Resumo em Português:

Neste trabalho investigou-se a atividade fotodinâmica de octaetilporfirina (OEP), octaetilporfirina de vanadil (VOOEP) e meso-tetramesitilporfirina (m-TMP). Este estudo foi realizado através da determinação da constante da velocidade de fotoxidação (k f) do aminoácido triptofano (Trp). A participação do oxigênio singlete nesta fotoxidação foi determinada através da adição de azida de sódio e água deuterada no meio de reação. Os valores de k f/10-4s-1 para a fotoxidação de Trp demonstraram que OEP (2,80 ± 0.05) é mais eficiente do que m-TMP (1,62 ± 0,07) e VOOEP (0,81 ± 0,08). Os valores de k f foram menores na presença de azida de sódio e maiores na presença de água deuterada, sugerindo que o oxigênio singlete é o responsável pela atividade fotodinâmica de OEP, VOOEP e m-TMP. Estes resultados sugerem também que as diferenças na atividade fotodinâmica entre as porfirinas podem ser associadas com as diferenças na estrutura molecular das mesmas. A presença do grupo vanadil (V=O) interfere claramente na atividade fotodinâmica de OEP causando considerável redução na sua eficiência.

Resumo em Inglês:

In this work an investigation of the photodynamic efficiency of octaethylporphyrin (OEP), vanadyl octaethylporphyrin (VOOEP), and meso-tetramesitylporphyrin (m-TMP) was done. This study was performed by the determination of photoxidation rate constants (k f) of the tryptophan amino acid (Trp). The mechanism involved in the photoxidation of Trp was also studied using sodium azide (singlet oxygen scavenger) and deuterium oxide. The values of k f/10-4s-1 for Trp photoxidation demonstrated that OEP (2.80 ± 0.05) is more efficient than m-TMP (1.62 ± 0.07) and VOOEP (0.81 ± 0.08). The values of k f were reduced by the presence of sodium azide and increased by deuterium oxide indicating that singlet oxygen is responsible by OEP, VOOEP, and m-TMP photoactivity. These results indicated that differences in the photodynamic activity between porphyrins could be associated with differences in their molecular structures. The presence of vanadyl group (V=O) interferes clearly in the photodynamic activity of OEP causing a considerable reduction in its efficiency.

Resumo em Inglês:

Specific combustion programs (Gaseq, Chemical equilibria in perfect gases, Chris Morley) are used to model dioxin and formation in the incineration processes of urban solid wastes. Thanks to these programs, it is possible to establish correlations with the formation mechanisms postulated in literature on the subject. It was found that minimum oxygen quantities are required to obtain a significant formation of these compounds and that more furans than dioxins are formed. Likewise, dioxin and furan formation is related to the presence of carbon monoxide, and dioxin and furan distribution among its different compounds depends on the chlorine and hydrogen relative composition. This is due to the fact that an increased chlorine availability leads to the formation of compounds bearing a higher chlorine concentration (penta-, hexa-, hepta-, and octachlorides), whereas an increased hydrogen availability leads to the formation of compounds bearing a lower chlorine number (mono, di-, tri-, and tetrachlorides).

Resumo em Inglês:

Two simple, rapid and cost-effective methods based on titrimetric and spectrophotometric techniques are described for the assay of RNH in bulk drug and in dosage forms using silver nitrate, mercury(II)thiocyanate and iron(III)nitrate as reagents. In titrimetry, an aqueous solution of RNH is treated with measured excess of silver nitrate in HNO3 medium, followed by determination of unreacted silver nitrate by Volhard method using iron(III) alum indicator. Spectrophotometric method involve the addition a known excess of mercury(II)thiocyanate and iron(III)nitrate to RNH, followed by the measurement of the absorbance of iron(III)thiocyante complex at 470 nm. Titrimetric method is applicable over 4-30 mg range and the reaction stoichiometry is found to be 1:1 (RNH: AgNO3). In the spectrophotometric method, the absorbance is found to increase linearly with concentration of RNH which is corroborated by the correlation coefficient of 0.9959. The system obey Beer's law for 5-70 µg mL-1. The calculated apparent molar absorptivity and sandell sensitivity values are found to be 3.27 <FONT FACE=Symbol>´</FONT> 10³ L mol-1 cm-1, 0.107 µg cm-2 respectively. The limits of detection and quantification are also reported for the spectrophotometric method. Intra-day and inter-day precision and accuracy of the methods were evaluated as per ICH guidelines. The methods were successfully applied to the assay of RNH in formulations and the results were compared with those of a reference method by applying Student's t and F-tests. No interference was observed from common pharmaceutical excipients. The accuracy of the methods was further ascertained by performing recovery tests by standard addition method.

Resumo em Português:

A degradação fotocatalítica de imazetapir, um herbicida da família das imidazolinonas, em suspensão aquosa de dióxido titânio foi investigada na presença de dois receptores de elétrons como persulfato de potássio e periodato de sódio, assim como na presença de dois sais inorgânicos como sulfato de sódio e dihidrogenofosfato de sódio a 30ºC. O modelo cinético de pseudo-primeira ordem foi empregado para discutir os resultados. O desaparecimento de imazetapir em função do tempo de irradiação foi analisado por cromatografia líquida de alta eficiência. Entre os dois oxidantes estudados a degradação foi mais rápida quando se adicionou o periodato de sódio, enquanto a presença do sulfato de sódio retarda a degradação de imazetapir mais que o dihidrogenofosfato na suspensão de TiO2.

Resumo em Inglês:

Photocatalytic degradation of imazethapyr, an imidazolinone family herbicide, was investigated in titanium dioxide aqueous suspension in the presence of electron acceptors such as potassium persulfate and sodium periodate, as well as in the presence of two inorganic salts such as sodium sulfate and sodium dihydrogen phosphate at 30ºC. A pseudo-first order kinetic model was used to discuss the results. The imazethapyr disappearance as a function of the radiation time was analyzed by high performance liquid chromatography. In comparison between two oxidants, the degradation was faster in the presence of periodate, meanwhile in the presence of the inorganic salt sodium sulfate retarded the oxidation more than dihydrogen phosphate ions in the TiO2 suspension.

Resumo em Inglês:

The need to clean-up heavy metal contaminated environment can not be over emphasized. This paper describes the adsorption isotherm studies of Cd (II), Pb (II) and Zn (II) ions from aqueous solution using unmodified and EDTA-modified maize cob. Maize cob was found to be an excellent adsorbent for the removal of these metal ions. The amount of metal ions adsorbed increased as the initial concentration increased. Also, EDTA - modification enhanced the adsorption capacity of maize cob probably due to the chelating ability of EDTA. Among the three adsorption isotherm tested, Dubinin-Radushkevich gave the best fit with R² value ranging from 0.9539 to 0.9973 and an average value of 0.9819. This is followed by Freundlich isotherm (Ave. 0.9783) and then the Langmuir isotherm (Ave. 0.7637). The sorption process was found to be a physiosorption process as seen from the apparent energy of adsorption which ranged from 2.05KJ\mol to 4.56KJ\mol. Therefore, this study demonstrates that maize cob which is an environmental pollutant could be used to adsorb heavy metals and achieve cleanliness thereby abating environmental nuisance caused by the maize cob.

Resumo em Português:

Foi desenvolvido um método espectrofotométrico para a determinação de biureto em fertilizantes à base de uréia empregando Cu(OH)2(s) como reagente analítico. O método se baseia na reação entre biureto e Cu(OH)2(s) e formação do complexo Cu(C2N3O2H5)2 de coloração violeta cujo espectro apresenta máximo de absorção em 510 nm. Após o estabelecimento das melhores condições analíticas, o método proposto foi aplicado na determinação de biureto em duas amostras comerciais de uréia, uma para pecuária e outra para agricultura. Curvas analíticas construídas no intervalo de concentrações de 0,1 a 0,5% (m/v) em biureto produziram coeficientes de correlação típicos > 0,9990. Os resultados obtidos pelo método proposto foram concordantes ao nível de 95% de confiança com os obtidos por um método alternativo empregando espectrometria de absorção atômica. A exatidão do método foi também avaliada por meio de testes de adição e recuperação de padrão. Recuperações de 92 a 100% foram obtidas e o desvio padrão relativo calculado para 12 medidas sucessivas de uma amostra contendo 0,31% (m/v) foi 2%.

Resumo em Inglês:

A spectrophotometric method for the determination of biuret in urea-based fertilizers using Cu(OH)2(s) as analytical reagent is proposed. The principle of the method is the reaction between biuret and Cu(OH)2 (s) and formation of the purple complex Cu(C2N3O2H5)2 that presents absorption maximum at 510 nm. After establishment of analytical conditions, the method was applied to the determination of biuret in two commercial urea samples used as fertilizer and foodstuffs in agriculture. For analytical solutions prepared in the 0.1 - 0.5% (m/v) biuret, analytical curves with typical correlation coefficient of 0.9990 were always obtained. Results obtained by the proposed procedure were in agreement with those obtained by atomic absorption spectrometry at 95% confidence level. Accuracy was also evaluated by means of addition and recovery tests using spiked samples with biuret. Recoveries in the 92 - 100% were obtained and the calculated relative standard deviation of a sample containing 0.31% (m/v) biuret after twelve successive measurements was 2%.

Resumo em Português:

Neste trabalho realizou-se a extração das substâncias húmicas (SH) provenientes da turfa coletada às margens do rio Mogi-Guaçu, segundo metodologia descrita por Rosa et al., 2000. As SH foram fracionadas em um equipamento de ultrafiltração em três faixas de tamanhos moleculares 30 - 100 KDa, <30 KDa e >100 KDa. As frações foram caracterizadas por diferentes técnicas analíticas, infravermelho (IV), análise elementar, espectroscopia na região do ultravioleta/visível (UV/Vis) e ressonância paramagnética eletrônica (EPR). Verificou-se que as frações de menor tamanho molecular (30 - 100 KDa e <30 KDa) possuem um maior número de moléculas com oxigênio ligados, enquanto que a fração de maior tamanho molecular (>100 KDa) apresentou um maior número de moléculas aromáticas. Através dos resultados das análises elementares e de ressonância paramagnética eletrônica, constatou-se que a fração <30 KDa apresentou uma menor porcentagem de carbono, nitrogênio e hidrogênio e uma menor quantidade de radicais livres em relação as demais, indicando que esta fração possui um menor número de anéis aromáticos conjugados. Já nas análises por IV foram observadas bandas características das SH.

Resumo em Inglês:

In this work have been realized the extration of húmic substances (SH) proceeding from the peat collected to the edges of the river Mogi-Guaçu, according to described methodology for Rosa et al., 2000. The SH had been fractions in an equipment of ultrafiltration in three molecular sizes: between molecular sizes 30 -100 KDa, less than 30 KDa molecular sizes and more than 100 KDa. The fractions had been characterized by different analytical techniques such electron paramagnetic resonance (EPR), infrared spectroscopy, elemental analysis and spectroscopy in the region visible (UV/Vis). It was verified that the fractions of lesser molar mass between 30 - 100 KDa molecular sizes and less than molecular sizes presented a bigger on molecule number with oxygen while that the fraction of bigger molar mass more than100 KDa molecular sizes presented a bigger number aromatical molecules. Through the results of the elementary analyses and eletronic paramagnetic resonance, the fraction evidenced less than 30 KDa showing smaller percentagens of carbon, nitrogen and hydrogen and a smaller amount of free radicals in relation to the othess, indicating that this fraction possess a smaller number of conjugated aromatical rings. Already in the analyses for IV characteristic bands of the SH had been observed.

Resumo em Inglês:

Two sensitive spectrophotometric methods are described for the determination of lansoprazole (LPZ) in bulk drug and in capsule formulation. The methods are based on the oxidation of lansoprazole by insitu generated bromine followed by determination of unreacted bromine by two different reaction schemes. In one procedure (method A), the residual bromine is treated with excess of iron (II), and the resulting iron (III) is complexed with thiocyanate and measured at 470 nm. The second approach (method B) involves treating the unreacted bromine with a measured excess of iron (II) and remaining iron (II) is complexed with orthophenanthroline at a raised pH, and measured at 510 nm. In both methods, the amount of bromine reacted corresponds to the amount of LPZ. The experimental conditions were optimized. In method A, the absorbance is found to decrease linearly with the concentration of LPZ (r = -0.9986) where as in the method B a linear increase in absorbance occurs (r = 0.9986) The systems obey Beer's law for 0.5-4.0 and 0.5-6.0 µg mL-1 for method A and method B, respectively. The calculated molar absorptivity values are 3.97µ10(4) and 3.07µ10(4) L mol-1cm-1 for method A and method B, respectively, and the corresponding Sandell sensitivity values are 0.0039 and 0.0013 µg cm-2. The limit of detection (LOD) and quantification (LOQ) are also reported for both methods. Intra-day and inter-day precision, and accuracy of the methods were established as per the current ICH guidelines. The methods were successfully applied to the determination of LPZ in capsules and the results tallied well with the label claim and the results were statistically compared with those of a reference method by applying the Student's t-test and F-test. No interference was observed from the concomitant substances normally added to capsules. The accuracy and validity of the methods were further ascertained by performing recovery experiments via standard-addition method.

Resumo em Português:

A nicotina, um agente oxidante, é certamente um dos alcalóides mais amplamente utilizados no mundo. Juntamente com seu principal metabolito, a cotinina, a nicotina é responsável pela tabaco-dependência. O uso de tabaco está intimamente associado a doenças pulmonares, modificações morfológicas em leucócitos e a geração de espécies oxidantes. O principal objetivo deste estudo foi identificar uma possível relação entre cotinina, geração de espécies reativas do oxigênio e processos oxidativos. Após o estudo da ação da cotinina em diferentes modelos químicos e em cinéticas enzimáticas com peroxidases (mieloperoxidase e peroxidase de raiz forte), conclui-se que a cotinina não age diretamente sobre H2O2, HOCl, taurine cloramina, peroxidase de raiz forte ou mieloperoxidase.

Resumo em Inglês:

Nicotine, an oxidizing agent, is certainly one of the most widely used alkaloids in the world. It is, together with its main metabolite, cotinine, responsible for tobacco-dependence. The use of tobacco is closely associated with lung disease, morphological leukocyte modification and generation of oxidant species. The aim of this study was to look for a possible relationship between cotinine, oxidant species generation and oxidative processes. After studying the action of cotinine in some chemical oxidation models and on the enzymatic kinetics of peroxidases (myeloperoxidase and horseradish peroxidase), we concluded that cotinine does not act directly upon H2O2, HOCl, taurine chloramines, horseradish peroxidase or myeloperoxidase.

Resumo em Português:

A estequiometria de poliânions formados pela ação do ácido nítrico sobre a solução de tungstato de sódio (< 0,01M) foi estudada por meio de técnicas eletrométricas envolvendo titulações potenciométricas e condutométricas. As inflexões e degraus bem definidas nas curvas de titulações forneceram evidências convincentes pela existência de poliânions, para-W12O41(10-) e meta-W12O39(6-) nas faixas do pH 5,7-6,0 e 3,6-4,1; correspondendo a razão H+:WO4(2-) como 7:6 e 9:6, respectivamente. A interação entre soluções de nitrato de lantânio e tungstato de sódio a específicos níveis de pH 8,0; 5,9 e 4,0 também foi estudada por titulações potenciométricas e condutométricas, nos meios aquoso e etanólico, com cada reagente usado alternadamente como titulante. Os experimentos eletrométricos forneceram evidências incontestáveis sobre a formação de tungstatos normal-La2O3.3WO3, para-5La2O3.36WO3 e meta-La2O3.12WO3 nas proximidades de valores de pH 6,3; 5,0 e 4,2; respectivamente. Investigações analíticas sobre os precipitados formados confirmam os resultados do estudo eletrométrico.

Resumo em Inglês:

The stoichiometry of the polyanions formed by the action of nitric acid on sodium tungstate (< 0.01M) has been studied by means of electrometric techniques involving pH-potentiometric and conductometric titrations. The well defined inflections and breaks in the titration curves provide evidence for the existence of the polyanions, para-W12O41(10-) and meta-W12O39(6-) corresponding to the ratio of H+:WO4(2-) as 7:6 and 9:6 in the pH ranges 5.7-6.0 and 3.6-4.1, respectively. The interaction of lanthanum nitrate with sodium tungstate solutions, at specific pH levels 8.0, 5.9 and 4.0 was also studied by pH and conductometric titrations, in aqueous and alcoholic media, with each of the reagents alternatively used as titrant. The electrometric experiments provide definite evidence of the formation of normal-La2O3.3WO3, para-5La2O3.36WO3 and meta-La2O3.12WO3 tungstates in the vicinity of pH 6.3, 5.0 and 4.2, respectively. Analytical investigations on the precipitates formed confirm the results of the electrometric study.