Uso de membranas de Nafion para a construção de sensores ópticos para medidas de pH

The behaviour of Nafion® polymeric membranes containing acid-base dyes, bromothymol blue (BB) and methyl violet (MV), were studied aiming at constructing an optical sensor for pH measurement. BB revealed to be inadequate for developing sensing phases due to the electrostatic repulsion between negative groups of their molecules and the negative charge of the sulfonate group of the Nafion®, which causes leaching of the dye from the membrane. On the other hand, MV showed to be suitable due to the presence of positive groups in its structure. The membrane prepared from a methanolic solution whose Nafion®/dye molar ratio was 20 presented the best analytical properties, changing its color from green to violet in the pH range from 0.6 to 3.0. The membrane can be prepared with good reproducibility, presenting durability of ca. 6 months and response time of 22 s, making possible its use for pH determination in flow analysis systems.

Quantificação de fluxos de mercúrio gasoso na interface solo/atmosfera utilizando câmara de fluxo dinâmica: aplicação na bacia do Rio Negro

Gaseous mercury sampling conditions were optimized and a dynamic flux chamber was used to measure the air/surface exchange of mercury in some areas of the Negro river basin with different vegetal coverings. At the two forest sites (flooding and non-flooding), low mercury fluxes were observed: maximum of 3 pmol m-2 h-1 - day and minimum of -1 pmol m-2 h-1 - night. At the deforested site, the mercury fluxes were higher and always positive: maximum of 26 pmol m-2 h-1 - day and 17 pmol m-2 h-1 - night. Our results showed that deforestation could be responsible for significantly increasing soil Hg emissions, mainly because of the high soil temperatures reached at deforested sites.

Óxido nítrico: propriedades e potenciais usos terapêuticos

Nitric oxide ( NO) is a substance that acts as a second-messenger and is associated with a number of important physiological functions such as regulation of the vascular tonus, immune modulation and neurotransmission. As a physiological mediator, alteration of its concentration level may cause pathophysiological disfunctions such as hypertension, septic shock and impotence. Possible therapeutic approaches are being developed to control NO levels in vivo. We review herein the main physical and chemical properties of NO, its biological functions and available chemical interventions to reduce and increment its physiological concentration levels. Recent developments in the field are also highlighted.

Polímeros biomiméticos em química analítica. Parte 1: preparo e aplicações de MIP (Molecularly Imprinted Polymers) em técnicas de extração e separação

MIPs are synthetic polymers that are used as biomimetic materials simulating the mechanism verified in natural entities such as antibodies and enzymes. Although MIPs have been successfully used as an outstanding tool for enhancing the selectivity or different analytical approaches, such as separation science and electrochemical and optical sensors, several parameters must be optimized during their synthesis. Therefore, the state-of-the-art of MIP production as well as the different polymerization methods are discussed. The potential selectivity of MIPs in the extraction and separation techniques focusing mainly on environmental, clinical and pharmaceutical samples as applications for analytical purposes is presented.

Polímeros biomiméticos em química analítica. Parte 2: aplicações de MIP (Molecularly Imprinted Polymers) no desenvolvimento de sensores químicos

The aim of this paper is the description of the strategies and advances in the use of MIP in the development of chemical sensors. MIP has been considered an emerging technology, which allows the synthesis of materials that can mimic some highly specific natural receptors such as antibodies and enzymes. In recent years a great number of publications have demonstrated a growth in their use as sensing phases in the construction of sensors . Thus, the MIP technology became very attractive as a promising analytical tool for the development of sensors.

O modelamento estatístico de misturas: experimento tutorial usando voltametria de redissolução anódica

This work illustrates the modeling procedure for a solvent mixture using the simplex- centroid approach. The selected experiment was the optimization of the peak current observed in the direct determination of nickel by anodic stripping voltammetry (ASV) in a solvent mixture composed of N,N-dimethylformamide, ethanol and water. The text is presented in a tutorial way, showing in detail the several steps which must be followed in such a process. Since not all possible mixtures lead to a measurable instrumental response, pseudocomponents had to be used to rescale the experimental design. This also allows to show how to apply this tool, usually troublesome for non-specialists in mixture modeling procedures.

Contribuição à organização da pesquisa em Química e os desafios da interação com outras áreas do conhecimento

This article provides some aspects that allow making a current reading of the situation of the Brazilian Chemistry that permit us considerate it as a strategic area. They are still presented some initial proposals related to the organization of the research as well as to win the challenges of the relationship with the other areas of the knowledge.

Organização de pesquisa no Brasil: lições do passado, propostas para o futuro

Chemical research in Brazil has grown significantly in the past 20 years, largely thanks to the Brazilian S&T Development Program of the federal government (PADCT). However, the newly achieved levels of highly qualified manpower and research infra-structure require new research organization frameworks to make science, technology and innovation really useful and meaningful for the citizens. The current requirements for creating viable networks of academic and industry researchers are presented and discussed as well as some structural and procedural bottlenecks that have to be eliminated, to achieve maximum high-quality science, technology and relevant innovation output.

Comparação da eficiência do processo de ozonização e ozonização catalítica (Mn II e Cu II) na degradação de fenol

This paper discusses the results obtained with homogeneous catalytic ozonation [Mn (II) and Cu (II)] in phenol degradation. The reduction of total phenols and total organic carbon (TOC) and the ozone consumption were evaluated. The efficiency in phenol degradation (total phenol removal) at pH 3, with the catalytic process (Mn (II)), increased from 37% to 55% while the TOC removal increased from 4 to 63% in a seven-minute treatment. The ozonation process efficiency at pH 10 was 43% and 39% for phenol and TOC removal, respectively. The presence of both metallic ions (Mn2+ and Cu+2) in the ozonation process resulted in a positive effect.

Ação de colorantes na degradação e estabilização de polímeros

Dyes and pigments are additives used in polymers to improve mainly the aesthetic properties of the material. However, the incorporation of these additives can directly affect polymer stability. The colorants can drastically decrease the lifetime and the performance of the material or can act as a stabilizer, improving significantly the stability of the polymer against degradation. Interaction between colorants and polymers is the cause of the stability changes. Some mechanisms are proposed to explain the action of colorants on polymers. However it is difficult to foresee this action without experiments. This work reviews the main mechanisms involved in the degradation and stabilization of polymers containing colorants.

Determinação direta de molibdênio em comprimidos polivitamínicos por voltametria em meio não aquoso

Adsorptive stripping voltammetry carried out in a homogeneous ternary solvent composed of N,N-dimethylformamide, water and ethanol, with alpha-benzoinoxime (alphaBO) as the complexing agent for Mo(VI) and a 0.5 mol L-1 acetic acid - sodium acetate buffer as supporting electrolyte was successfully used for the determination of molybdenum in polyvitamin-polymineral tablets. Tablet samples were analyzed and the results were compared with those obtained both by graphite furnace atomic absorption and by recovery tests, with good correlations, indicating that this may be considered as an alternative procedure for routine determination of Mo(VI) in pharmaceutical samples.

A importância da Química Analítica Qualitativa nos cursos de Química das instituições de ensino superior brasileiras

The results of a survey of institutions offering undergraduate studies, with the objective of evaluating the importance of Qualitative Analytical Chemistry for Chemistry courses in Brazil, are presented and discussed. Judging by the data, the content of the course of Qualitative Analytical Chemistry is considered by the Brazilian institutions offering undergraduate studies to be a body of knowledge essential for the formation of the chemist. This aspect is deemed valid for both baccalaureate and teaching license studies.

Cálculos teóricos de afinidades por próton de n-alquilaminas usando o método ONIOM

The ONIOM method was used to calculate the proton affinities (PA) of n-alkylamines (CnH2n+1NH2, n = 3 to 6, 8, 10, 12, 14, 16 and 18). The calculations were carried out at several levels (HF, MP2, B3LYP, QCISD(T), ...) using Pople basis sets and at the QCISD(T) level using basis sets developed by the generator coordinate method (GCM) and adapted to effective core potentials. PAs were also obtained through the GCM and high level methods, like ONIOM[QCISD(T)/6-31+G(2df,p):MP2/6-31G+G(d,p))//ONIOM[MP2/6-31+G(d,p):HF/6-31G]. The average error using the GCM, with respect to experimental data, was 3.4 kJ mol-1.

Azul de metileno imobilizado na celulose/TiO2 e SiO2/TiO2: propriedades eletroquímicas e planejamento fatorial

The electrochemical properties of methylene blue immobilized on cellulose/TiO2 and mixed oxide SiO2/TiO2 matrices were investigated by means of cyclic voltammetry. The electron mediator property of the methylene blue was optimized using a factorial design, consisting of four factors in two levels. The experimental observations and data analyses on the system indicate that the lowest peak separation occurs for Sil/TiOAM, 1.0 mol L-1 KCl solution and 20 mV s-1 scan rate, while values of current ratio closest to unity were found for Cel/TiOAM independent of electrolyte concentration, 0.2 or 1.0 mol L-1, and scan rate, 20 mV s-1 or 60 mV s-1.

Variabilidade espacial e sazonal da concentração de elementos-traço em sedimentos do sistema estuarino de Santos-Cubatão (SP)

Multi-element analyses of sediment samples from the Santos-Cubatão Estuarine System were carried out to investigate the spatial and seasonal variability of trace-element concentrations. The study area contains a rich mangrove ecosystem that is a habitat for tens of thousands of resident and migratory birds, some of them endangered globally. Enrichments of metals in fine-grained surface sediments are, in decreasing order, Hg, Mn, La, Ca, Sr, Cd, Zn, Pb, Ba, Cu, Cr, Fe, Nb, Y, Ni and Ga, relative to pre-industrial background levels. The maximum enrichment ranged from 49 (Hg) to 3.1 (Ga). Mercury concentrations were greater in the Cubatão river than in other sites, while the other elements showed greater concentrations in the Morrão river. Concentrations of Mn were significantly greater in winter and autumn than in summer and spring. However, other elements (e.g. Cd and Pb) showed the opposite, with greater concentrations in summer and spring. This study suggests that seasonal changes in physical and chemical conditions may affect the degree of sediment enrichment and therefore make the assessment of contamination difficult. Consequently, these processes need to be considered when assessing water quality and the potential contamination of biota.