Comparative study on the far-field spectra and near-field amplitudes for silver and gold nanocubes irradiated at 514, 633 and 785 nm as a function of the edge length

We describe a systematic investigation by the discrete dipole approximation on the optical properties of silver (Ag) and gold (Au) nanocubes as a function of the edge length in the 20-100 nm range. Our results showed that, as the nanocube size increased, the plasmon resonance modes shifted to higher wavelengths, the contribution from scattering to the extinction increased, and the quadrupole modes became more intense in the spectra. The electric field amplitudes at the surface of the nanocubes were calculated considering 514, 633 and 785 nm as the excitation wavelengths. While Ag nanocubes displayed the highest electric field amplitudes (vertical bar E vertical bar(max)) when excited at 514 nm, the Au nanocubes displayed higher vertical bar E vertical bar(max) values than Ag, for all sizes investigated, when the excitation wavelength was either 633 or 785 nm. The variations in vertical bar E vertical bar(max) as a function of size for both Ag and Au nanocubes could be explained based on the relative position of the surface plasmon resonance peak relative to the wavelength of the incoming electromagnetic wave. Our results show that not only size and composition, but also the excitation wavelength, can play an important role over the maximum near-field amplitudes values generated at the surface of the nanocubes.

ESTIMATING REACTION CONSTANTS BY AB INITIO MOLECULAR MODELING: A STUDY ON THE OXIDATION OF PHENOL TO CATECHOL AND HYDROQUINONE IN ADVANCED OXIDATION PROCESSES

Molecular modeling is growing as a research tool in Chemical Engineering studies, as can be seen by a simple research on the latest publications in the field. Molecular investigations retrieve information on properties often accessible only by expensive and time-consuming experimental techniques, such as those involved in the study of radical-based chain reactions. In this work, different quantum chemical techniques were used to study phenol oxidation by hydroxyl radicals in Advanced Oxidation Processes used for wastewater treatment. The results obtained by applying a DFT-based model showed good agreement with experimental values available, as well as qualitative insights into the mechanism of the overall reaction chain. Solvation models were also tried, but were found to be limited for this reaction system within the considered theoretical level without further parameterization.

Burden of maternal bipolar disorder on at-risk offspring: A controlled study on family planning and maternal care

Introduction: Bipolar disorder (BD) is a highly incapacitating disease typically associated with high rates of familial dysfunction. Despite recent literature suggesting that maternal care is an important environmental factor in the development of behavioral disorders, it is unclear how much maternal care is dysfunctional in BD subjects. Objective: The objective of this study was to characterize maternal care in DSM-IV/SCID diagnosed BD type I subjects compared to healthy controls with (PD) and without (NPD) other psychiatric diagnoses. Materials and methods: Thirty-four BD mothers and 106 controls underwent an interview about family planning and maternal care, obstetrical complications, and mother-child interactions. K-SADS-PL questions about violence exposure were used to ascertain domestic violence and physical/sexual abuse. Results: BD mothers were less likely to have stable unions (45.5%; p < 0.01) or to live with the biological father of their children (33.3%; p < 0.01), but had higher educational level and higher rates of social security use/retirement. They also had fewer children and used less contraceptive methods than controls. Children of BD women had higher rates of neonatal anoxia, and reported more physical abuse (16.1%; p = 0.02) than offspring of NPD mothers. Due to BD mothers' symptoms, 33.3% of offspring suffered physical and/or psychological abuse. Limitations: Post hoc analysis, and the use of questions as a surrogate of symptoms as opposed to validated instruments. Conclusion: This is one of few reports confirming that maternal care given by BD women is dysfunctional. BD psychopathology can lead to poor maternal care and both should be considered important environmental risk factors in BD, suggesting that BD psychoeducation should include maternal care orientation. (C) 2012 Elsevier B.V. All rights reserved.

Experimental and Theoretical Study on the One- and Two-Photon Absorption Properties of Novel Organic Molecules Based on Phenylacetylene and Azoaromatic Moieties

This Article reports a combined experimental and theoretical analysis on the one and two-photon absorption properties of a novel class of organic molecules with a pi-conjugated backbone based on phenylacetylene (JCM874, FD43, and FD48) and azoaromatic (YB3p2S) moieties. Linear optical properties show that the phenylacetylene-based compounds exhibit strong molar absorptivity in the UV and high fluorescence quantum yield with lifetimes of approximately 2.0 ns, while the azoaromatic-compound has a strong absorption in the visible region with very low fluorescence quantum yield. The two-photon absorption was investigated employing nonlinear optical techniques and quantum chemical calculations based on the response functions formalism within the density functional theory framework. The experimental data revealed well-defined 2PA spectra with reasonable cross-section values in the visible and IR. Along the nonlinear spectra we observed two 2PA allowed bands, as well as the resonance enhancement effect due to the presence of one intermediate one-photon allowed state. Quantum chemical calculations revealed that the 2PA allowed bands correspond to transitions to states that are also one-photon allowed, indicating the relaxation of the electric-dipole selection rules. Moreover, using the theoretical results, we were able to interpret the experimental trends of the 2PA spectra. Finally, using a few-energy-level diagram, within the sum-over-essential states approach, we observed strong qualitative and quantitative correlation between experimental and theoretical results.

Spectroscopic Study on the Structural Differences of Thermally Induced Cross-Linking Segments in Emeraldine Salt and Base Forms of Polyaniline

This paper reports the spectroscopic study on the structural differences of thermally induced cross-linking segments in polyaniline in its emeraldine salt (PANI-ES) and base (PANI-EB) forms. Casting films of PANI-ES (ES-film) and PANI-EB (EB-film) were prepared and heated at 150 degrees C under atmospheric air for 30 min. Raman spectra excited at 632.8 nm of heated ES-film presented the characteristic bands of phenazine-like structures at 1638, 1392, and 575 cm(-1), whereas EB-film showed lower relative intensities for these bands. The lower content of phenazine-like segments in heated EB-film is related to residual polaronic segments from preparation procedures, as revealed by Raman. This statement was confirmed by a sequence of thermal and doping experiments in both films. Quantum-chemical calculations by density functional theory (DFT) and time-dependent density functional theory (TD-DFT) showed that the phenazine-like structure presents the intense Raman band at 1350 cm(-1) due to heterocycle breathing mode, and the non-phenazine-like structure (substituted hydrophenazine-type) presents higher energy for HOMO-LUMO transition, indicating the lack of conjugation in the heterocycle compared with the phenazine-like structure. According to experimental and theoretical data reported here, it is proposed that only thermally treated PANI-ES presents phenazine-like rings, whereas PANI-EB presents heterocyclic non-aromatic structures.

Experimental study on vortex-induced motions of a semi-submersible platform with four square columns, Part I: Effects of current incidence angle and hull appendages

An experimental study on Vortex-Induced Motion (VIM) of the semi-submersible platform concept with four square columns is presented. Model tests were carried out to check the influence of different headings and hull appendages (riser supports located at the pontoons; fairleads and the mooring stretches located vertically at the external column faces; and hard pipes located vertically at the internal column faces). The results comprise in-line, transverse and yaw motions, as well as combined motions in the XY plane, drag and lift forces and spectral analysis. The main results showed that VIM in the transverse direction occurred in a range of reduced velocity 4.0 up to 14.0 with amplitude peaks around reduced velocities around 7.0 and 8.0. The largest transverse amplitudes obtained were around 40% of the column width for 30 degrees and 45 degrees incidences. Another important result observed was a considerable yaw motion oscillation, in which a synchronization region could be identified as a resonance phenomenon. The largest yaw motions were verified for the 0 degrees incidence and the maxima amplitudes around 4.5 degrees. The hull appendages located at columns had the greatest influence on the VIM response of the semi-submersible. (C) 2012 Elsevier Ltd. All rights reserved.

Spray Congealing of Pharmaceuticals: Study on Production of Solid Dispersions Using Box-Behnken Design

This work aimed at evaluating the spray congealing method for the production of microparticles of carbamazepine combined with a polyoxylglyceride carrier. In addition, the influence of the spray congealing conditions on the improvement of drug solubility was investigated using a three-factor, three-level Box-Behnken design. The factors studied were the cooling air flow rate, atomizing pressure, and molten dispersion feed rate. Dependent variables were the yield, solubility, encapsulation efficiency, particle size, water activity, and flow properties. Statistical analysis showed that only the yield was affected by the factors studied. The characteristics of the microparticles were evaluated using X-ray powder diffraction, scanning electron microscopy, differential scanning calorimetry, and hot-stage microscopy. The results showed a spherical morphology and changes in the crystalline state of the drug. The microparticles were obtained with good yields and encapsulation efficiencies, which ranged from 50 to 80% and 99.5 to 112%, respectively. The average size of the microparticles ranged from 17.7 to 39.4 mu m, the water activities were always below 0.5, and flowability was good to moderate. Both the solubility and dissolution rate of carbamazepine from the spray congealed microparticles were remarkably improved. The carbamazepine solubility showed a threefold increase and dissolution profile showed a twofold increase after 60 min compared to the raw drug. The Box-Behnken fractional factorial design proved to be a powerful tool to identify the best conditions for the manufacture of solid dispersion microparticles by spray congealing.

A cross-sectional study on canine Leishmania (L.) infantum chagasi infection in Amazonian Brazil ratifies a higher prevalence of specific IgG-antibody response than delayed-type hypersensitivity in symptomatic and asymptomatic dogs

This was a cross-sectional study which analyzed the prevalence and the clinical and immunological spectrum of canine Leishmania (L.) infantum chagasi infection in a cohort of 320 mongrel dogs living in an endemic area of American visceral leishmaniasis in the Amazonian Brazil by using, mainly, the indirect fluorescence antibody test (IFAT-IgG) and the delayed-type hypersensitivity (DTH), and the parasite research by the popliteal lymph node aspiration. The IFAT and DTH reactivity recognized three different immune response profiles: (1) IFAT((+))/DTH(-) (107 dogs), (2) IFAT((-))/DTH(+) (18 dogs), and (3) IFAT((+))/DTH(+) (13 dogs), providing an overall prevalence of infection of 43 % (138/320). Thus, the specific prevalence of IFAT ((+)) /DTH ((-)) 33.4 % (107/320) was higher than those of IFAT ((-)) /DTH ((+)) 5.6 % (18/320) and IFAT ((+)) /DTH ((+)) 4.0 % (13/320). Moreover, the frequency of these profiles among 138 infected dogs showed that the IFAT ((+)) /DTH ((-)) rate of 77.5 % (107/138) was also higher than those of 13.0 % (18/138) of IFAT ((-)) /DTH ((+)) and 9.5 % (13/138) of IFAT ((+)) /DTH ((+)) rates. The frequency of asymptomatic dogs (76 %-105) was higher than those of symptomatic (16.6 %-23) and oligosymptomatic ones (7.4 %-10). A total of 16 (11.6 %) L. (L.) i. chagasi isolates were obtained from infected dogs, all from the IFAT ((+)) /DTH ((-)) profile: 41 % (9/22) from symptomatic, 33.3 % (3/9) from oligosymptomatic, and 5.2 % (4/76) from asymptomatic dogs. These findings strongly suggested that despite the higher frequency of asymptomatic dogs (76 %-105), the majority (72.4 %-76) was characterized by the IFAT ((+)) /DTH ((-)) profile with a doubtful immunogenetic resistance against infection.

Taxonomic study on the molluscs collected in Marion-Dufresne expedition (MD55) to SE Brazil: Xenophoridae, Cypraeoidea, mitriforms and Terebridae (Caenogastropoda)

The deep-water molluscs collected during the expedition MD55 off SE Brazil have been gradually studied in some previous papers. The present one is focused on samples belonging to caenogastropod taxa Xenophoridae Troschel, 1852, Cypraeoidea Rafinesque, 1815, mitriforms and Terebridae Morch, 1852. Regarding the Xenophoridae, Onustus aquitanus n. sp. is a new species, collected off the littoral of Espirito Santo and Rio de Janeiro, Brazil, 430-637 m depth (continental slope). The main characters of the species include the small size (c. 20 mm), the proportionally wide shell, the white colour, the short peripheral flange, the oblique riblets weakly developed and a brown multispiral protoconch. This appears to be the smallest living species of the family, resembling in this aspect fossil species. In respect to the Cypraeoidea, the following results were obtained: family Cypraeidae Rafinesque, 1815: Erosaria acicularis (Gmelin, 1791) and Luria cinerea (Gmelin, 1791) had the deepest record, respectively 607-620 m and 295-940 m, although the samples were all dead, eroded shells. Family Lamellariidae d'Orbigny, 1841: a total of three lots were collected, provisionally identified as Lamellaria spp. as the samples consist of only vestigial shells; possibly each lot represents a different species. Family Pediculariidae Gray, 1853: a sample of Pedicularia tibia Simone, 2005 was found, expanding the range c. 1000 km southwards, from Ceara to Espirito Santo. Family Ovulidae Fleming, 1822: Pseudosimnia lacrima n. sp., collected off Espirito Santo, 607-620 m depth, is described here and is mainly characterised by its strong biconic outline, small size (c. 7 mm), and a thick peripheral callus. Family Triviidae Troschel, 1863: Cleotrivia antillarum (Schilder, 1922) is recorded for the first time as deep as 620 m, and its distribution expanded from Rio Grande do Norte to Espirito Santo; Dolichupis akangus n. sp. with rounded outline and c. 15 transverse ribs; D. pingius n. sp. with the outer lip expanded posteriorly and c. 10 ribs. In respect to the mitriform neogastropods, the following species are emphasised: family Costellariidae MacDonald, 1860: Vexillum sp., 607-620 m depth; Turricostellaria amphissa n. sp., 295 m depth; T. jukyry n. sp.; T. apyrahi n. sp., both 790-1575 m depth; T. ovir n. sp., 1200 m depth; Nodicostellaria crassa (Simone, 1995), 240-600 m depth, with extension northwards of the range up to Espirito Santo; Austromitra decresca n. sp., 60-105 m depth. Family Mitridae Swainson, 1829: Subcancilla joapyra n. sp., 295 m depth; S. cf. straminea (Adams, 1853), 607-620 m depth. Family Volutomitridae Gray, 1854: Microvoluta corona n. sp., 1500-1575 m depth. Family Mitromorphidae Casey, 1904: Mitromorpha sama n. sp., 607-940 m depth; M. mirim n. sp., 60105 m depth. Regarding the conoidean Terebridae, this paper is a complement of a previous study. It deals with a new species Terebra assu Simone n. sp., from the Abrolhos Bank, 295 m depth, characterised by its narrow outline, yellowish colour, weak sculpture on the last whorls, and a proportionally broad, paucispiral protoconch. A second finding of Terebra alagoensis Lima, Tenorio & Barros, 2007 expands the geographic range from Alagoas to north Espirito Santo. A discussion on the systematics of the "complex Terebra doellojuradoi" in South American coast is also provided, highlighting the improbability of synonymy between T. leptapsis Simone, 1999 and T doellojuradoi Carcelles, 1953. Differences in size, sculpture, spire angulation, aperture, and mainly in protoconch, indicate specific separations. The presently studied terebrids belong to the "complex Terebra doellojuradoi", which encompasses closely related, deep-water, small species, possessing a relatively high degree of endemicity.

A 15-year study on the treatment of undernourished children at a nutrition rehabilitation centre (CREN), Brazil

Objective: To build a life table and determine the factors related to the time of treatment of undernourished children at a nutrition rehabilitation centre (CREN), Sao Paulo, Brazil. Design: Nutritional status was assessed from weight-for-age, height-for-age and BMI-for-age Z-scores, while neuropsychomotor development was classified according to the milestones of childhood development. Life tables, Kaplan-Meier survival curves and Cox multiple regression models were employed in data analysis. Setting: CREN (Centre of Nutritional Recovery and Education), Sao Paulo, Brazil. Subjects: Undernourished children (n 228) from the southern slums of Sao Paulo who had received treatment at CREN under a day-hospital regime between the years 1994 and 2009. Results: The Kaplan-Meier curves of survival analysis showed statistically significant differences in the periods of treatment at CREN between children presenting different degrees of neuropsychomotor development (log-rank = 6.621; P = 0.037). Estimates based on the multivariate Cox model revealed that children aged >= 24 months at the time of admission exhibited a lower probability of nutritional rehabilitation (hazard ratio (HR) = 0.49; P = 0.046) at the end of the period compared with infants aged up 12 months. Children presenting slow development were better rehabilitated in comparison with those exhibiting adequate evolution (HR = 4.48; P = 0.023). No significant effects of sex, degree of undernutrition or birth weight on the probability of nutritional rehabilitation were found. Conclusions: Age and neuropsychomotor developmental status at the time of admission to CREN are critical factors in determining the duration of treatment.

STUDY ON IMPLANT STABILITY IN CEMENTLESS TOTAL KNEE ARTHROPLASTY

Objetives: Determine the stability of tibial and femoral components of 20 cementless knee arthroplasties with rotating platform. Methods: The 20 patients (20 knees) underwent an analysis of dynamic radiographs with an image amplifier and maneuvers of varus and valgus which were compared to static frontal and lateral radiographs of the knees and analyzed by two experienced surgeons in a double-blind way. Results: We could observe in this study that both methods showed very similar results for the stability of the tibial and femoral components (p<0.001) using the Kappa method for comparison. Conclusion: The tibial component was more unstable in relation to the femoral component in both static and dynamic studies. Level of Evidence IV, Case Series.

Systematic UPLC-ESI-MS/MS Study on the Occurrence of Staurosporine and Derivatives in Associated Marine Microorganisms from Eudistoma vannamei

Former bioactivity-guided analysis of the marine invertebrate Eudistoma vannamei led to the isolation of staurosporine derivatives, which revealed strong cytotoxic activity against several human cancer cell lines. The occurrence of such alkaloids in E. vannamei may be correlated to the presence of associated biota, such as Streptomyces bacteria. In agreement to this hypothesis, marine microorganisms associated with E. vannamei were recovered and cultured, leading to a total of 84 isolated bacterial strains. Gas phase fragmentation reactions of staurosporine and derivatives were systematically studied and the analyzed results further supported by computational chemistry studies. The resulting fragment patterns were used to search for the presence of different derivatives in extracts of isolated microorganisms, thereby using LC-MS/MS analysis in MRM mode. These results evidenced that one isolated Streptomyces sp. was able to generate staurosporine, while none of the hydroxy-7-oxo derivatives were detected. Finally, significant cytotoxic activity against human cancer lines was observed for one of the extracts.

A comparative study on multiscale fractal dimension descriptors

Fractal theory presents a large number of applications to image and signal analysis. Although the fractal dimension can be used as an image object descriptor, a multiscale approach, such as multiscale fractal dimension (MFD), increases the amount of information extracted from an object. MFD provides a curve which describes object complexity along the scale. However, this curve presents much redundant information, which could be discarded without loss in performance. Thus, it is necessary the use of a descriptor technique to analyze this curve and also to reduce the dimensionality of these data by selecting its meaningful descriptors. This paper shows a comparative study among different techniques for MFD descriptors generation. It compares the use of well-known and state-of-the-art descriptors, such as Fourier, Wavelet, Polynomial Approximation (PA), Functional Data Analysis (FDA), Principal Component Analysis (PCA), Symbolic Aggregate Approximation (SAX), kernel PCA, Independent Component Analysis (ICA), geometrical and statistical features. The descriptors are evaluated in a classification experiment using Linear Discriminant Analysis over the descriptors computed from MFD curves from two data sets: generic shapes and rotated fish contours. Results indicate that PCA, FDA, PA and Wavelet Approximation provide the best MFD descriptors for recognition and classification tasks. (C) 2012 Elsevier B.V. All rights reserved.

Brazilian multicenter study on prevalence of preterm birth and associated factors

Abstract Background The occurrence of preterm birth remains a complex public health condition. It is considered the main cause of neonatal morbidity and mortality, resulting in a high likelihood of sequelae in surviving children. With variable incidence in several countries, it has grown markedly in the last decades. In Brazil, however, there are still difficulties to estimate its real occurrence. Therefore, it is essential to establish the prevalence and causes of this condition in order to propose prevention actions. This study intend to collect information from hospitals nationwide on the prevalence of preterm births, their associated socioeconomic and environmental factors, diagnostic and treatment methods resulting from causes such as spontaneous preterm labor, prelabor rupture of membranes, and therapeutic preterm birth, as well as neonatal results. Methods/Design This proposal is a multicenter cross-sectional study plus a nested case-control study, to be implemented in 27 reference obstetric centers in several regions of Brazil (North: 1; Northeast: 10; Central-west: 1; Southeast: 13; South: 2). For the cross sectional component, the participating centers should perform, during a period of six months, a prospective surveillance of all patients hospitalized to give birth, in order to identify preterm birth cases and their main causes. In the first three months of the study, an analysis of the factors associated with preterm birth will also be carried out, comparing women who have preterm birth with those who deliver at term. For the prevalence study, 37,000 births will be evaluated (at term and preterm), corresponding to approximately half the deliveries of all participating centers in 12 months. For the case-control study component, the estimated sample size is 1,055 women in each group (cases and controls). The total number of preterm births estimated to be followed in both components of the study is around 3,600. Data will be collected through a questionnaire all patients will answer after delivery. The data will then be encoded in an electronic form and sent online by internet to a central database. The data analysis will be carried out by subgroups according to gestational age at preterm birth, its probable causes, therapeutic management, and neonatal outcomes. Then, the respective rates, ratios and relative risks will be estimated for the possible predictors. Discussion These findings will provide information on preterm births in Brazil and their main social and biological risk factors, supporting health policies and the implementation of clinical trials on preterm birth prevention and treatment strategies, a condition with many physical and emotional consequences to children and their families.

Physical activity counseling in primary health care in Brazil: a national study on prevalence and associated factors

Abstract Background The aim of this study was to determine the prevalence and correlates of physical activity counseling among physicians and nurses working in primary health care in Brazil. Methods A phone survey was carried out in 2011 with professionals working in primary health care in Brazil. The target sample consisted of 1,600 randomly selected primary care units covering all regions of the country. We successfully interviewed 529 professionals within the sampled units; 182 physicians and 347 nurses. The overall response rate was 49.6%. Multivariable logistic regression was used to estimate correlates of counseling in the whole sample and separately for physicians and nurses. Results The prevalence of regular physical activity counseling for at least six months was 68.9% (95% CI 64.9; 72.8) and was significantly higher among physicians compared to nurses (p < 0.05). Most professionals (93.2%) interviewed were unfamiliar with current physical activity recommendations for health. In the adjusted analysis, physical activity counseling was more frequent among those who report assessing patient’s physical activity (OR = 2.16; 95% CI 1.41; 3.29), those reporting that lack of time was not a barrier for counseling (OR = 0.62 95% CI 0.42-0.93), those who felt prepared to provide physical activity counseling (OR = 2.34; 95% CI 1.50-3.66), and those working at primary care units offering physical activity programs for patients (OR = 2.06; 95% CI 1.33-3.20). In the stratified analysis, only assessing patient’s physical activity was a significant correlate among physicians whereas assessing patient’s physical activity, feeling prepared to provide counseling and working in units with physical activity interventions were significant correlates among nurses. Conclusions Physicians and nurses deemed physical activity counseling of great importance in primary health care in Brazil. However, in order to increase the quality of counseling and the number of professionals engaging in this activity, these health teams require greater knowledge about physical activity (global recommendations for health) as well as training on the application of instruments for assessing physical activity. Moreover, sufficient time must be allowed during consultations for the counseling process, and physical activity promotion programs should be implemented within the primary health care units.