemar tests compared both the proportion of positive responses detected by 2 observers and the 2 study phases. The κ coefficients estimated interobserver agreement in determining endpoints. Sensitivity (384 tests) and specificity (128 tests) were evaluated for each nociceptive stimulus to assess the evaluators' accuracy in detecting real and sham stimuli. Nociceptive thresholds were 3.1 ± 2 N (M), 8.1 ± 3.8 V (E), 51.4 ± 5.5°C (TL) and 55.2 ± 5.3°C (TT). The level of agreement after all tests, M, E, TL and TT, was 90, 100, 84, 98 and 75%, respectively. Sensitivity was 89, 100, 89, 98 and 70% and specificity 92, 97, 88, 91 and 94%, respectively. The high interobserver agreement, sensitivity and specificity suggest that M, E and TL tests are valid for pain studies in horses and are suitable tools for investigating antinociceptive effects of analgesics in horses.

O uso de elementos da criptografia como estímulo matemático na sala de aula

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

O uso de elementos da criptografia como estímulo matemático na sala de aula

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

In vivo accuracy of conventional and digital radiographic methods in confirming root canal working length determination by Root ZX

Objectives: To compare, in vivo, the accuracy of conventional and digital radiographic methods in determining root canal working length. Material and Methods: Twenty-five maxillary incisor or canine teeth from 22 patients were used in this study. Considering the preoperative radiographs as the baseline, a 25 K file was inserted into the root canal to the point where the Root ZX electronic apex locator indicated the APEX measurement in the screen. From this measurement, 1 mm was subtracted for positioning the file. The radiographic measurements were made using a digital sensor (Digora 1.51) or conventional type-E films, size 2, following the paralleling technique, to determine the distance of the file tip and the radiographic apex. Results: The Student "t" test indicated mean distances of 1.11 mm to conventional and 1.20 mm for the digital method and indicated a significant statistical difference (p<0.05). Conclusions: The conventional radiographic method was found to be superior to the digital one in determining the working length of the root canal.

Variance Reduction in Analytical Chemistry : New Numerical Methods in Chemometrics and Molecular Simulation

This thesis is based on five papers addressing variance reduction in different ways. The papers have in common that they all present new numerical methods. Paper I investigates quantitative structure-retention relationships from an image processing perspective, using an artificial neural network to preprocess three-dimensional structural descriptions of the studied steroid molecules. Paper II presents a new method for computing free energies. Free energy is the quantity that determines chemical equilibria and partition coefficients. The proposed method may be used for estimating, e.g., chromatographic retention without performing experiments. Two papers (III and IV) deal with correcting deviations from bilinearity by so-called peak alignment. Bilinearity is a theoretical assumption about the distribution of instrumental data that is often violated by measured data. Deviations from bilinearity lead to increased variance, both in the data and in inferences from the data, unless invariance to the deviations is built into the model, e.g., by the use of the method proposed in paper III and extended in paper IV. Paper V addresses a generic problem in classification; namely, how to measure the goodness of different data representations, so that the best classifier may be constructed. Variance reduction is one of the pillars on which analytical chemistry rests. This thesis considers two aspects on variance reduction: before and after experiments are performed. Before experimenting, theoretical predictions of experimental outcomes may be used to direct which experiments to perform, and how to perform them (papers I and II). After experiments are performed, the variance of inferences from the measured data are affected by the method of data analysis (papers III-V).

Heteronuclear recoupling methods in solid-state NMR

This thesis is focused on the development of heteronuclear correlation methods in solid-state NMR spectroscopy, where the spatial dependence of the dipolar coupling is exploited to obtain structural and dynamical information in solids. Quantitative results on dipolar coupling constants are extracted by means of spinning sideband analysis in the indirect dimension of the two-dimensional experiments. The principles of sideband analysis were established and are currently widely used in the group of Prof. Spiess for the special case of homonuclear 1H double-quantum spectroscopy. The generalization of these principles to the heteronuclear case is presented, with special emphasis on naturally abundant 13C-1H systems. For proton spectroscopy in the solid state, line-narrowing is of particular importance, and is here achieved by very-fast sample rotation at the magic angle (MAS), with frequencies up to 35 kHz. Therefore, the heteronuclear dipolar couplings are suppressed and have to be recoupled in order to achieve an efficient excitation of the observed multiple-quantum modes. Heteronuclear recoupling is most straightforwardly accomplished by performing the known REDOR experiment, where pi-pulses are applied every half rotor period. This experiment was modified by the insertion of an additional spectroscopic dimension, such that heteronuclear multiple-quantum experiments can be carried out, which, as shown experimentally and theoretically, closely resemble homonuclear double-quantum experiments. Variants are presented which are well-suited for the recording of high-resolution 13C-1H shift correlation and spinning-sideband spectra, by means of which spatial proximities and quantitative dipolar coupling constants, respectively, of heteronuclear spin pairs can be determined. Spectral editing of 13C spectra is shown to be feasible with these techniques. Moreover, order phenomena and dynamics in columnar mesophases with 13C in natural abundance were investigated. Two further modifications of the REDOR concept allow the correlation of 13C with quadrupolar nuclei, such as 2H. The spectroscopic handling of these nuclei is challenging in that they cover large frequency ranges, and with the new experiments it is shown how the excitation problem can be tackled or circumvented altogether, respectively. As an example, one of the techniques is used for the identification of a yet unknown motional process of the H-bonded protons in the crystalline parts of poly(vinyl alcohol).