Potencialidades da utilização de compostos de ródio na confecção de sensores eletroquímicos: uma breve revisão

The electrochemistry field has increased in recent years, specially in the search for new sensors to monitor specific analyte in complex samples. In order to improve electrodes, many rhodium compounds have been used as electron mediators for novel sensors development. The most used compounds for this purpose are metal, metal complexes and some organic dyes. Rhodium complexes are known by their good catalytic properties and it could be useful in the sensor field. However, there are only a few reports, on the use of rhodium complexes in sensors and biosensors. A brief review of the electrochemistry of rhodium complexes and some discription of their properties which make those compounds suitable for development of sensor and biosensor.

Métodos matemáticos para correção de interferências espectrais e efeitos interelementos na análise quantitativa por fluorescência de raios-X

One of the main problems in quantitative analysis of complex samples by x-ray fluorescence is related to interelemental (or matrix) effects. These effects appear as a result of interactions among sample elements, affecting the x-ray emission intensity in a non-linear manner. Basically, two main effects occur; intensity absorption and enhancement. The combination of these effects can lead to serious problems. Many studies have been carried out proposing mathematical methods to correct for these effects. Basic concepts and the main correction methods are discussed here.

Determination of Ni(II) in metal alloys by spectrophotometry UV-Vis using dopasemiquinone

A spectrophotometric method was proposed for Ni(II) determination in alloys using a dopa-semiquinone (L-1) to form [Ni(II)(L1-)3]1-, ε = 9.3 x 10³ L mol-1 cm-1. The optimal conditions for the determination were: wavelength 590 nm, temperature 25 °C, reaction time 45 min and pH 7.5. The Beer's law was obeyed for nickel from 3.33 x 10-5 to 1.78 x 10-4 mol L-1. The method was applied to complex samples, such as inox, nickel-titanium and cobalt-chromium alloys. A study of the potential interferents revealed that Mn was the major interferent. The limit of detection and quantification were 2.88 x 10-5 mol L-1 and 3.06 x 10-5 mol L-1, respectively.

Metabolômica, uma abordagem otimizada para exploração da biodiversidade brasileira: estado da arte, perspectivas e desafios

Brazilian biodiversity is a colossal source of secondary metabolites with remarkable structural features, which are valuable in further biodiscovery studies. In order to fully understand the relations and interactions of a living system with its surroundings, efforts in natural product chemistry are directed toward the challenge of detecting and identifying all the molecular components present in complex samples. It is plausible that this endeavor was born out of recent technological sophistication in secondary metabolite identification with sensitive spectroscopic instruments (MS and NMR) and higher resolving power of chromatographic systems, which allow a decrease in the amount of required sample and time to acquire data. Nevertheless, the escalation of data acquired in these analyses must be sorted with statistical and multi-way tools in order to select key information. Chromatography is also of paramount importance, more so when selected compounds need to be isolated for further investigation. However, in the course of pursuing a "greener" environment, new policies, with an aim to decrease the use of energy and solvents, are being developed and incorporated into analytical methods. Metabolomics could be an effective tool to answer questions on how living organisms in our huge biodiversity work and interact with their surroundings while also being strategic to the development of high value bio-derived products, such as phytotherapeutics and nutraceuticals. The incorporation of proper phytotherapeutics in the so-called Brazilian Unified Health System is considered an important factor for the urgent improvement and expansion of the Brazilian national health system. Furthermore, this approach could have a positive impact on the international interest toward scientific research developed in Brazil as well as the development of high value bio-derived products, which appear as an interesting economic opportunity in national and global markets. Thus, this study attempts to highlight the recent advances in analytical tools used in detection of secondary metabolites, which can be useful as bioproducts. It also emphasizes the potential avenues to be explored in Brazilian biodiversity, known for its rich chemical diversity.

BIOSSENSOR ELETROQUÍMICO BASEADO NA ENZIMA TIROSINASE PARA A DETERMINAÇÃO DE FENOL EM EFLUENTES

AbstractThis work describes the development of a biosensor based on the tyrosinase enzyme (Tyr) for the determination of phenol (PHEN) in laboratory effluent samples derived from ammoniacal nitrogen analysis of the water samples from the Muquém dam in the city of Cariús, CE, using square-wave voltammetry (SWV). The electrode modification consisted of the immobilization of gold nanoparticles, multi-walled carbon nanotubes, cobalt phthalocyanine, and Tyr on a glassy carbon electrode. The electrolyte, pH, enzyme quantity, and voltammetric parameters were optimized to detect PHEN. The analytical curves presented a linear range from 4.97 × 10-6 mol L-1 to 6.10 × 10-5 mol L-1, and the detection limit (DL) and quantitation limit (QL) values were 4.81 × 10-6 mol L-1 and 4.97 × 10-6mol L-1, respectively. The repetition of measurements with the same biosensor and repetition for three other prepared biosensors exhibited a relative standard deviation (RSD) of 5.50 and 1.75%, respectively. The percentage recovery of PHEN in effluent samples varied from 86.40 to 105.04%. The stability of the biosensor was evaluated (at 21 days) with satisfactory results, showing 97.86% of the initial response. Moreover, the DL and recovery percentages agreed with the established values from CONAMA and ABNT, respectively. Thus, the electrode configuration developed seems a promising tool in the detection and quantification of PHEN in complex samples.

FASES ESTACIONÁRIAS DE LÍQUIDOS IÔNICOS EM CROMATOGRAFIA GASOSA: FUNDAMENTOS, AVANÇOS RECENTES E PERSPECTIVAS

Since their original discovery in 1914, ionic liquids (IL) have been widely examined and explored in chemistry due to their unique physical and chemical properties. Ionic liquids are collectively known as organic salts and have melting points of 100 °C or under. The molten salts most employed in analytical chemistry, including gas chromatography (GC), consist of an organic cation paired with an organic or inorganic anion. This class of materials exhibits negligible vapor pressure and may have their properties (e.g.thermal stability and selectivity) structurally tuned by imparting different moieties to the cation/anion. Currently, there are an estimated 1018possible combinations of IL. In this context, the prospection of highly selective IL-based stationary phases for gas-liquid chromatography has enabled high peak capacity and efficient separations of many critical pairs in complex samples. In this review, we present and discuss fundamental characteristics of ionic liquids and introduce important solvation models for gas-liquid systems. In addition, recent advances and applications of IL in conventional and multidimensional gas chromatography are outlined.

Electroanalytical determination of promethazine hydrochloride in pharmaceutical formulations on highly boron-doped diamond electrodes using square-wave adsorptive voltammetry

The electrochemical oxidation of promethazine hydrochloride was made on highly boron-doped diamond electrodes. Cyclic voltammetry experiments showed that the oxidation mechanisms involved the formation of an adsorbed product that is more readily oxidized, producing a new peak with lower potential values whose intensity can be increased by applying the accumulation potential for given times. The parameters were optimized and the highest current intensities were obtained by applying +0.78 V for 30 seconds. The square-wave adsorptive voltammetry results obtained in BR buffer showed two well-defined peaks, dependent on the pH and on the voltammetric parameters. The best responses were obtained at pH 4.0, frequency of 50 s(-1), step of 2 mV, and amplitude of 50 mV. Under these conditions, linear responses were obtained for concentrations from 5.96 x 10(-7) to 4.76 x 10(-6) mol L-1, and calculated detection limits of 2.66 x 10(-8) mol L-1 (8.51 mu g L-1) for peak 1 and of 4.61 x 10(-8) mol L-1 (14.77 mu g L-1) for peak 2. The precision and accuracy were evaluated by repeatability and reproducibility experiments, which yielded values of less than 5.00% for both voltammetric peaks. ne applicability of this procedure was tested on commercial formulations of promethazine hydrochloride by observing the stability, specificity, recovery and precision of the procedure in complex samples. All results obtained were compared to recommended procedure by British Pharmacopeia. The voltammetric results indicate that the proposed procedure is stable and sensitive, with good reproducibility even when the accumulation steps involve short times. It is therefore very suitable for the development of the electroanalytical procedure, providing adequate sensitivity and a reliable method.

Proteômica diferencial da Chromobacterium violaceum em resposta ao estresse oxidativo induzido por peróxido de hidrogênio

The β-proteobacterium Chromobacterium violaceum is a Gram-negative, free-living, saprophytic and opportunistic pathogen that inhabits tropical and subtropical ecosystems among them, in soil and water of the Amazon. It has great biotechnological potential, and because of this potential, its genome was completely sequenced in 2003. Genome analysis showed that this bacterium has several genes with functions related to the ability to survive under different kinds of environmental stresses. In order to understand the physiological response of C. violaceum under oxidative stress, we applied the tool of shotgun proteomics. Thus, colonies of C. violaceum ATCC 12472 were grown in the presence and absence of 8 mM H2O2 for two hours, total proteins were extracted from bacteria, subjected to SDS-PAGE, stained and hydrolysed. The tryptic peptides generated were subjected to a linear-liquid chromatography (LC) followed by mass spectrometer (LTQ-XL-Orbitrap) to obtain quantitative and qualitative data. A shotgun proteomics allows to compare directly in complex samples, differential expression of proteins and found that in C. Violaceum, 131 proteins are expressed exclusively in the control condition, 177 proteins began to be expressed under oxidative stress and 1175 proteins have expression in both conditions. The results showed that, under the condition of oxidative stress, this bacterium changes its metabolism by increasing the expression of proteins capable of combating oxidative stress and decreasing the expression of proteins related processes bacterial growth and catabolism (transcription, translation, carbon metabolism and fatty acids). A tool with of proteomics as an approach of integrative biology provided an overview of the metabolic pathways involved in the response of C. violaceum to oxidative stress, as well as significantly amplified understanding physiological response to environmental stress. Biochemical and "in silico" assays with the hypothetical ORF CV_0868 found that this is part of an operon. Phylogenetic analysis of superoxide dismutase, protein belonging to the operon also showed that the gene is duplicated in genome of C. violaceum and the second copy was acquired through a horizontal transfer event. Possibly, not only the SOD gene but also all genes comprising this operon were obtained in the same manner. It was concluded that C. violaceum has complex, efficient and versatile mechanisms in oxidative stress response

Aleitamento materno e alimentação complementar em crianças menores de um ano: chamada neonatal, RN, 2010

Avaliar os dados de aleitamento materno e alimentação complementar de crianças menores de um ano, do Rio Grande do Norte (RN), de acordo com o que é preconizado pelas políticas e ações de alimentação e nutrição. Métodos: Foi analisado o banco de dados da Chamada Neonatal do RN, pesquisa realizada pelo Ministério da Saúde em 2010. A amostra analisada foi de 837 pares mãe/filho que responderam ao questionário da pesquisa nos municípios investigados. Foram analisadas a prevalência de dados de aleitamento materno exclusivo (AME), na primeira hora de vida, parcial (AMP) e total (AMT), assim como dos alimentos ingeridos, pelas crianças, nas ultimas 24 horas anterior a entrevista. As frequências e médias foram feitas pelo comando Complex samples, no SPSS® 20.0, com IC95%. Foram estimadas as medianas de tempo de AME e AMT, assim como a mediana de tempo de introdução dos grupos de alimentos consumidos, em relação a idade da criança pelo método de probitos. Foi feita associação das probabilidades de tempo de AME e AMT com as variáveis sociodemográficas e de pré-natal (p<0.05). Resultados: Foram encontradas médias de idades de 5,28 ± 3,4 meses e 25,9 ± 6,4 anos, para crianças e mães, respectivamente. A prática de aleitamento na primeira hora de vida foi considerada boa (66,6%) e o percentual de AME (20%) razoável,segundo a Organização Mundial da Saúde, 2008. Mais da metade das crianças (55,1%) estavam em AMP. No total 60% estavam sendo amamentadas (AMT) ao final do primeiro ano de vida. O AME teve mediana de 63 dias e AMT de 358 dias. Estes dados não se diferenciaram muito entre a capital e os municípios do interior. A maioria das mães entrevistadas (73,8%) referiu ter tido orientação sobre aleitamento no pré- natal, tendo associação (p=0,03) com a probabilidade de tempo de AME, porém com pouca explicabilidade (R2= 0,011). Água ou chá, alimentos lácteos, frutas, legumes e verduras foram introduzidos precocemente com medianas menores que 180 dias. O aleitamento tende a diminuir e os alimentos tendem a aumentar o consumo de acordo com a idade da criança, com aumento exponencial do grupo calorias vazias . Conclusões: Conclui-se que mesmo com maioria das crianças amamentadas até um ano de vida, poucas estavam em AME e introduziram alimentos precocemente, não tendo resultado satisfatório frente ao preconizado pelas políticas públicas de alimentação e nutrição

Análise da toxicidade no açude Riacho da Cachoeira, Lajes Pintadas (RN): um desafio interdisciplinar

Contamination by complex mixtures of various origins has been explored and studied for decades. Radon is a naturally occurring environmental contaminant that causes carcinogenic effects. These emissions can cause mutations in the lung tissue, which can initiate a carcinogenic process. Thus the dam Creek Falls, located in the municipality of Lajes Pintadas, was chosen for the development of this study, since cancer rates in the region reach 9% of the population annually, with this, the main objective of this study was evaluate the mutagenicity and toxicity of Riacho da Cachoeira damunder the influence of radon. The methodology ecotoxicological tests were performed with Ceriodaphinia dubia, as well as tests with Tradescantia pallida genotoxicologicos and Oreochromis niloticus. To understand how the population of Pintadas Slabs realizes the environment, we performed a study of environmental perception. The test results indicated that the reservoir water is toxic to test organimos exposed, found heavy metals, chloride, total and fecal coliforms as well as radon levels above the maximum allowed under Brazilian law. These results can be justified because it is so complex samples composed of different compounds that interact only with each other or causing synergistic effects. It was concluded that the dam Creek Waterfall, is contaminated with radon, as well as heavy metals, coliforms and chloride, causing toxic effects to the natural community. Thus, further studies should be performed with the human population of the region, to verify that the high rates of cancer in the population of the municipality may be linked to the presence of natural radiation. Thus, it is expected that the competent bodies that administer the municipality of Lajes Pintadas take reasonable steps to minimize risks and ensure the health of the community that still makes use of the weir

Orpotrin: A novel vasoconstrictor peptide from the venom of the Brazilian Stingray Potamotrygon gr. orbignyi

Characterization of the peptide content of venoms has a number of potential benefits for basic research, clinical diagnosis, development of new therapeutic agents, and production of antiserum. In order to analyze in detail the peptides and small proteins of crude samples, techniques such as chromatography and mass spectrometry have been employed. The present study describes the isolation, biochemical characterization, and sequence determination of a novel peptide, named Orpotrin from the venom of Potamotrygon gr. orbignyi. The natural peptide was shown to be effective in microcirculatory environment causing a strong vasoconstriction. The peptide was fully sequenced by de novo amino acid sequencing with mass spectrometry and identified as the novel peptide. Its amino acid sequence, HGGYKPTDK, aligns only with creatine kinase residues 97-105, but has no similarity to any bioactive peptide. Therefore, possible production of this peptide from creatine kinase by limited proteolysis is discussed. Taken together, the results indicate the usefulness of this single-step approach for low molecular mass compounds in complex samples such as venoms. (c) 2006 Elsevier B.V. All rights reserved.

Desenvolvimento de sistemas de screening utilizando procedimentos em fluxo para monitoramento de sulfonamidas em urina e produtos de origem animal

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Aplicação da cromatografia líquida de alta eficiência na investigação de hidrocarbonetos policíclicos aromáticos em testemunhos sedimentares

Hidrocarbonetos policíclicos aromáticos (HPAs) são compostos orgânicos originários de fontes naturais e antrópicas e, por apresentarem potencial carcinogênico e mutagênico, são considerados poluentes prioritários por agências ambientais. Desta forma, métodos analíticos para investigação de tais compostos que sejam rápidos e de baixo custo são de relevância considerável para o monitoramento ambiental. O presente trabalho teve como objetivos otimizar um método analítico para HPAs utilizando cromatografia líquida com detecção por arranjo de diodos (HPLC-DAD) e aplicar em testemunho sedimentar de região estuarina. Para otimização e avaliação do método, uma coluna sedimentar de 46 cm de comprimento foi coletada na foz do Rio Tucunduba (Belém, Pará) e seccionada em porções de 2 cm (subamostras). Após secagem, 30 g de cada porção foram extraídos com mistura de diclorometano em acetona (1:1) em ultrassom por 40 min. Os extratos obtidos foram centrifugados, purificados em sílica-gel, adaptação em funil necessária principalmente para reter partículas finas, e em seguida concentrados em rotaevaporador à vácuo e, por fim, filtrados com membrana de nylon 0,22 μm antes da injeção no HPLC. Amostras fortificadas com padrões analíticos de 16 HPAs e brancos também foram processados da mesma maneira. Um conjunto de parâmetros para validação do método foi investigado e observou-se: (1) boa linearidade: as curvas de calibração (analíticas) apresentaram coeficientes de correlação elevadas; (2) precisão adequada: obteve-se desvio padrão relativo dentro do aceitável, sendo o mínimo de 2,1% para acenaftileno e máximo de 19,7% para o fluoranteno; (3) limites de detecção baixos: entre 0,004 a 1,085 ng g g^-1, viabilizando análises em concentrações reais in situ; (4) recuperação adequada para traços: sendo a mínima de 40,0% para o acenaftileno e máxima de 103,1% para o benzo(k)fluoranteno. As concentrações de HPAs totais variaram nas seções do testemunho sedimentar entre 60,77 - 783,3 ng g^-1 de sedimento seco. O método otimizado mostrou-se vantajoso com relação aos tradicionais que utilizam extrator soxhlet e colunas de adsorventes para purificação de extratos por minimizar o tempo de extração e reduzir custos com uso de volumes menores de solventes para purificação do extrato. A limitação do método, porém, foi a coeluição do criseno e do benzo(a)antraceno e a sobreposição do fluoreno e acenafteno, além da quantificação benzo(g,h,i)perileno. Essa limitação provavelmente está associada à eficiência da coluna cromatográfica disponível para a análise, que é para aplicação geral. O método mostrou-se aplicável a amostras estuarinas complexas e ricas em silte e argila. Razões diagnósticas de HPAs parentais indicam fontes petrogênicas a profundidades de 24 – 26 cm, 28 – 30 cm; e fontes pirolíticas a profundidades de 6 – 8 cm, 10 – 12 cm e 14 – 16 cm respectivamente.

Desenvolvimento de métodos para determinação de sulfonamidas, dipirona e citrato de sildenafil em matrizes diversas

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estudo SABE: Sintomas depressivos em idosos do município de São Paulo

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)