Development and characterization of concentric capillary nebulizer used in inductively coupled plasma analysis /

A simple, low-cost concentric capillary nebulizer (CCN) was developed and evaluated for ICP spectrometry. The CCN could be operated at sample uptake rates of 0.050-1.00 ml min'^ and under oscillating and non-oscillating conditions. Aerosol characteristics for the CCN were studied using a laser Fraunhofter diffraction analyzer. Solvent transport efficiencies and transport rates, detection limits, and short- and long-term stabilities were evaluated for the CCN with a modified cyclonic spray chamber at different sample uptake rates. The Mg II (280.2nm)/l\/lg 1(285.2nm) ratio was used for matrix effect studies. Results were compared to those with conventional nebulizers, a cross-flow nebulizer with a Scott-type spray chamber, a GemCone nebulizer with a cyclonic spray chamber, and a Meinhard TR-30-K3 concentric nebulizer with a cyclonic spray chamber. Transport efficiencies of up to 57% were obtained for the CCN. For the elements tested, short- and long-term precisions and detection limits obtained with the CCN at 0.050-0.500 ml min'^ are similar to, or better than, those obtained on the same instrument using the conventional nebulizers (at 1.0 ml min'^). The depressive and enhancement effects of easily ionizable element Na, sulfuric acid, and dodecylamine surfactant on analyte signals with the CCN are similar to, or better than, those obtained with the conventional nebulizers. However, capillary clog was observed when the sample solution with high dissolved solids was nebulized for more than 40 min. The effects of data acquisition and data processing on detection limits were studied using inductively coupled plasma-atomic emission spectrometry. The study examined the effects of different detection limit approaches, the effects of data integration modes, the effects of regression modes, the effects of the standard concentration range and the number of standards, the effects of sample uptake rate, and the effect of Integration time. All the experiments followed the same protocols. Three detection limit approaches were examined, lUPAC method, the residual standard deviation (RSD), and the signal-to-background ratio and relative standard deviation of the background (SBR-RSDB). The study demonstrated that the different approaches, the integration modes, the regression methods, and the sample uptake rates can have an effect on detection limits. The study also showed that the different approaches give different detection limits and some methods (for example, RSD) are susceptible to the quality of calibration curves. Multicomponents spectral fitting (MSF) gave the best results among these three integration modes, peak height, peak area, and MSF. Weighted least squares method showed the ability to obtain better quality calibration curves. Although an effect of the number of standards on detection limits was not observed, multiple standards are recommended because they provide more reliable calibration curves. An increase of sample uptake rate and integration time could improve detection limits. However, an improvement with increased integration time on detection limits was not observed because the auto integration mode was used.

Investigations into the determination of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) by capillary gas chromatography

Factors involved in the determination of PAHs (16 priority PAHs as an example) and PCBs (10 PCB congeners, representing 10 isomeric groups) by capillary gas chromatography coupled with mass spectrometry (GC/MS, for PAHs) and electron capture detection (GC/ECD , for PCBs) were studied, with emphasis on the effect of solvent. Having various volatilities and different polarities, solvent studied included dichloromethane, acetonitrile, hexan e, cyclohexane, isooctane, octane, nonane, dodecane, benzene, toluene, p-xylene, o-xylene, and mesitylene. Temperatures of the capillary column, the injection port, the GC/MS interface, the flow rates of carrier gas and make-up gas, and the injection volume were optimized by one factor at a time method or simplex optimization method. Under the optimized conditions, both peak height and peak area of 16 PAHs, especially the late-eluting PAHs, were significantly enhanced (1 to 500 times) by using relatively higher boiling point solvents such as p-xylene and nonane, compared with commonly used solvents like benzene and isooctane. With the improved sensitivity, detection limits of between 4.4 pg for naphthalene and 30.8 pg for benzo[g,h,i]perylene were obtained when p-xylene was used as an injection solvent. Effect of solvent on peak shape and peak intensity were found to be greatly dependent on temperature parameters, especially the initial temperature of the capillary column. The relationship between initial temperature and shape of peaks from 16 PAHs and 10 PCBs were studied and compared when toluene, p-xylene, isooctane, and nonane were used as injection solvents. If a too low initial temperature was used, fronting or split of peaks was observed. On the other hand, peak tailing occurred at a too high initial column temperature. The optimum initial temperature, at which both peak fronting and tailing were avoided and symmetrical peaks were obtained, depended on both solvents and the stationary phase of the column used. On a methyl silicone column, the alkane solvents provided wider optimum ranges of initial temperature than aromatic solvents did, for achieving well-shaped symmetrical GC peaks. On a 5% diphenyl: 1% vinyl: 94% dimethyl polysiloxane column, when the aromatic solvents were used, the optimum initial temperature ranges for solutes to form symmetrical peaks were improved to a similar degree as those when the alkanes were used as injection solvents. A mechanism, based on the properties of and possible interactions among the analyte, the injection solvent, and the stationary phase of the capillary column, was proposed to explain these observations. The effect of initial temperature on peak height and peak area of the 16 PAHs and the 10 PCBs was also studied. The optimum initial temperature was found to be dependent on the physical properties of the solvent used and the amount of the solvent injected. Generally, from the boiling point of the solvent to 10 0C above its boiling point was an optimum range of initial temperature at which cthe highest peak height and peak area were obtained.

Avaliação do apêndice atrial esquerdo pela ecocardiografia transtorácica com imagem harmônica após evento neurológico agudo

Introdução: Embora a imagem com segunda harmônica esteja largamente disponível na maioria dos aparelhos de ultra-sonografia, sua acurácia para avaliar a morfologia e a função do apêndice atrial esquerdo (AAE) permanece precariamente caracterizada. Objetivos: Explorar o desempenho diagnóstico da ecocardiografia transtorácica com segunda harmônica (ETTsh) na avaliação do AAE após eventos neurológicos agudos. Métodos: Realizamos um estudo transversal em pacientes com eventos neurológicos isquêmicos agudos, encaminhados para realização de ETTsh e Ecocardiografia Transesofágica (ETE). As análises da área longitudinal máxima e do pico da velocidade de esvaziamento de fluxo do AAE foram realizadas por observadores cegos. Resultados: Foram avaliados 51 pacientes (49% femininas, 62 ± 12 anos) com eventos neurológicos isquêmicos agudos. Contraste ecocardiográfico espontâneo foi observado em 11 (22%) pacientes no AE, em 7(14%) no AAE e em 3 (6%) na aorta torácica descendente. Trombo no AAE foi identificado em apenas 2 (4%) pacientes. O mapeamento e a análise do AAE foi factível na maioria dos casos (98%), tanto para o estudo com Doppler quanto para avaliação da área do AAE. Observamos uma associação positiva e significativa entre o ETTsh e o ETE, tanto para a avaliação das velocidades máximas de esvaziamento do AAE (r=0,63; p<0,001) quanto para a área longitudinal máxima do AAE (r=0,73; p<0,001). Ademais, todos os pacientes com trombos no AAE ou contraste espontâneo (n=7) tiveram velocidade de esvaziamento inferior a 50 cm/s no mapeamento transtorácico (valor preditivo negativo de 100%). Na análise multivariada ajustada para diversos potenciais preditores transtorácicos de risco, a velocidade máxima de esvaziamento do AAE permaneceu independentemente associada com trombos no AAE ou contraste espontâneo. Conclusão: ETTsh pode fornecer informações relevantes a respeito da morfologia e dinâmica do AAE. Em particular, pacientes com velocidades altas de esvaziamento do AAE podem não necessitar de avaliação adicional com ETE.

Development and Validation of an UV-Derivative Spectrophotometric Method for Determination of Glimepiride in Tablets

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

Malformação arteriovenosa uterina após doença trofoblástica gestacional

OBJETIVO: investigar a presença e resultados de malformações vasculares uterinas (MAVU) após doença trofoblástica gestacional (DTG). MÉTODOS: estudo retrospectivo com inclusão de casos diagnosticados entre 1987 e 2004; 2764 pacientes após DTG foram acompanhadas anualmente com ultra-sonografia transvaginal e Doppler colorido no Centro de Neoplasia Trofoblástica Gestacional da Santa Casa da Misericórdia (Rio de Janeiro, RJ, Brasil). Sete pacientes tiveram diagnóstico final de MAVU baseado em análise ultra-sonográfica - índice de pulsatilidade (IP), índice de resistência (IR) e velocidade sistólica máxima (VSM) - e achados de imagens de ressonância nuclear magnética (RNM). Dosagens negativas de beta-hCG foram decisivas para estabelecer o diagnóstico diferencial com DTG recidivante. RESULTADOS: a incidência de MAVU após DTG foi 0,2% (7/2764). Achados ultra-sonográficos de MAVU: IP médio de 0,44±0,058 (extremos: 0,38-0,52); IR médio de 0,36±0,072 (extremos: 0,29-0,50); VSM média de 64,6±23,99 cm/s (extremos: 37-96). A imagem de RNM revelou útero aumentado, miométrio heterogêneo, espaços vasculares tortuosos e vasos parametriais com ectasia. A apresentação clínica mais comum foi hemorragia transvaginal, presente em 52,7% (4/7) dos casos. Tratamento farmacológico com 150 mg de acetato de medroxiprogesterona foi empregado para controlar a hemorragia, após a estabilização hemodinâmica. Permanecem as pacientes em seguimento, assintomáticas até hoje. Duas pacientes engravidaram com MAVU, com gestações e partos exitosos. CONCLUSÃO: presente sangramento transvaginal em pacientes com beta-hCG negativo e história de DTG, deve-se considerar a possibilidade de MAVU e solicitar avaliação ultra-sonográfica com dopplervelocimetria. O tratamento conservador é a melhor opção na maioria dos casos de MAVU pós-DTG.

Gelatinization properties of native starches and their Naegeli dextrins

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

Principais normas e recomendações existentes para o controle de vibrações provocadas pelo uso de explosivos em áreas urbanas: parte II

As atividades que envolvem o uso de explosivos devem ser controladas, não só com relação ao desmonte de estruturas (rocha e outros materiais), mas também quanto a danos estruturais em edificações próximas (casas, edificações históricas, etc.) e outros impactos ambientais como vibração, propagação de ruídos, ultralançamentos e sobrepressão atmosférica. Tais atividades são regidas por normas técnicas que sugerem parâmetros de medição e limites definidos na avaliação de prováveis danos. No caso específico de minerações em áreas urbanas, a velocidade de vibração de partícula (Vp), normalmente expressa em mm/s, é o parâmetro que tem dado melhor correlação na avaliação de possíveis danos às estruturas civis, atribuídos às vibrações do terreno. As diferentes normas existentes apresentam valores de Vp que variam de 2mm/s para edifícios históricos até 150mm/s para construções em concreto armado. A maioria delas considera na avaliação de danos estruturais, além da velocidade, a freqüência da vibração. Algumas normas foram elaboradas com base em dados experimentais, analisando parâmetros como o tipo de construção e o material nela utilizados, outras se basearam apenas em valores empíricos, mas todas apresentam valores conservativos. A norma brasileira não avalia o parâmetro freqüência e não classifica os diferentes tipos de estruturas civis, restringindo-se ao valor resultante da velocidade de vibração como parâmetro medido, sendo, assim, limitada e deficiente em relação às normas internacionais. A coletânea aqui apresentada reuniu as normas nas Américas e em outros continentes, além de uma comparação com as normas européias mais importantes em âmbito mundial.

Optimization of photo-polymerized sol gel monolithic stationary phases prepared in polyacrylate-coated fused-silica capillaries for capillary electrochromatography

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Unusual early morning development of the equatorial anomaly in the Brazilian sector during the Halloween magnetic storm

The solar events that occurred at the end of October 2003 gave rise to very strong geomagnetic disturbances that peaked twice with Dst values reaching -345 nT around 0000 UT on 30 October and -400 nT around 2300 UT, on the same day. Disturbances in several ionospheric parameters were observed over Brazil. This work will focus on the ionospheric response to the initial westward prompt penetration electric field and on the strong intensification of the equatorial ionization anomaly that occurred because of the electric field polarity reversal that followed in the early morning hours of 29 October. The F layer peak height over the equator first decreased under the strong prompt penetration westward electric field, which was followed by significant height increase under eastward electric field. We have used Sheffield University Plasmasphere Ionosphere Model (SUPIM) with an intensified westward disturbed electric field in the presunrise hours, presumably due to prompt penetration from the magnetosphere, in order to study the effect of such a field in the ionosphere. The simulation results showed that prompt penetration of magnetospheric electric fields of westward polarity to the nightside equatorial region seems to be the most probable cause of the initial F layer height decreases. The intensification of the equatorial ionization anomaly and the unusual enhancement on F layer peak density, which was not modeled by the SUPIM, are explained as caused by the strong eastward electric field that followed the initial phase in combination with a highly variable disturbed meridional/transequatorial wind system as inferred from the F2 layer peak height variations. The highly dynamic wind pattern, with a short-term response (2-4 hours), is compatible with the predictions of some previous theoretical model calculations reported in the literature.

Statistical methods applied to the analysis of blasting vibrations in a diabase quarry in the city of Campinas, (SP) Brazil

Statistical methods of multiple regression analysis, trend surface analysis and principal components analysis were applied to seismographic data recorded during production blasting at a diabase quarry in the urban area of Campinas (SP), Brazil. The purpose of these analyses was to determine the influence of the following variables: distance (D), charge weight per delay (W), and scaled distance (SD) associated with properties of the rock body (orientation, frequency and angle of geological discontinuities; depth of bedrock and thickness of the soil overburden) in the variation of the peak particle velocity (PPV). This approach yielded variables with larger influences (loads) on the variation of ground vibration, as well as behavior and space tendency of this variation. The results showed a better relationship between PPV and D, with D being the most important factor in the attenuation of the ground vibrations. The geological joints and the depth to bedrock have a larger influence than the explosive charges in the variation of the vibration levels, but frequencies appear to be more influenced by the amount of soil overburden.

Efeito do envelhecimento sobre o comportamento mecânico dos músculos papilares de ratos Wistar.

PURPOSE--To evaluate the effects of age on mechanical performance of rat myocardium. METHODS--Left ventricular papillary muscles were isolated from male Wistar rats at 1, 3, 6 and 12 months of age. Muscles were studied isometrically and isotonically, stimulated at 0.2 Hz, perfused with Krebs-Henseleit solution having an external calcium concentration of 2.52 mM, and maintained at 28 degrees C. RESULTS--Peak isometric developed tension was significantly higher in 1 month than 3, 6 and 12 months. Peak rate of isometric tension rise decreased substantially between 1, 3 and 12 months. Time to peak isometric developed tension showed a significant increase of both 3 and 12 months of age. Time to half relaxation increased significantly from 3 to 6 and from 3 to 12 months. Maximum rate of tension decline decreased from 3 to 6 and from 3 to 12 months. No difference in resting tension was noted among any group. Isotonically, peak shortening and time to peak shortening increased from 1 to 3 months of age. Time to half re-lengthening increased from 3 to 6 and from 3 to 12 months of age. No difference in peak shortening velocity, peak relaxation velocity and relative change in muscle length was noted among any groups. CONCLUSION--The maturation affects the mechanical performance of cardiac muscle.

Foetal echoencephalography and Doppler ultrasonography of the middle cerebral artery in canine foetuses

Objectives: This study aimed to evaluate the characteristics of the brain and vascular indicesof the middle cerebral artery of canine foetuses. Methods: Twenty-five bitches were selected. Tissue development, echogenicity, echotexture and brain echobiometric data were studied, and the major structures were identified between the 5th and 8th gestational weeks. The area and volume of the brain mass (BMA and BMV), cranial area and volume (AC and VC), brain mass index (BMI) and brain volume index (BVI) were determined. A single ultrasound examination was performed during each studied week (6th, 7th and 8th). Doppler ultrasonography was performed to assess the maximum and minimum velocity, resistance and pulsatility index of middle cerebral artery of the foetuses. Results: Echoencephalography was performed to evaluate the morphological characteristics of the central nervous system. Cerebral echobiometry indicated an increase in area and volume of the hemispheres and cranium (P<0·001) but no changes in BMI or BVI over the gestational period studied. Doppler ultrasonography identified increases in peak systolic velocity (P=0·0188) and end diastolic velocity (P=0·0274) and decreases in resistance index (P=0·0002) and pulsatility index (P<0·001). Clinical Significance: Echoencephalography and spectral Doppler ultrasonography of the middle cerebral artery in canine foetuses might be a useful technique for prenatal care. © 2013 British Small Animal Veterinary Association.

Comportamento dopplervelocimétrico das artérias oftálmicas nas síndromes hipertensivas da gestação

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

Estudo Power Doppler das lesões mamárias

Pós-graduação em Ginecologia, Obstetrícia e Mastologia - FMB

Efeito do exercício excêntrico sobre as propriedades mecânicas do músculo e índices de aptidão aeróbia

Pós-graduação em Ciências da Motricidade - IBRC