Validação da eficácia dos procedimentos de limpeza, no equipamento de fabrico e embalagem, na indústria farmacêutica

Na indústria farmacêutica, a limpeza dos equipamentos e superfícies é muito importante no processo de fabrico/embalagem dos produtos farmacêuticos. Possíveis resíduos contaminantes devem ser removidos dos equipamentos e das superfícies envolvidas no processo. De acordo com as Boas Práticas de Fabrico (GMP), os procedimentos de limpeza e os métodos analíticos usados para determinar as quantidades de resíduos devem ser validados. O método analítico combinado com o método de amostragem utilizado na colheita de amostras deve ser sujeito a um ensaio de “recovery”. Neste trabalho apresenta-se uma estratégia inovadora para a validação de limpeza de formas farmacêuticas semi-sólidas. Propõe-se o uso de um método de amostragem que consiste na colheita direta de amostra após o seu fabrico, sendo a análise de resíduos feita directamente nesta amostra. Os produtos escolhidos para a avaliação da estratégia foram dois medicamentos dermatológicos, apresentados na forma de pomada e produzidos numa unidade de fabrico de vários produtos, pela Schering Plough Farma/ Merck Sharp & Dohme (Cacém, Portugal). Como métodos analíticos para a quantificação dos resíduos, utilizaram-se métodos validados por via espectrofotométrica (HPLC), usados na análise do produto acabado. A validação de limpeza foi avaliada através da análise de uma quantidade conhecida de pomada (produto B (*)), usando o método de análise da pomada fabricada anteriormente (produto A (*)), de modo a verificar-se a existência ou não de agente de limpeza e substâncias ativas deixadas após a limpeza do produto A, e vice-versa. As concentrações residuais das substâncias ativas e do agente de limpeza encontradas após a limpeza foram nulas, ou seja, inferiores ao limite de deteção (LOD), sendo que o critério de aceitação da limpeza utilizado foi de 6,4 x 10-4 mg/g para a substância ativa 1 (*); 1,0 x 10-2 mg/g para a substância ativa 2 (*); 1,0 x 10-3 mg/g para a substância ativa 3 (*) e de 10 ppm para o agente de limpeza. No ensaio de “recovery”, obtiveram-se resultados acima de 70% para todas as substâncias ativas e para o agente de limpeza nas duas pomadas. Antes de se proceder a este ensaio de “recovery”, houve a necessidade de ajustar as condições cromatográficas dos métodos analíticos de ambos os produtos e do agente de limpeza, por forma a obter-se valores da conformidade do sistema (fator de tailling e de resolução) de acordo com as especificações. A precisão dos resultados, reportada como desvio padrão relativo (RSD), deu abaixo de 2,0%, excepto nos ensaios que envolvem a substância ativa 3, cuja especificação é inferior a 10,0%. Os resultados obtidos demonstraram que os procedimentos de limpeza usados na unidade de fabrico em causa são eficazes, eliminando assim a existência de contaminação cruzada.

Development of a simple analytical method for the simultaneousdetermination of paracetamol, paracetamol-glucuronide andp-aminophenol in river water

Paracetamol is among the most worldwide consumed pharmaceuticals. Although its occurrence in the environment is well documented, data about the presence of its metabolites and transformation products is very scarce. The present work describes the development of an analytical method for the simultaneous determination of paracetamol, its principal metabolite (paracetamol-glucuronide) and its main transformation product (p-aminophenol) based on solid phase extraction (SPE) and high performance liquid chromatography coupled to diode array detection (HPLC-DAD). The method was applied to analysis of river waters, showing to be suitable to be used in routine analysis. Different SPE sorbents were compared and the use of two Oasis WAX cartridges in tandem proved to be the most adequate approach for sample clean up and pre-concentration. Under optimized conditions, limits of detection in the range 40–67 ng/L were obtained, as well as mean recoveries between 60 and 110% with relative standard deviations (RSD) below 6%. Finally, the developed SPE-HPLC/DAD method was successfully applied to the analysis of the selected compounds in samples from seven rivers located in the north of Portugal. Nevertheless all the compounds were detected, it was the first time that paracetamol-glucuronide was found in river water at concentrations up to 3.57 μg/L.

Développement de méthodes d’analyse directe de polluants organiques volatils à l’état de traces dans l’air et les biogaz

Il est reconnu que le benzène, le toluène, l’éthylbenzène et les isomères du xylène, composés organiques volatils (COVs) communément désignés BTEX, produisent des effets nocifs sur la santé humaine et sur les végétaux dépendamment de la durée et des niveaux d’exposition. Le benzène en particulier est classé cancérogène et une exposition à des concentrations supérieures à 64 g/m3 de benzène peut être fatale en 5–10 minutes. Par conséquent, la mesure en temps réel des BTEX dans l’air ambiant est essentielle pour détecter rapidement un danger associé à leur émission dans l’air et pour estimer les risques potentiels pour les êtres vivants et pour l’environnement. Dans cette thèse, une méthode d’analyse en temps réel des BTEX dans l’air ambiant a été développée et validée. La méthode est basée sur la technique d’échantillonnage direct de l’air couplée avec la spectrométrie de masse en tandem utilisant une source d’ionisation chimique à pression atmosphérique (APCI-MS/MS directe). La validation analytique a démontré la sensibilité (limite de détection LDM 1–2 μg/m3), la précision (coefficient de variation CV < 10%), l’exactitude (exactitude > 95%) et la sélectivité de la méthode. Des échantillons d’air ambiant provenant d’un site d’enfouissement de déchets industriels et de divers garages d’entretien automobile ont été analysés par la méthode développée. La comparaison des résultats avec ceux obtenus par la technique de chromatographie gazeuse on-line couplée avec un détecteur à ionisation de flamme (GC-FID) a donné des résultats similaires. La capacité de la méthode pour l’évaluation rapide des risques potentiels associés à une exposition aux BTEX a été prouvée à travers une étude de terrain avec analyse de risque pour la santé des travailleurs dans trois garages d’entretien automobile et par des expériences sous atmosphères simulées. Les concentrations mesurées dans l’air ambiant des garages étaient de 8,9–25 µg/m3 pour le benzène, 119–1156 µg/m3 pour le toluène, 9–70 µg/m3 pour l’éthylbenzène et 45–347 µg/m3 pour les xylènes. Une dose quotidienne environnementale totale entre 1,46 10-3 et 2,52 10-3 mg/kg/jour a été déterminée pour le benzène. Le risque de cancer lié à l’exposition environnementale totale au benzène estimé pour les travailleurs étudiés se situait entre 1,1 10-5 et 1,8 10-5. Une nouvelle méthode APCI-MS/MS a été également développée et validée pour l’analyse directe de l’octaméthylcyclotétrasiloxane (D4) et le décaméthylcyclopentasiloxane (D5) dans l’air et les biogaz. Le D4 et le D5 sont des siloxanes cycliques volatils largement utilisés comme solvants dans les processus industriels et les produits de consommation à la place des COVs précurseurs d’ozone troposphérique tels que les BTEX. Leur présence ubiquitaire dans les échantillons d’air ambiant, due à l’utilisation massive, suscite un besoin d’études de toxicité. De telles études requièrent des analyses qualitatives et quantitatives de traces de ces composés. Par ailleurs, la présence de traces de ces substances dans un biogaz entrave son utilisation comme source d’énergie renouvelable en causant des dommages coûteux à l’équipement. L’analyse des siloxanes dans un biogaz s’avère donc essentielle pour déterminer si le biogaz nécessite une purification avant son utilisation pour la production d’énergie. La méthode développée dans cette étude possède une bonne sensibilité (LDM 4–6 μg/m3), une bonne précision (CV < 10%), une bonne exactitude (> 93%) et une grande sélectivité. Il a été également démontré qu’en utilisant cette méthode avec l’hexaméthyl-d18-disiloxane comme étalon interne, la détection et la quantification du D4 et du D5 dans des échantillons réels de biogaz peuvent être accomplies avec une meilleure sensibilité (LDM ~ 2 μg/m3), une grande précision (CV < 5%) et une grande exactitude (> 97%). Une variété d’échantillons de biogaz prélevés au site d’enfouissement sanitaire du Complexe Environnemental de Saint-Michel à Montréal a été analysée avec succès par cette nouvelle méthode. Les concentrations mesurées étaient de 131–1275 µg/m3 pour le D4 et 250–6226 µg/m3 pour le D5. Ces résultats représentent les premières données rapportées dans la littérature sur la concentration des siloxanes D4 et D5 dans les biogaz d’enfouissement en fonction de l’âge des déchets.

Optimierung von Betriebsstrategien für elektrifizierte Antriebskonzepte

Im Rahmen dieser Arbeit wird eine gemeinsame Optimierung der Hybrid-Betriebsstrategie und des Verhaltens des Verbrennungsmotors vorgestellt. Die Übernahme von den im Steuergerät verwendeten Funktionsmodulen in die Simulationsumgebung für Fahrzeuglängsdynamik stellt eine effiziente Applikationsmöglichkeit der Originalparametrierung dar. Gleichzeitig ist es notwendig, das Verhalten des Verbrennungsmotors derart nachzubilden, dass das stationäre und das dynamische Verhalten, inklusive aller relevanten Einflussmöglichkeiten, wiedergegeben werden kann. Das entwickelte Werkzeug zur Übertragung der in Ascet definierten Steurgerätefunktionen in die Simulink-Simulationsumgebung ermöglicht nicht nur die Simulation der relevanten Funktionsmodule, sondern es erfüllt auch weitere wichtige Eigenschaften. Eine erhöhte Flexibilität bezüglich der Daten- und Funktionsstandänderungen, sowie die Parametrierbarkeit der Funktionsmodule sind Verbesserungen die an dieser Stelle zu nennen sind. Bei der Modellierung des stationären Systemverhaltens des Verbrennungsmotors erfolgt der Einsatz von künstlichen neuronalen Netzen. Die Auswahl der optimalen Neuronenanzahl erfolgt durch die Betrachtung des SSE für die Trainings- und die Verifikationsdaten. Falls notwendig, wird zur Sicherstellung der angestrebten Modellqualität, das Interpolationsverhalten durch Hinzunahme von Gauß-Prozess-Modellen verbessert. Mit den Gauß-Prozess-Modellen werden hierbei zusätzliche Stützpunkte erzeugt und mit einer verminderten Priorität in die Modellierung eingebunden. Für die Modellierung des dynamischen Systemverhaltens werden lineare Übertragungsfunktionen verwendet. Bei der Minimierung der Abweichung zwischen dem Modellausgang und den Messergebnissen wird zusätzlich zum SSE das 2σ-Intervall der relativen Fehlerverteilung betrachtet. Die Implementierung der Steuergerätefunktionsmodule und der erstellten Steller-Sensor-Streckenmodelle in der Simulationsumgebung für Fahrzeuglängsdynamik führt zum Anstieg der Simulationszeit und einer Vergrößerung des Parameterraums. Das aus Regelungstechnik bekannte Verfahren der Gütevektoroptimierung trägt entscheidend zu einer systematischen Betrachtung und Optimierung der Zielgrößen bei. Das Ergebnis des Verfahrens ist durch das Optimum der Paretofront der einzelnen Entwurfsspezifikationen gekennzeichnet. Die steigenden Simulationszeiten benachteiligen Minimumsuchverfahren, die eine Vielzahl an Iterationen benötigen. Um die Verwendung einer Zufallsvariablen, die maßgeblich zur Steigerung der Iterationanzahl beiträgt, zu vermeiden und gleichzeitig eine Globalisierung der Suche im Parameterraum zu ermöglichen wird die entwickelte Methode DelaunaySearch eingesetzt. Im Gegensatz zu den bekannten Algorithmen, wie die Partikelschwarmoptimierung oder die evolutionären Algorithmen, setzt die neu entwickelte Methode bei der Suche nach dem Minimum einer Kostenfunktion auf eine systematische Analyse der durchgeführten Simulationsergebnisse. Mit Hilfe der bei der Analyse gewonnenen Informationen werden Bereiche mit den bestmöglichen Voraussetzungen für ein Minimum identifiziert. Somit verzichtet das iterative Verfahren bei der Bestimmung des nächsten Iterationsschrittes auf die Verwendung einer Zufallsvariable. Als Ergebnis der Berechnungen steht ein gut gewählter Startwert für eine lokale Optimierung zur Verfügung. Aufbauend auf der Simulation der Fahrzeuglängsdynamik, der Steuergerätefunktionen und der Steller-Sensor-Streckenmodelle in einer Simulationsumgebung wird die Hybrid-Betriebsstrategie gemeinsam mit der Steuerung des Verbrennungsmotors optimiert. Mit der Entwicklung und Implementierung einer neuen Funktion wird weiterhin die Verbindung zwischen der Betriebsstrategie und der Motorsteuerung erweitert. Die vorgestellten Werkzeuge ermöglichten hierbei nicht nur einen Test der neuen Funktionalitäten, sondern auch eine Abschätzung der Verbesserungspotentiale beim Verbrauch und Abgasemissionen. Insgesamt konnte eine effiziente Testumgebung für eine gemeinsame Optimierung der Betriebsstrategie und des Verbrennungsmotorverhaltens eines Hybridfahrzeugs realisiert werden.

Prevalencia del deterioro cognitivo leve en pacientes adultos mayores con y sin hipertensión arterial

Study of cross section in 280 patients who attended the Internal Medicine consultation with ages between 60 and 85 years. The cognitive impairment was evaluated with the Neuropsi test developed in Mexico and validated for the Hispanic speaking population.(5) Once performed the data collection was made the statistical handling which included for the qualitative variables absolute and relative frequencies distribution in percentage; for the quantitative variables were made measures of central tendency as the average and the median and of dispersion the range and the standard deviation. Besides, for the association evaluation between the different factors of risk and cognitive impairment were used tests like the T of Student, the Pearson Chi-square or the Fisher’s exact test.(expected value <5)

Fast separation of selective serotonin reuptake inhibitors antidepressants in plasma sample by nonaqueous capillary electrophoresis

A simple, fast, and sensitive liquid-liquid extraction method followed by nonaqueous capillary electrophoresis (LLE/NACE) was developed and validated for Simultaneous determination of four antidepressants (fluoxetine, sertraline, citalopram and paroxetine) in human plasma. Several experimental separation conditions using aqueous and nonaqueous media separation were tested by varying the electrolyte pH value (for aqueous medium) and the ionic strength concentration considering the similar mobility of the compounds. High-resolution separation was achieved with a mixture of 1.25 mol L(-1) of phosphoric acid in acetonitrile. The quantification limits of the LLE/CE method varied between 15 and 30 ng mL(-1), with a relative standard deviation (RSD) lower than 10.3%. The method was successfully applied in therapeutic drug monitoring and should be employed in the evaluation of plasma levels in urgent toxicological analysis. (C) 2009 Elsevier B.V. All rights reserved.

Essays on health care reform, wealth inequality, and demography

This thesis contains three chapters. The first chapter uses a general equilibrium framework to simulate and compare the long run effects of the Patient Protection and Affordable Care Act (PPACA) and of health care costs reduction policies on macroeconomic variables, government budget, and welfare of individuals. We found that all policies were able to reduce uninsured population, with the PPACA being more effective than cost reductions. The PPACA increased public deficit mainly due to the Medicaid expansion, forcing tax hikes. On the other hand, cost reductions alleviated the fiscal burden of public insurance, reducing public deficit and taxes. Regarding welfare effects, the PPACA as a whole and cost reductions are welfare improving. High welfare gains would be achieved if the U.S. medical costs followed the same trend of OECD countries. Besides, feasible cost reductions are more welfare improving than most of the PPACA components, proving to be a good alternative. The second chapter documents that life cycle general equilibrium models with heterogeneous agents have a very hard time reproducing the American wealth distribution. A common assumption made in this literature is that all young adults enter the economy with no initial assets. In this chapter, we relax this assumption – not supported by the data – and evaluate the ability of an otherwise standard life cycle model to account for the U.S. wealth inequality. The new feature of the model is that agents enter the economy with assets drawn from an initial distribution of assets. We found that heterogeneity with respect to initial wealth is key for this class of models to replicate the data. According to our results, American inequality can be explained almost entirely by the fact that some individuals are lucky enough to be born into wealth, while others are born with few or no assets. The third chapter documents that a common assumption adopted in life cycle general equilibrium models is that the population is stable at steady state, that is, its relative age distribution becomes constant over time. An open question is whether the demographic assumptions commonly adopted in these models in fact imply that the population becomes stable. In this chapter we prove the existence of a stable population in a demographic environment where both the age-specific mortality rates and the population growth rate are constant over time, the setup commonly adopted in life cycle general equilibrium models. Hence, the stability of the population do not need to be taken as assumption in these models.

A sensitive microextraction by packed sorbent-based methodology combined with ultra-high pressure liquid chromatography as a powerful technique for analysis of biologically active flavonols in wines

A new approach based on microextraction by packed sorbent (MEPS) and reversed-phase high-throughput ultra high pressure liquid chromatography (UHPLC) method that uses a gradient elution and diode array detection to quantitate three biologically active flavonols in wines, myricetin, quercetin, and kaempferol, is described. In addition to performing routine experiments to establish the validity of the assay to internationally accepted criteria (selectivity, linearity, sensitivity, precision, accuracy), experiments are included to assess the effect of the important experimental parameters such as the type of sorbent material (C2, C8, C18, SIL, and C8/SCX), number of extraction cycles (extract-discard), elution volume, sample volume, and ethanol content, on the MEPS performance. The optimal conditions of MEPS extraction were obtained using C8 sorbent and small sample volumes (250 μL) in five extraction cycle and in a short time period (about 5 min for the entire sample preparation step). Under optimized conditions, excellent linearity View the MathML source(Rvalues2>0.9963), limits of detection of 0.006 μg mL−1 (quercetin) to 0.013 μg mL−1 (myricetin) and precision within 0.5–3.1% were observed for the target flavonols. The average recoveries of myricetin, quercetin and kaempferol for real samples were 83.0–97.7% with relative standard deviation (RSD, %) lower than 1.6%. The results obtained showed that the most abundant flavonol in the analyzed samples was myricetin (5.8 ± 3.7 μg mL−1). Quercetin (0.97 ± 0.41 μg mL−1) and kaempferol (0.66 ± 0.24 μg mL−1) were found in a lower concentration. The optimized MEPSC8 method was compared with a reverse-phase solid-phase extraction (SPE) procedure using as sorbent a macroporous copolymer made from a balanced ratio of two monomers, the lipophilic divinylbenzene and the hydrophilic N-vinylpyrrolidone (Oasis HLB) were used as reference. MEPSC8 approach offers an attractive alternative for analysis of flavonols in wines, providing a number of advantages including highest extraction efficiency (from 85.9 ± 0.9% to 92.1 ± 0.5%) in the shortest extraction time with low solvent consumption, fast sample throughput, more environmentally friendly and easy to perform.

Development of a novel microextraction by packed sorbent-based approach followed by ultrahigh pressure liquid chromatography as a powerful technique for quantification phenolic constituents of biological interest in wines

A novel analytical approach, based on a miniaturized extraction technique, the microextraction by packed sorbent (MEPS), followed by ultrahigh pressure liquid chromatography (UHPLC) separation combined with a photodiode array (PDA) detection, has been developed and validated for the quantitative determination of sixteen biologically active phenolic constituents of wine. In addition to performing routine experiments to establish the validity of the assay to internationally accepted criteria (linearity, sensitivity, selectivity, precision, accuracy), experiments are included to assess the effect of the important experimental parameters on the MEPS performance such as the type of sorbent material (C2, C8, C18, SIL, and M1), number of extraction cycles (extract-discard), elution volume, sample volume, and ethanol content, were studied. The optimal conditions of MEPS extraction were obtained using C8 sorbent and small sample volumes (250 μL) in five extraction cycle and in a short time period (about 5 min for the entire sample preparation step). The wine bioactive phenolics were eluted by 250 μL of the mixture containing 95% methanol and 5% water, and the separation was carried out on a HSS T3 analytical column (100 mm × 2.1 mm, 1.8 μm particle size) using a binary mobile phase composed of aqueous 0.1% formic acid (eluent A) and methanol (eluent B) in the gradient elution mode (10 min of total analysis). The method gave satisfactory results in terms of linearity with r2-values > 0.9986 within the established concentration range. The LOD varied from 85 ng mL−1 (ferulic acid) to 0.32 μg mL−1 ((+)-catechin), whereas the LOQ values from 0.028 μg mL−1 (ferulic acid) to 1.08 μg mL−1 ((+)-catechin). Typical recoveries ranged between 81.1 and 99.6% for red wines and between 77.1 and 99.3% for white wines, with relative standard deviations (RSD) no larger than 10%. The extraction yields of the MEPSC8/UHPLC–PDA methodology were found between 78.1 (syringic acid) and 99.6% (o-coumaric acid) for red wines and between 76.2 and 99.1% for white wines. The inter-day precision, expressed as the relative standard deviation (RSD%), varied between 0.2% (p-coumaric and o-coumaric acids) and 7.5% (gentisic acid) while the intra-day precision between 0.2% (o-coumaric and cinnamic acids) and 4.7% (gallic acid and (−)-epicatechin). On the basis of analytical validation, it is shown that the MEPSC8/UHPLC–PDA methodology proves to be an improved, reliable, and ultra-fast approach for wine bioactive phenolics analysis, because of its capability for determining simultaneously in a single chromatographic run several bioactive metabolites with high sensitivity, selectivity and resolving power within only 10 min. Preliminary studies have been carried out on 34 real whole wine samples, in order to assess the performance of the described procedure. The new approach offers decreased sample preparation and analysis time, and moreover is cheaper, more environmentally friendly and easier to perform as compared to traditional methodologies.

A fast method using a new hydrophilic–lipophilic balanced sorbent in combination with ultra-high performance liquid chromatography for quantification of significant bioactive metabolites in wines

This manuscript describes the development and validation of an ultra-fast, efficient, and high throughput analytical method based on ultra-high performance liquid chromatography (UHPLC) equipped with a photodiode array (PDA) detection system, for the simultaneous analysis of fifteen bioactive metabolites: gallic acid, protocatechuic acid, (−)-catechin, gentisic acid, (−)-epicatechin, syringic acid, p-coumaric acid, ferulic acid, m-coumaric acid, rutin, trans-resveratrol, myricetin, quercetin, cinnamic acid and kaempferol, in wines. A 50-mm column packed with 1.7-μm particles operating at elevated pressure (UHPLC strategy) was selected to attain ultra-fast analysis and highly efficient separations. In order to reduce the complexity of wine extract and improve the recovery efficiency, a reverse-phase solid-phase extraction (SPE) procedure using as sorbent a new macroporous copolymer made from a balanced ratio of two monomers, the lipophilic divinylbenzene and the hydrophilic N-vinylpyrrolidone (Oasis™ HLB), was performed prior to UHPLC–PDA analysis. The calibration curves of bioactive metabolites showed good linearity within the established range. Limits of detection (LOD) and quantification (LOQ) ranged from 0.006 μg mL−1 to 0.58 μg mL−1, and from 0.019 μg mL−1 to 1.94 μg mL−1, for gallic and gentisic acids, respectively. The average recoveries ± SD for the three levels of concentration tested (n = 9) in red and white wines were, respectively, 89 ± 3% and 90 ± 2%. The repeatability expressed as relative standard deviation (RSD) was below 10% for all the metabolites assayed. The validated method was then applied to red and white wines from different geographical origins (Azores, Canary and Madeira Islands). The most abundant component in the analysed red wines was (−)-epicatechin followed by (−)-catechin and rutin, whereas in white wines syringic and p-coumaric acids were found the major phenolic metabolites. The method was completely validated, providing a sensitive analysis for bioactive phenolic metabolites detection and showing satisfactory data for all the parameters tested. Moreover, was revealed as an ultra-fast approach allowing the separation of the fifteen bioactive metabolites investigated with high resolution power within 5 min.

Light exercise causes adaptive changes in muscles of young Brasileiro de Hipismo horses

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

Development and validation of HPLC method for analysis of dexamethasone acetate in microemulsions

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A rapid, environmentally friendly, and reliable method for pesticide analysis in high-fat samples

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

Mathematical equation correction to spectral and transport interferences in high-resolution continuum source flame atomic absorption spectrometry: determination of lead in phosphoric acid

Um método de correção de interferência espectral e de transporte é proposto, e foi aplicado para minimizar interferências por moléculas de PO produzidas em chama ar-acetileno e de transporte causada pela variação da concentração de ácido fosfórico. Átomos de Pb e moléculas de PO absorvem a 217,0005 nm, então Atotal217,0005 nm = A Pb217,0005 nm + A PO217,0005 nm. Monitorando o comprimento de onda alternativo de PO em 217,0458 nm, é possível calcular a contribuição relativa de PO na absorbância total a 217,0005 nm: A Pb217,0005 nm = Atotal217,0005 nm - A PO217,0005 nm = Atotal217,0005 nm - k (A PO217,0458 nm). O fator de correção k é a razão entre os coeficientes angulares de duas curvas analíticas para P obtidas a 217,0005 e 217,0458 nm (k = b217,0005 nm/b217,0458 nm). Fixando-se a taxa de aspiração da amostra em 5,0 ml min-1, e integrando-se a absorbância no comprimento de onda a 3 pixels, curvas analíticas para Pb (0,1 - 1,0 mg L-1) foram obtidas com coeficientes de correlação típicos > 0,9990. As correlações lineares entre absorbância e concentração de P nos comprimentos de onda 217,0005 e 217,0458 foram > 0,998. O limite de detecção de Pb foi 10 µg L-1. O método de correção proposto forneceu desvios padrão relativos (n=12) de 2,0 a 6,0%, ligeiramente menores que os obtidos sem correção (1,4-4,3%). As recuperações de Pb adicionado às amostras de ácido fosfórico variaram de 97,5 a 100% (com correção pelo método proposto) e de 105 a 230% (sem correção).

Effect of Ionic Liquid on the Determination of Aromatic Amines as Contaminants in Hair Dyes by Liquid Chromatography Coupled to Electrochemical Detection

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