Desenvolveu-se um biossensor para ácido L-ascórbico empregando ascorbato oxidase. A enzima foi extraída do mesocarpo de pepino com solução tampão fosfato 0,05 mol L-1, pH 5,8 contendo NaCl 0,5 mol L-1. Após diálise versus solução tampão fosfato 0,05 mol L-1, pH 5,8 a enzima foi imobilizada em rede de nylon através de ligação covalente com glutaraldeído. A membrana foi acoplada em eletrodo de O2 e a reação monitorada pelo consumo de oxigênio a -600 mV em análise em fluxo (solução tampão fosfato 0,05 mol L-1, pH 5,8 como carregador e vazão 0,5 mL min-1). A curva analítica apresentou-se linear entre 1,2x10-4 a 1,0x10-3 mol L-1. O tempo de vida do biossensor foi de 500 análises. Amostras de medicamentos foram analisadas com a metodologia proposta e os resultados comparados com os obtidos com HPLC.

A L-ascorbic acid biosensor based on ascorbate oxidase has been developed. The enzyme was extracted from the mesocarp of cucumber (Cucumis sativus) by using 0.05 mol L-1 phosphate buffer, pH 5.8 containing 0.5 mol L-1 NaCl. After the dialysis versus phosphate buffer 0.05 mol L-1 pH 5.8, the enzyme was immobilized onto nylon net through glutaraldehyde covalent bond. The membrane was coupled to an O2 electrode and the yielding reaction monitored by oxygen depletion at -600 mV using flow injection analysis optimized to 0.1 mol L-1 phosphate buffer pH 5.8, as the carrier solution and flow-rate of 0.5 mL min-1. The ascorbic acid calibration curve was linear from 1.2x10-4 to 1.0x10-3 mol L-1. The evaluation of biosensor lifetime leads to 500 injections. Commercial pharmaceutical samples were analyzed with the proposed method and the results were compared with those obtained by high-performance liquid chromatography (HPLC).

A calorimetria Exploratória Diferencial (DSC) foi utilizada para estudar o comportamento térmico de amostras de cabelo e verificar a possibilidade de identificar um indivíduo com base nas curvas DSC de um banco de dados. Amostras de cabelo de estudantes e funcionários do Instituto de Química de Araraquara UNESP, foram obtidas para construir um banco de dados. Procurou-se assim identificar de um indivíduo sob incógnita, utilizando-se a curva DSC deste banco de dados.

The Differential Scanning Calorimetry (DSC) was used to study the thermal behavior of hair samples and to verify the possibility of identifying an individual based on DSC curves from a data bank. Hair samples of students and officials from Instituto de Química de Araraquara, UNESP were obtained to build up a data bank. Thus to sought an individual, under incognito participant of this data bank, was identified using DSC curves.

O comportamento eletroquímico e espectroeletroquímico do sistema montmorilonita-azul de metileno (MM-AM)/AMsolução foi investigado empregando-se a técnica de voltametria cíclica e de transiente, I x t (corrente versus tempo) sobre eletrodo de vidro ITO modificado pela deposição mecânica de filmes do compósito MM-AM. Os filmes foram preparados empregando três procedimentos: 1- na ausência de CTACl (surfactante, cloreto de cetiltrimetilamônio); 2- com incorporação do CTACl à região interlamelar; e 3- na presença do CTACl, porém, não incorporado à região interlamelar. A técnica espectrofotométrica foi empregada para a caracterização e para o estudo eletrocrômico dos filmes formados. Os resultados experimentais permitiram observar que: i- os filmes preparados com a incorporação prévia do AM a região interlamelar fornecem uma resposta eletroquímica mais eficiente com o aparecimento de um par de picos bem definido; ii- a adição do CTACl, de forma geral permite a obtenção de filmes mecanicamente mais estáveis; iii- com a inclusão prévia do CTACl na região interlamelar não ocorre o aparecimento da forma protonada do AM (AMH+); iv- na ausência da forma protonada o compósito não apresenta comportamento eletrocrômico.

The eletrochemical and espectroelectrochemical behavior of the montmorilonita methylene-blue system (MM-AM)/AMsolution have been investigated using cyclic volta mmetry and transient (I x t) techniques on modified ITO glass electrodes by film of composite (MM-AM) mechanically deposited. These films were prepared by three way: 1- in the absence of surfactant CTACl (cetyltrimethyl-ammonuim chloride); 2- with incorporation of CTACl into the interlayer region; and 3- in the presence of CTACl, however, not incorporated into the interlayer region. The spectroelectrochemistry technique was used for characterization and study of the formed films. The experimental results allowed assumptions as follows: 1- films prepared with AM previous incorporated into interlayer region supply a more efficient electrochemistry answer with the appearance of a couple of well defined peaks; 2- CTACl, in general, allows to obtain mechanically stable films; 3- when CTACl is previously included into interlayer region it doesn't exist intercalated protonated specie, AMH+; 4- when protonated specie is absent the composite doesn't shows electrochromic behavior.

Cyclic voltammetry and surface analysis techniques (EDX microanalysis, mapping of elements and SEM images) have been used to study the solid state reactions of Ir in blank solution or Hg(I)-containing solution. The studies in KNO3/HNO3 solution permit to suggest the formation of a thin oxide layer film deposited in the substrate. The RCV process exhibits the decrease of capacitive current associated to the substrate surface restructuring. The electro deposition of Hg occurs initially in UPD condition from Hg(I)-containing solution, C Hg(I) = 3.51x10-7 mol L-1. The electro deposition of bulk mercury occurs from Hg(I)-containing solution, C Hg(I) = 3.51x10-5 mol L-1. It was observed the deposition of Hg in the substrate in open circuit for all employed conditions.

Cyclic voltammetry and controlled potential electrolysis, and other analytical techniques were used to study the reactions of mercury with iridium oxides formed by repetitive cyclic voltammetry (RCV) or by controlled potential electrolysis (CPE) on pure iridium substrate. The oxides were formed in a Hg(I)-containing solution. The SEM images, XPS spectra and CV obtained after the RCV treatment showed a more attacked surface with less mercury on the Ir. On the contrary, the SEM images, XPS spectra and the CV for the electrode prepared by CPE indicated a less attacked surface with more Hg. The oxides formed when the CPE condition was applied inhibited the UPD of mercury.