Sample preparation of polymers for halogen determination requires special attention because they are difficult to bring into solution and due to the risk of analyte losses when using acid digestion. A method using microwave-induced combustion (MIC) was optimized for accurate determination of halogens in polymeric parts obtained in waste of electrical and electronic equipment. Results were compared with those by using microwave-assisted extraction (MAE) with alkaline solution and microwave-assisted wet digestion (MAWD) using concentrated nitric acid, which are common choices for sample preparation. In this particular case, the MAE method was not suitable and underestimated results were obtained, showing the necessity for the complete digestion. Even with the use of MAWD under high temperature and pressure, incomplete digestion and high acid content were obtained, which were unsuitable for analysis and resulted in poor recovery. Only by using MIC (diluted ammonia as absorbing solution) acceptable recoveries (95 to 104%) and agreement with certified values for the certified reference materials (CRMs) of polymers were obtained. Thus, a suitable method for all halogen to be determined by ion chromatography (IC) or inductively coupled plasma mass spectrometry (ICP-MS), with the exception of F, was obtained in agreement with the requirements by the Restriction of the Use of Certain Hazardous Substances (RoHS) European directive.

Oxidation using diluted HNO3 solution is dependent on reactions taking place in the gas phase, resulting in HNO3 regeneration, thus allowing sub stoichiometric reactions (16.7 mmol of C oxidized with 10.4 mmol of HNO3). Reactions for HNO3 regeneration are dependent on temperature gradient along reaction vessel. Thermographic images were obtained of external vessel wall after 2.5, 5 and 7.5 min of heating. Temperature inside reaction vessel was directly measured using a sapphire thermocouple in four different depth (3, 6, 12 and 16 cm). Reactions under inert atmosphere (7.5 bar Ar) were evaluated and normally presented higher temperature gradient than that performed with O2 pressure, since HNO3 regeneration reactions are exothermic. A better understanding of the regeneration of HNO3 and the dependence on the whole reaction vessel temperature in this system was possible combined to residual carbon content and residual acidity measurements to estimate the extent of organic matter oxidation.

A method for digestion of crude oil distillation residues (atmospheric residue, AR and vacuum residue, VR) using microwave-induced combustion (MIC) was developed for simultaneous determination of metals (Ba, Co, Fe, Mg, Mn, Ni and V) and sulfur by inductively coupled plasma optical emission spectrometry (ICP-OES). Samples were wrapped in polyethylene films and combusted using 20 bar of oxygen. Nitric acid solutions were evaluated using 5 min of reflux after combustion. Accuracy was evaluated using certified reference material and comparison with the results obtained by microwave-assisted wet digestion (MAWD). No statistical difference was observed between the certified values and those obtained using MIC as well as between the values obtained using MAWD or MIC. In spite of both methods have been apparently suitable for crude oil digestion, MIC was preferable in view of the possibility of using 3 mol L-1 HNO3 as absorbing solution. Furthermore, it is important to notice that using MIC, C content in digests was lower than 10 mg L-1, preventing interferences in ICP-OES. In addition, the simultaneous digestion of eight samples was possible in less than 30 min and without using concentrated acids and/or longer heating times, making the proposed method well-suited for routine analysis.

In this work, a method using microwave-induced combustion (MIC) was optimized in order to obtain a fast, simple, efficient and greener sample preparation method for coal digestion and further determination of sulfur by inductively coupled plasma optical emission spectrometry (ICP OES). Accuracy was evaluated by comparison of the results with those obtained using elemental analysis by UV-fluorescence, microwave-assisted acid digestion with determination by ICP OES and by analysis of certified reference materials of coal. Some parameters that influence MIC method, such as the type and concentration of absorbing solution, the necessity of using a reflux step as well as the cooling time were carefully optimized. No statistical difference was observed for combustion without reflux followed by 5 min of cooling, in comparison to the reference values obtained by elemental analysis. Complete digestion was obtained with this fast and simple method (total digestion program required only 6 min) and using a diluted acid solution for quantitative recovery. The feasibility of digests for sulfur determination as sulfate by ion chromatography (IC) with conductivity detection was also demonstrated. The possibility of determining other elements, commonly monitored in coals, is another advantage of this high-efficiency digestion method (MIC) combined with the multielemental capacity of ICP OES or IC instruments.

In this work, solutions of oxidant salts were evaluated as alternative to nitrate solution for the ignition step in microwave-induced combustion (MIC) method. Aqueous solutions of KClO4, K2Cr2O7, KMnO4 and K2S2O8 in several concentrations were evaluated and it was observed that the ignition was dependent on the concentration and type of igniter solution. Moreover, it was possible to observe that ignition and combustion times are not related with sample mass, which was confirmed by evaluating sample masses ranging from 100 to 500 mg of whole milk powder. Certified reference materials were digested using K2Cr2O7 as igniter solution and digests analyzed by inductively coupled plasma optical emission spectrometry (ICP OES), with good agreement to certified values. The obtained results suggest that MIC can be performed using solutions of oxidants salts. In addition, the proposed study contributed to a better undestanding and explaining the ignition with microwaves.

We herein described the preparation of a novel series of limonin derivatives (modification in A-ring), which was synthesized efficiently using methodology in solution as well as in heterogeneous medium (K-10). In addition, we obtained derivatives by inserting the 1,2,3-triazole nucleus via click reaction and also prepared derivatives from reactions with limonin-7-oxime. All compounds were submitted to investigation of the antimicrobial activity against a collection of microorganisms. The results of the antimicrobial activity, in general, demonstrated that a relevant number of synthetic derivatives presented higher activity than the natural product.

Este trabalho tem como objetivo determinar a eficácia do óleo essencial deA. gratissima como anestésico para jundiás, bem como realizar o fracionamento bio-guiado do óleo essencial a fim de isolar os compostos responsáveis pelos efeitos observados. Os peixes foram submetidos ao banho-anestésico com óleo essencial, suas frações e compostos isolados para determinar o tempo de indução e recuperação da anestesia. O eugenol (50 mg L-1) foi utilizado como controle positivo. O óleo essencial deA. gratissima promoveu anestesia em concentrações de 300 a 900 mg L-1. Os peixes apresentaram contrações musculares involuntárias durante indução e recuperação. Com o fracionamento bio-guiado do óleo essencial foram obtidos E-(-)-pinocanfona, (-)-óxido de cariofileno, (-)-guaiol e (+)-espatulenol. A E-(-)-pinocanfona promoveu os mesmos efeitos adversos observados com o óleo essencial. (-)-Óxido de cariofileno, (-)-guaiol e (+)-espatulenol demonstraram apenas efeitos sedativos nas concentrações proporcionais ao óleo essencial. O (+)-espatulenol (51.2 mg L-1) promoveu anestesia profunda sem efeitos adversos. Uma maior concentração de (+)-espatulenol e menores quantidades ou ausência deE-(-)-pinocanfona poderiam contribuir para melhorar a atividade anestésica e segurança do óleo essencial de A. gratissima. O (+)-espatulenol apresentou potente atividade sedativa e anestésica em jundiás, e poderia ser considerado um composto viável para o desenvolvimento de um novo anestésico.

This work aimed to determine the efficacy of the essential oil of A. gratissima as anesthetic for silver catfish, and to perform the bio-guided fractionation of essential oil aiming to isolate compounds responsible for the noted effects. Fish were submitted to anesthesia bath with essential oil, its fractions and isolated compounds to determine time of anesthetic induction and recovery. Eugenol (50 mg L-1) was used as positive control. Essential oil of A. gratissima was effective as an anesthetic at concentrations of 300 to 900 mg L-1. Fish presented involuntary muscle contractions during induction and recovery. The bio-guided fractionation of essential oil furnishedE-(-)-pinocamphone, (-)-caryophyllene oxide, (-)-guaiol and (+)-spathulenol. E-(-)-pinocamphone caused the same side effects observed for essential oil. (-)-Caryophyllene oxide, (-)-guaiol and (+)-spathulenol showed only sedative effects at proportional concentrations to those of the constituents in essential oil. (+)-Spathulenol (51.2 mg L-1) promoted deep anesthesia without side effects. A higher concentration of (+)-spathulenol, and lower or absent amounts ofE-(-)-pinocamphone could contribute to increase the activity and safety of the essential oil of A. gratissima. (+)-Spathulenol showed potent sedative and anesthetic activities in silver catfish, and could be considered as a viable compound for the development of a new anesthetic.

A solid sampling electrothermal vaporization inductively coupled plasma optical emission spectrometry (ETV-ICP OES) method for determination of As, Cd, Cr, Cu, Mn, Mo, Ni, Pb, Pd, Pt, Rh, Ru and V in pharmaceuticals is proposed. Tricyclic pharmaceuticals were directly analyzed due to their difficult decomposition with acids. Pyrolysis and vaporization temperature, sample mass, and reaction gas (Freon) flow rate were evaluated. The effect of organic and inorganic compounds was evaluated for matrix matching. The limits of detection ranged from 0.04 µg g−1 (Cu) to 107 µg g−1 (As) and the relative standard deviation was lower than 10%. The investigated elements were not detected in the analyzed samples with the exception of Cr in cyclobenzaprine hydrochloride. Since there was no certified reference materials available for metals and metalloids in pharmaceuticals, the accuracy of the method was evaluated by an independent technique and by analyte recovery. Inductively coupled plasma mass spectrometry was employed for analyte determination after sample decomposition by microwave induced combustion. The agreement of the results found by both techniques was better than 87% and analyte recoveries ranged from 91 to 103%.

A pirohidrólise foi utilizada no preparo de amostras de carbeto de silício (SiC) para posterior determinação de B usando espectrometria de emissão óptica com plasma indutivamente acoplado (ICP-OES) e espectrometria de massa com plasma indutivamente acoplado (ICP-MS). Parâmetros importantes como temperatura, fluxo de água e ar, tempo de reação e uso de V2O5 foram avaliados. Adicionalmente, foi avaliada a interferência de W sobre as linhas de emissão de B durante as determinações por ICP-OES. A exatidão foi avaliada usando material de referência certificado (CRM BAM S003) e valor de bias inferior a 1% foi encontrado entre os valores de referência e obtido experimentalmente. Limite de detecção (LOD) de 0,010 μg g−1 foi obtido usando pirohidrólise e determinação por ICP-MS. A pirohidrólise é um método de preparo de amostras simples que permitiu a utilização de água deionizada como solução absorvedora para a determinação de B em SiC.

Pyrohydrolysis was used for sample preparation of silicon carbide (SiC) and subsequent determination of B using inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). Important parameters for pyrohydrolysis method as temperature, air and water flow rates, reaction time and use of V2O5 were evaluated. In addition, a study of W spectral interference on B emission lines was evaluated for ICP-OES determination. Accuracy was evaluated using certified reference material (CRM BAM S003) and bias value lower than 1% between the certified and determined value was achieved. Limit of detection (LOD) of 0.010 μg g−1 was obtained using pyrohydrolysis and ICP-MS. Pyrohydrolysis is a very simple sample preparation method that allowed the use of deionized water as absorbing solution for B determination in SiC.

Radiação micro-ondas em sistema fechado foi utilizada para a remoção de sedimentos de emulsão de petróleo para a posterior caracterização em laboratório. O programa de aquecimento do forno de micro-ondas foi otimizado através da avaliação do tempo de aquecimento (5 a 30 s) e da potência de micro-ondas (300 a 1400 W). O teor de sedimentos foi determinado usando um procedimento de filtração com membrana conforme recomendado pela norma ASTM D 4807-05, antes e após a remoção de sedimentos. Os teores de água e cloreto foram determinados no óleo obtido após a remoção de sedimentos. Até oito amostras de 20 g puderam ser processadas simultaneamente. A eficiência de remoção de sedimentos foi superior a 95%. Foi possível a obtenção de petróleo virtualmente isento de água, sal e sedimentos, permitindo a determinação de parâmetros como gravidade API, densidade, viscosidade e número de acidez total sem interferências causadas por sedimentos ou mesmo sal e água.

Microwave radiation in closed vessels was applied for removal of sediments from crude oil allowing the subsequent crude oil characterization in laboratory. Heating time and microwave power were evaluated in the range of 5 to 30 s and 300 to 1400 W, respectively. Sediment content was determined using the method recommended by ASTM D 4807-05 based on a filtration step in a membrane before and after sediment removal. Water and chloride contents were determined in the oil phase obtained after sediment removal. Up to eight samples of 20 g of crude oil could be simultaneously processed. Sediment removal efficiency was better than 95%. It was possible to obtain crude oil in a suitable condition for determination of routine parameters as API gravity, density, viscosity and total acid number without interferences caused by sediments or even water and salt.

A method based on pyrohydrolysis was proposed for cement sample preparation and further chloride determination by spectrophotometry using flow injection analysis. Analytical parameters were evaluated and, under the selected conditions, the calibration curve was linear in the range of 0.2 to 10.0 µg mL-1 with r2 = 0.998. The limit of detection was5 µg g-1 of chloride and the relative standard deviation was less than 7%. The proposed pyrohydrolysis method is relatively simple and can be used for sample preparation for further spectrophotometric determination of low concentrations of chloride in cement.

A determinação de fluoreto por eletrodo íon seletivo (ISE) em nanotubos de carbono (CNTs) é proposta após a decomposição por piroidrólise. Até 1 g de amostra pode ser decomposta, obtendo-se assim baixos limites de detecção (1,5 μg g-1), boa precisão (RSD < 5%) e exatidão (concordância maior do que 95% com os valores dos materiais de referencia certificados (CRMs) e combustão iniciada por microondas (MIC)). O fluoreto é absorvido em água e a solução resultante pode ser analisada diretamente por ISE. A pirohidrólise é simples de ser executada e não requer instrumentação sofisticada, sendo bastante atrativa para controle de fluoreto em NTCs em análises de rotina.

Fluoride determination by ion selective electrode (ISE) in carbon nanotubes (CNTs) is proposed after pyrohydrolysis decomposition. Up to 1 g of CNTs could be decomposed improving the limit of detection (1.5 μg g-1), precision (RSD < 5%) and accuracy (agreement higher than 95% with values of certified reference materials (CRMs) and microwave-induced combustion (MIC)). Fluoride could be absorbed in water and the resulting solution can be analyzed by ISE. Pyrohydrolysis is easy to be performed and does not require any sophisticated instrumentation, which is attractive for routine fluoride control in CNTs.

Elementos traço e majoritários foram determinados em mexilhão dourado (Limnoperna fortunei) coletados no canal São Gonçalo (Rio Grande-RS, Brasil). Digestão assistida por microondas em sistema fechado foi utilizada para decomposição das amostras com subsequente determinação elementar por técnicas espectrométricas. Os resultados mostraram que o tecido de mexilhão contém Ag, Al, As, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, Li, Mg, Mn, Mo, P, Pb, S, Sn, Sr, Ti, V e Zn, enquanto que na casca foram encontrados os mesmo elementos, exceto Ag e Hg, evidenciando seu potencial como biomarcador. Neste sentido, estes resultados podem ser utilizados para estabelecer um panorama inicial e contribuir para futuros estudos relacionados a contaminantes inorgânicos na área estudada.

Major and trace element content was determined in golden mussel (Limnoperna fortunei) collected in the São Gonçalo Channel (Rio Grande City, Brazil). A microwave-assisted digestion procedure in closed vessels was applied to mussel decomposition and subsequent determination of elements by spectrometric techniques. Results showed that the mussel tissue contains Ag, Al, As, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, Li, Mg, Mn, Mo, P, Pb, S, Sn, Sr, Ti, V and Zn, while the same elements (except Ag and Hg) were quantified in its shell, demonstrating its potential as a biomarker. In this sense, these results can be used to establish an initial view and to contribute to further studies related to element contamination in the area under study.

Neste trabalho foi utilizada a piroidrólise para a decomposição de suplemento mineral utilizado na nutrição animal, para a posterior determinação de F, Br e I. Flúor foi determinado por potenciometria utilizando eletrodo íon-seletivo para fluoreto, enquanto que Br e I foram determinados por espectrometria de massa com plasma indutivamente acoplado. Os principais parâmetros que influenciam a piroidrólise foram investigados e, após a devida avaliação dos mesmos, foram fixadas as seguintes condições: a temperatura do reator em 1000 °C durante 10 min; a proporção entre a massa de amostra e a massa de acelerador em 1 + 5 e a vazão do gás carreador em 200 mL min-1. A exatidão do método foi avaliada usando teste de recuperação do analito e análise de materiais de referência certificados de rocha fosfática e de solo. O método foi aplicado para análise de suplemento mineral. Os limites de quantificação foram de 16, 0,3 e 0,07 µg g-1 para F, Br e I, respectivamente. Assim, usando-se um método relativamente simples e de baixo custo é possível a decomposição de até 5 amostras por hora. Portanto, a piroidrólise pode ser usada como um método de rotina para o preparo de amostra de suplemento mineral para a determinação de F, Br e I.

Pyrohydrolysis was employed for mineral supplements decomposition prior to F, Br and I determination. Fluoride determination was carried out by potentiometry using a fluoride-ion selective electrode, whereas Br and I were determined by inductively coupled plasma mass spectrometry. The main parameters that influence on pyrohydrolysis were investigated. After evaluation, the following conditions were established: reactor temperature of 1000 ºC during 10 min; sample plus accelerator mass ratio of 1 + 5 and carrier gas (air) flow rate of 200 mL min-1. The accuracy of the proposed method was evaluated by analyte recovery tests and analysis of certified reference materials of phosphate rock and soil. Commercial mineral supplement samples were analyzed. The limits of quantification were 16, 0.3 and 0.07 µg g-1 for F, Br and I, respectively. By using a relatively simple and low cost pyrohydrolysis system up to 5 samples can be processed per hour. The developed sample preparation procedure can be routinely employed for F, Br and I determination in mineral supplements.

Um método para determinação simultânea de ácido clavulânico (CA) e amoxicilina (AMO) foi desenvolvido utilizando a técnica de espectroscopia no infravermelho médio com transformada de Fourier acoplada ao acessório de reflexão total atenuada (ATR/FTIR). Utilizaram-se 27 e 8 amostras para os conjuntos de calibração e previsão, respectivamente. Os modelos de calibração foram desenvolvidos utilizando os algoritmos por mínimos quadrados parciais (PLS), PLS por intervalo (iPLS), PLS por sinergismo (siPLS) e PLS por exclusão (biPLS). Os melhores modelos foram aqueles que utilizaram o algoritmo biPLS. Obtiveram-se erro padrão relativo de previsão (RSEP) de 3,8 e 5,1% para CA e AMO, respectivamente. Os resultados obtidos pela metodologia proposta foram comparados com os obtidos por cromatografia líquida de alta eficiência (HPLC) e nenhuma diferença significativa foi observada. O método proposto utilizando ATR/FTIR associado a métodos de análise multivariados foi satisfatório para determinação de CA e AMO em produtos farmacêuticos.

A method for simultaneous determination of clavulanic acid (CA) and amoxicillin (AMO) was developed using Fourier transform mid infrared technique coupled with attenuated total reflectance (ATR/FTIR) accessory. 27 samples were used as calibration set and 8 samples were used for prediction set. Calibration models were developed using partial least squares (PLS), interval PLS (iPLS), synergy PLS (siPLS) and backward PLS (biPLS). Multiplicative scatter correction and the mean centering were used and produced the best models. Relative standard error of prediction (RSEP) of 3.8% for CA and 5.1% for AMO were obtained using biPLS algorithm for ATR/FTIR data. Results obtained by the proposed methodology were compared with those using high performance liquid chromatography (HPLC) and no significant differences were obtained. The proposed method using ATR/FTIR combined to multivariate analysis methods was suitable for the simultaneous determination of CA and AMO in commercial pharmaceutical products.