Previous studies on Passiflora edulis (sour passion fruit) rinds reported some biological activities and there is a growing interest on rinds flour as a possible functional food, but its alkaloid composition was not detailed investigated. This work reports on for the first time in the literature the identification of norharman in P. edulis rinds, by using stir bar sorptive extraction combined with ultra-fast liquid chromatography coupled to tandem mass spectrometry [SBSE(EG-Silicone)-UFLC-MS/MS)]. This β-carboline alkaloid is suspected to be neurotoxic. Therefore, another purpose of this study was to develop methods of targeted quantification of norharman in P. edulis rinds extracts using polydimethylsiloxane as stationary phase (SBSE(PDMS)) and a copolymer of polydimethylsiloxane and polyethylene glycol as stationary phase (SBSE(EG-Silicone)) combined with high performance liquid chromatography with fluorescence detection (HPLC-Flu) and ultra-fast liquid chromatography coupled with tandem mass spectrometry (UFLC-MS/MS). Norharman extraction by SBSE(PDMS) and SBSE(EG-Silicone) was optimized and compared, and the analytical performance of SBSE(EG-Silicone) method was superior to that of SBSE(PDMS). The analysis of a sample of dried P. edulis rind indicated (332.16 ± 8.43) pg g-1 of norharman.

Resumo O tratamento e a destinação dos resíduos sólidos ocorrem de diferentes formas mediante o desenvolvimento econômico, tecnológico e cultural de cada país. No Brasil, apesar das diversas legislações regulamentando o gerenciamento destes resíduos, vários impactos socioambientais têm sido constatados e associados ao descarte irregular e/ou inadequado dos mesmos. Entre os resíduos que possuem uma complexa problemática de gestão e possibilidade de aperfeiçoamento estão os resíduos sólidos volumosos. Neste estudo realizou-se uma análise do modelo atual de gerenciamento dos resíduos volumosos no município de São Paulo, com apontamento para os pontos críticos e propostas de diretrizes para um gerenciamento mais adequado do ponto de vista socioambiental. Os dados do modelo atual foram obtidos a partir da coleta de informações públicas e visitas in loco aos Ecopontos do município. Os resultados indicam a falta de gerenciamento de alguns resíduos volumosos pelos Ecopontos e que os resíduos que são recebidos por estas unidades são atualmente dispostos em aterros podendo ter direções de valorização. Destaca-se também a falta de programas de Educação Ambiental e uma má qualidade da segregação na fonte. As diretrizes de gerenciamento e valorização propostas estão baseadas nos modelos em funcionamento no exterior e em sistemas de reaproveitamento, preconizados nas legislações Brasileiras.

Abstract The treatment and the disposal of solid wastes occur in different ways through the economic, technological and cultural development of each country. In Brazil, despite the various legislations regulating the management of these wastes, several socio-environmental impacts have been found associated with the irregular and/or inappropriate disposal of these wastes. Among the wastes that have a complex problem of management and the possibility of improvement are the bulky wastes. In this study, an analysis of the current model of management of the bulky waste in the municipality of São Paulo was carried out, aiming at the critical points and proposals of guidelines for more appropriate management of the socio-environmental point of view. The data of the current model were obtained from the collection of public information and on-site visits to the Ecopoints of the municipality. The results indicate the lack of management of some bulky wastes by the Ecopoints and that the wastes that are received by these units are currently disposed in landfills and may have directions of valorization. It also highlights the lack of environmental education programs and a low quality of segregation at the source. The proposed management and valorization guidelines are based on models operating abroad and in reutilization system proposed in Brazilian legislation.

Lambda-cyhalothrin is a widely employed pyrethroid insecticide and is potentially toxic to the environment and to human health. Several reports indicate the presence of this insecticide in water samples worldwide, but more data about its behavior in waters and its derivative products are required. This study shows the behavior of the pesticide lambda-cyhalothrin in aqueous solution at different pH and temperature that were simulated by using water contaminated with a toxic concentration of lambda-cyhalothrin and chemical oxidative process. Lambda-cyhalothrin and its derivative products were monitored employing stir bar sorptive extraction (SBSE), using liquid and thermal desorption, combined with gas chromatography coupled with ion trap mass spectrometry (GC-IT-MS) technology. GC-IT-MS enabled the proposal of the lambda-cyhalothrin chemical transformation pathway and the full identification of twelve derivative products. Among them, only 3-phenoxybenzaldehyde is reported as a degradation product of lambda-cyhalothrin, and this compound is an environmental pollutant with endocrine disrupting activity.

RESUMO Objetivo Elaborar um instrumento para avalição de compreensão de leitura textual e verificar a influência do vocabulário receptivo na compreensão de leitura de escolares típicos de 3º, 4º e 5º anos do ensino fundamental. Método Todos os preceitos éticos foram realizados. Participaram do estudo 69 estudantes de 3º, 4º e 5º anos, com média de idade de 8,2, 9,2 e 10 anos, respectivamente, sendo 35 meninas, que tiveram classificação típica no Teste de Desempenho Escolar. Metade da amostra realizou a prova de compreensão de leitura pelo método de perguntas e respostas, e a outra metade fez a prova com a técnica de Cloze. Todos os escolares realizaram o Teste de Vocabulário de Figuras USP com 139 estímulos. Resultados Os escolares apresentaram bom desempenho em vocabulário receptivo, apesar do nível socioeconômico baixo. Os escolares tiveram melhor desempenho em perguntas explícitas do que em implícitas. Demonstraram desempenho mais homogêneo e semelhante entre os anos escolares na técnica de Cloze . Não foram observados resultados conclusivos quanto à correlação entre vocabulário receptivo e compreensão de leitura pelos dois métodos. Conclusão Há indícios da influência do vocabulário sobre a compreensão de leitura textual, principalmente no método de perguntas e respostas. O instrumento elaborado, incluindo dois métodos avaliativos da compreensão de leitura, é eficiente para investigação e caracterização da compreensão de leitura textual em escolares típicos do 3º, 4º e 5º anos, sendo que ambos os métodos diferenciaram de forma significativa os escolares de 3º e 5º anos.

ABSTRACT Purpose Prepare an instrument to evaluate reading comprehension and verify the influence of receptive vocabulary on the reading comprehension of 3rd to 5th-grade Elementary School students with typical development. Methods All ethical precepts were accomplished. Study participants were 69 3rd-, 4th- and 5th-grade students (35 girls) with mean ages of 8.2, 9.2, and 10 years, respectively, with typical development in the School Performance Test. Half of the sample underwent the reading comprehension test using the question-and-answer method and the other half took the test using the Cloze technique. All students completed the Teste de Vocabulário por Figuras USP (TVFUSP) with 139 stimuli. Results The schoolchildren presented good performance in receptive vocabulary despite their low socioeconomic level. Better performance was observed in explicit questions compared with that in implicit questions. Students demonstrated more homogeneous and similar performance between the school years in the Cloze technique. No conclusive results were found regarding the correlation between receptive vocabulary and reading comprehension by the two methods. Conclusion There is evidence of the influence of receptive vocabulary on the reading comprehension of texts, mainly in the question-and-answer method. The prepared instrument, including both assessment methods of reading comprehension, is efficient to investigate and characterize the reading comprehension of 3rd to 5th-grade Elementary School students, and both methods significantly differentiated students in the 3rd and 5th grades.

The pyrethroids, their metabolites and by-products have been recognized as toxic to environment and human health. Despite several studies about esfenvalerate toxicity and its detection in water and sediments, information about its degradation products is still scanty. In this work, esfenvalerate degradation products were obtained by chemical oxidation with hydrogen peroxide and their structure was elucidated using a procedure known as stir bar sorptive extraction (SBSE) probe desorption gas chromatography-ion trap mass spectrometry (GC-IT-MS) analysis. This procedure consists of the thermal desorption of analytes extracted from a SBSE stir bar introduced by a probe into a gas chromatograph (GC) coupled to an ion trap mass spectrometry (IT-MS) system. Based on IT-MS data, a degradation pathway of esfenvalerate is proposed with ten products of chemical oxidation of esfenvalerate that are fully identified. Among these compounds, 3-phenoxybenzoic acid and 3-phenoxybenzaldehyde were detected, reported as being environmental metabolites of some pyrethroids, with endocrine-disrupting activity.

A simple procedure based on stir bar sorptive extraction and high-performance liquid chromatography-ultraviolet/photodiode array detection (SBSE/LC-UV/PAD) to determine intermediates and by-products of esfenvalerate is described. The influence of organic modifier, ionic strength, extraction time, temperature and pH were simultaneously evaluated by using a factorial experimental design. The utilization of different organic solvents and desorption times were also investigated to establish the optimal conditions for SBSE liquid desorption. Among the ten different peaks (intermediates and by-products) detected after degradation of esfenvalerate, eight (including 3-phenoxybenzoic acid and 3-phenoxybenzaldehyde) were successfully extracted by SBSE under the optimized conditions.

The use of activated carbon powder (ACP), red mud and oxidation with chlorine to remove mefenamic acid in water are described, aimed at their application as a complement to sewage treatment processes in Brazil. A study on the behavior of mefenamic acid in water was performed by evaluating its dissolution for different concentrations and times. Subsequently, the optimal conditions for removal of mefenamic acid were investigated using ACP adsorption at different pH and concentrations, and red mud adsorption using different pH. The utilization of different pH and times was also investigated to establish the ideal conditions for chemical oxidation of the drug. Among the different conditions studied, the best condition for drug removal by ACP and red mud were 100% and 96%, respectively, while the best condition for chemical oxidation occurred using solutions with pH 6 and 7 and reaction times of 30 and 60 minutes.

This paper reports on a modification of the procedures originally described in the French Pharmacopoeia for the UV-visible spectrometric analysis of flavonoids, and proposes a validation of the method and its application in the determination of total flavonoids from sugarcane (Saccharum officinarum) leaves and vinasse. An analysis of precision and accuracy revealed a low relative standard deviation (< 5.0%) and a good recovery percentages (99.79 and 98.34%). A comparison of the spectrometric results against those obtained by high performance liquid chromatography (HPLC-UV) demonstrated complete compatibility between the modified French Pharmacopoeia (spectrometric) and HPLC-UV methods

Myrcia uniflora Barb. Rodr., Myrtaceae, popularly known as "pedra-hume-caá" in Brazil, is sold as dry extracts in capsules or as tinctures for the treatment of diabetes mellitus. Previous phytochemical studies on this species described the occurrence of the flavonoids mearnsitrin and myricitrin. In the present study, the chromatographic profiles of M. uniflora leaves and commercial extracts were determined using HPLC-PAD. Myricitrin was used as an external standard in the development and validation of the HPLC method. The proposed method is simple, rapid and reliable and can be successfully applied in industry for standardization of herbs and phytomedicines commercialised in Brazil as "pedra-hume-caá".

Ptychopetalum olacoides Benth., Olacaceae, popularmente conhecida como marapuama, muirapuama ou miriantã, é uma espécie nativa da região da Amazônia do Brasil. Extratos das cascas da planta são tradicionalmente usados por suas propriedades estimulantes e afrodisíacas, e frequentemente comercializados como constituinte de uma grande variedade de formulações fitoterápicas. O fracionamento por coluna cromatográfica aberta seguida por CLAE-UV/PAD das cascas do caule de três extratos comerciais de P. olacoides permitiram o isolamento de três substâncias comuns em todos os extratos analisados. Os compostos foram identificados por RMN como ácido vanílico, ácido protocatecuíco e teobromina. O ácido vanílico foi utilizado como marcador fitoquímico para P. olacoides e empregado como padrão externo no desenvolvimento e validação de um método de análise qualitativo e quantitativo rápido por CLAE. O valor da recuperação do método desenvolvido foi de 99,02% e os valores de LOD e LOQ foram 0,033 e 0,11 mg.L-1; respectivamente. O método descrito poderá ser empregado para a padronização de plantas, extratos ou fitoterápicos comercializados como marapuama.

Ptychopetalum olacoides Benth., Olacaceae, popularly known as marapuama or muirapuama or miriantã, is a species native to the Amazonian region of Brazil. Extracts of the bark of the plant have been used traditionally for its stimulating and aphrodisiac properties and currently commercialised by the herbal industry as constituents in a wide range of phytomedicines. Fractionation by open column chromatography followed by preparative HPLC-UV/PAD of the stem bark and of three commercial extracts of P. olacoides allowed the isolation of three components that were common to all extracts analysed, and these were identified by NMR to be vanillic acid, protocatechuic acid and theobromine. Vanillic acid, which has been proposed as a phytochemical marker for P. olacoides, was employed as an external standard in the development and validation of a rapid qualitative and quantitative HPLC assay for the analyte. The recoveries values of the developed method were 99.02% and the LOD and LOQ values were 0.033 and 0.11 mg.L-1, respectively. The described method may be applied to the standardisation of herbs, extracts or phytomedicines commercialised as marapuama.

O objetivo deste trabalho foi avaliar os efeitos do solo (pH, macro e micronutrientes), fatores ambientais (temperatura, umidade, época do ano e período da coleta) e condições meteorológicas (chuva, sol, nublado, nublado com chuva) no teor de flavonoides das folhas de Passiflora incarnata L. (Passifloraceae), através do tratamento quimiométrico dos dados por PCA (análise de componentes principais) e HCA (análise hierárquica de agrupamentos). Os flavonoides totais foram quantificados por cromatografia líquida de alta eficiência-detecção por ultravioleta (CLAE-UV/DAD). As análises por PCA e HCA mostraram que as amostras de Passiflora não apresentam uma classificação específica em relação às variáveis estudadas e que as variáveis do meio ambiente não são relevantes para descrever o modelo estudado, porém os elementos do solo Fe, B e Cu demonstraram correlação inversa à concentração dos flavonoides totais.

The aim of the present study was to evaluate the effect of soil characteristics (pH, macro- and micro-nutrients), environmental factors (temperature, humidity, period of the year and time of day of collection) and meteorological conditions (rain, sun, cloud and cloud/rain) on the flavonoid content of leaves of Passiflora incarnata L., Passifloraceae. The total flavonoid contents of leaf samples harvested from plants cultivated or collected under different conditions were quantified by high-performance liquid chromatography with ultraviolet detection (HPLC-UV/PAD). Chemometric treatment of the data by principal component (PCA) and hierarchic cluster analyses (HCA) showed that the samples did not present a specific classification in relation to the environmental and soil variables studied, and that the environmental variables were not significant in describing the data set. However, the levels of the elements Fe, B and Cu present in the soil showed an inverse correlation with the total flavonoid contents of the leaves of P. incarnata.

Este trabalho apresenta a identificação "on line" de flavonas minoritárias do suco da cana-de-açúcar (Saccharum officinarum), por cromatografia líquida de alta eficiência com detector UV acoplada à espectrometria de massas (CL/UV/EM) com ionização química à pressão atmosférica, dissociação induzida por colisão (IQPA-DIC-EM/EM) e derivatização pós-coluna utilizando reagentes de deslocamento de UV. As análises CLAE-UV com reagentes de deslocamento forneceram informações sobre a posição da substituição no esqueleto dos flavonóides e, em combinação com dados de EM, estas técnicas permitiram a identificação "on-line" de cinco flavonas da garapa: luteolina-8-C-glucosil-7-O-glucuronídeo; tricina-7-O-neoesperosideo-4'-O-ramnosídeo; tricina-7-O-metilglucuronato-4'-O-ramnosídeo; tricina-7-O-metilglucuronídeo; swertisina; e outras quatro substâncias foram parcialmente identificadas como flavonas glicosiladas. Somente a swertisina (7-O-metilapigenina-6-C-glicosídeo) foi anteriormente descrita no bagaço da cana-de-açúcar.

This work describes the on-line characterization of minor flavones from sugarcane (Saccharum officinarum) juice by high-performance liquid chromatography coupled to diode array UV detection and mass spectrometry (LC/UV/MS) using atmospheric pressure chemical ionization-collision-induced dissociation (APCI-CID-MS/MS) and post-column derivatization using UV shift reagents. HPLC-UV analysis with shift reagents provided information about the substitution pattern in the flavonoid skeleton and, combined with MS data, these techniques allowed for the on-line identification of five "garapa" flavones: luteolin-8-C-glucosyl-7-O-glucuronide; tricin-7-O-neohesperoside-4'-O-rhamnoside; tricin-7-O-methylglucuronate-4'-O-rhamnoside; tricin-7-O-methylglucuronide; swertisin, while four other compounds were partially identified as glycosylflavones. Only swertisin (7-O-methylapigenin-6-C-glucoside) was reported previously in sugarcane molasses.

Os flavonóides presentes nos extratos de cana-de-açúcar (Saccharum officinarum) foram analisados por cromatografia líquida acoplada à espectrometria de massas (LC-MS), e o estudo da rota de fragmentação dos flavonóides selecionados foi realizado utilizando a espectrometria de massas com aceleração ortogonal por tempo de vôo e ionização eletrospray (ESI-oa-ToF MS). Sete flavonas C- e O-glicosiladas foram identificadas nos extratos: schaftosídeo, isoschaftosídeo, luteolina-8-C-(ramnosilglicosídeo), vitexina, orientina, tricina-7-O-neohesperidosídeo e tricina-7-O-glicosídeo. Destas, cinco foram identificadas sem comparação direta com seus respectivos padrões. O método descrito também permitiu a diferenciação das 6-C e 8-C flavonas isoméricas, schaftosídeo e isoschaftosídeo. A combinação dos dados de fragmentação e a medida de massa exata mostraram ser complementares às técnicas de HPLC-UV-MS previamente utilizadas para discriminação de isômeros nos estudos da cana-de-açúcar.

The flavonoids present in sugarcane (Saccharum officinarum) extracts were analyzed by liquid chromatography - mass spectrometry (LC-MS), and a study of the fragmentation patterns of selected flavonoids was conducted using orthogonal acceleration time-of-flight electrospray ionization mass spectrometry (ESI-oa-ToF MS). Seven C- and O-glycosylflavones were identified in the extracts, namely, schaftoside, isoschaftoside, luteolin-8-C-(rhamnosylglucoside), vitexin, orientin, tricin-7-O-neohesperidoside and tricin-7-O-glucoside. Of these, five were identified in the absence of direct comparison with their respective standards. The described method also permitted the differentiation of the 6-C and 8-C isomeric flavones, schaftoside and isoschaftoside. The combination of fragmentation data and exact mass measurement showed to be complimentary to the HPLC-UV-MS techniques previously utilized for isomers discrimination in sugarcane studies.

A atividade antioxidante do suco de cana-de-açúcar (Saccharum officinarum L.) frente ao reagente DPPH foi avaliada (EC50) e as principais substâncias com atividade seqüestradora de radicais livres do suco e extratos de folhas foram identificadas por CLAE-UV/DAD combinada com CLAE-microfracionamento monitorado por CCD, usando β-caroteno e DPPH como reagentes de detecção. As substâncias mais importantes com atividade seqüestradora de radicais livres foram: nas folhas, luteolina-8-C-(ramnosilglucosídeo) (1); no suco, as flavonas diosmetina-8-C-glucosídeo (2), vitexina (3), schaftosídeo (9), isoschaftosídeo (10) e 4',5'-dimetil-luteolina-8-C-glucosídeo (11). O conteúdo de flavonóides totais do suco (0,241 ± 0,001 mg flavonóides totais/mL suco), comparável ao de outras fontes de flavonóides, sugere o potencial da cana-de-açúcar como fonte alimentícia de antioxidantes naturais. Porém, a baixa capacidade antioxidante da garapa (EC50 = 100,2 ± 2,6 g L-1) indica a necessidade de estudos sobre o consumo na dieta e seus efeitos na saúde humana.

The antioxidant activity of sugarcane (Saccharum officinarum L.) juice towards DPPH reagent was determined (EC50) and the main compounds with radical scavenging activity in juice and leaves extracts were identified by HPLC-UV/PAD analysis combined with HPLC microfractionation monitored by TLC using β-carotene and DPPH as the detection reagents. In sugarcane leaves, luteolin-8-C-(rhamnosylglucoside) (1) was the most important compound with radical scavenging activity; in sugarcane juice, the flavones diosmetin-8-C-glucoside (2), vitexin (3) schaftoside (9), isoschaftoside (10) and 4',5'-dimethyl-luteolin-8-C-glucoside (11) were the most relevant compounds. The content of juice flavonoids (0.241 ± 0.001 mg total flavonoids/mL juice), comparable to other food sources of flavonoids, suggest the potential of sugarcane as a dietary source of natural antioxidants. However, the low antioxidant ability of sugarcane juice (EC50 = 100.2 ± 2.6 g L-1) also points to the need for further studies about the dietary intake of sugarcane flavonoids and its effects on human health.