A pH optode based on thymol blue: application to determination of CO2 using flow injection analysis system

An optode based on thymol blue (TB), an acid-based indicator, has been constructed and evaluated as a detector in FIA system for CO2 determination. The dye was chemically immobilised on the surface of a bifurcated glass optical fibre bundle, using silanisation in organic media. In FIA system, hydrogen carbonate or carbonate samples are injected in a buffer carrier solution, and then are mixed with phosphoric acid solution to generate CO2, which diffuses through a PTFE membrane, in order to be collected in an acceptor carrier fluid, pumped towards to detection cell, in which the optode was adapted. The proposed system presents two linear response ranges, from 1.0 x 10-3 to 1.0 x 10-2 mol l-1, and from 2.0 x 10-2 to 0.10 mol l-1. The sampling frequency was 11 sample h-1, with good repeatability (R.S.D < 4 %, n = 10). In flow conditions the optode lifetime was 170 h. The system was applied in the analysis of commercial mineral water and the results obtained in the hydrogen carbonate determination did not differ significantly from those obtained by potentiometry, at a confidence level of 95 %.Este trabalho mostra a construção de um optodo baseado no indicador ácido - base azul de timol (TB) e sua aplicação como detector de um sistema para análise por injeção em fluxo (FIA) para determinação de CO2. O indicador foi quimicamente imobilizado na superfície de um feixe bifurcado de fibras ópticas de vidro, usando silanização em meio orgânico. No sistema FIA, amostras de carbonato ou bicarbonato são injetadas em uma solução tampão carregadora, e a seguir são misturadas com solução de ácido fosfórico para gerar CO2, o qual se difunde através de uma membrana de PTFE, para ser coletado em um fluido carregador aceptor, o qual é bombeado em direção à cela de detecção, na qual encontra-se o optodo. O sistema proposto apresenta duas faixas lineares de resposta, entre 1,0 x 10-3 e 1,0 x 10-2 mol l-1, e entre 2,0 x 10-2 e 0,10 mol l-1. A freqüência de amostragem foi de 11 amostras h-1, com boa repetibilidade (R.S.D < 4 %, n = 10). Sob condições em fluxo o tempo de vida do optodo foi de 170 h. O sistema proposto foi aplicado na análise de águas minerais comerciais, e os resultados obtidos na determinação de bicarbonato foram similares daqueles obtidos pelo método potenciométrico, a um nível de confiança de 95%.3343Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Enzymeless Biosensors: A Novel Area For The Development Of Amperometric Sensors [enzymeless Biosensors: Uma Nova área Para O Desenvolvimento De Sensores Amperométricos]

The aim of this work is to describe the recent area that it has been developed for the construction of amperometric sensors, with the purpose to make possible a more effective electron transfer between enzyme and electrode. The advances reported in the literature will be described, such as enzymatic configurations that can be mimic using the chemistry of the artificial enzymes.251123128Schmidt, H.-L., Gutberlet, F., Schuhmann, W., (1993) Sens. Actuators B, 13-14, p. 366Liu, H., Ying, T., Sun, K., Li, H., Qi, D., (1997) Anal. Chim. Acta, 344, p. 187Okawa, Y., Nagano, M., Hirota, S., Kobayashi, H., Ohno, T., Watanabe, M., (1999) Bios. Bioelect., 14, p. 229Gorton, L., Lindgren, A., Larsson, T., Munteanu, F.D., Ruzgas, T., Gazaryan, I., (1999) Anal. Chim. Acta, 400, p. 91Lötzbeyer, T., Schuhmann, W., Schmidt, H.-L., (1996) Sens. Actuators B, 33, p. 50Lötzbeyer, T., Schuhmann, W., Schmidt, H.-L., (1997) Bioelect. Bioenerg., 42, p. 1Breslow, R., Overman, L.E., (1970) J. Am. Chem. Soc., 92, p. 1075Breslow, R., (1980) Acc. Chem. Res., 13, p. 170Breslow, R., (1995) Acc. Chem. Res., 28, p. 146Cram, D.J., (1988) Angew. Chem., Int. Ed., 27, p. 1009Lehn, J.-M., (1988) Angew. Chem., Int. Ed., 27, p. 89Pendersen, C.J., (1988) Angew. Chem., Int. Ed., 27, p. 1021Murakami, Y., Kikuchi, J., Hisaeda, Y., Hayashida, O., (1996) Chem. Rev., 96, p. 721Hisaeda, Y., Kihara, E., Nishioka, T., (1997) J. Inorg. Biochem., 67, p. 235Murakami, Y., Aoyama, Y., Kikushi, J., (1981) J. Chem. Soc., Perkin Trans. I, 11, p. 2809Kajiki, T., Moriya, H., Hoshino, K., Kuroi, T., Kondo, S., Nabeshima, T., Yano, Y., (1999) J. Org. Chem., 64, p. 9679Walliman, P., Mattei, S., Seiler, P., Diederich, F., (1997) Helv. Chim. Acta, 80, p. 2368Bonchio, M., Carofiglio, T., Di Furia, R., Fornasier, R., (1995) J. Org. Chem., 60, p. 5986Ikeda, H., Horimoto, Y., Nakata, M., Ueno, A., (2000) Tetrahedron Lett., 41, p. 6483Breslow, R., Chmielewski, J., Foley, D., Johson, B., Kumabe, N., Varney, M., Mehra, R., (1988) Tetrahedron, 44, p. 5515Suh, J., Noh, Y.S., (1998) Bioorg. Med. Chem. Lett., 8, p. 1327Jairam, R., Potvin, P.G., Balsky, S., (1999) J. Chem. Soc., Perkin Trans. 2, 2, p. 363Kikushi, J., Zhang, Z., Murakami, Y., (1994) Chem. Lett., 8, p. 1559Schreyer, S.K., Mikkelsen, S.R., (1999) Bioconjugate Chem., 10, p. 464Wang, J., (1999) J. Pharm. Biomed. Anal., 19, p. 47Suzuki, I., Chen, Q., Kashiwagi, Y., Osa, T., Ueno, A., (1993) Chem. Lett., 10, p. 1719Ye, H., Tong, W., D'Souza, V.T., (1994) J. Chem. Soc., Perkin Trans. 2, 12, p. 2431Ye, H., Tong, W., D'Souza, V.T., (1992) J. Am. Chem. Soc., 114, p. 5470Tong, W., Ye, H., Rong, D., D'Souza, V.T., (1992) J. Comput. Chem., 13, p. 614Ansell, R.J., Small, D.A.P., Lowe, C.R., (1999) J. Mol. Catal. B: Enzym., 6, p. 111Engbersen, J.F., Koudijs, A., Van Der Plas, H.C., (1990) J. Org. Chem., 55, p. 3647Miller, S.F., Babcock, G.T., (1996) Chem. Rev., 96, p. 2889Klinman, J.P., (1996) Chem. Rev., 96, p. 2541Solomon, F.I., Sundaram, U.M., Machonkin, T.E., (1996) Chem. Rev., 96, p. 2563Hasebe, Y., Akiyama, T., Yagisawa, T., Uchiyama, S., (1998) Talanta, 47, p. 1139Fernandes, J.C.B., Kubota, L.T., Oliveira-Neto, G., (1999) Electroanalysis, 11, p. 475Rover L., Jr., Fernandes, J.C.B., Oliveira-Neto, G., Kubota, L.T., (2000) J. Electroanal. Chem., 481, p. 34Hille, R., (1996) Chem. Rev., 96, p. 2757Dismukes, G.C., (1996) Chem. Rev., 96, p. 2909Johnson, M.K., Rees, D.C., Adams, M.W.W., (1996) Chem. Rev., 96, p. 2817Que L., Jr., Ho, R.Y.N., (1996) Chem. Rev., 96, p. 2607Costas, M., Chen, K., Que L., Jr., (2000) Coord. Chem. Rev., 200-202, p. 517Angnes, L., Azevedo, C.M.B., Araki, K., Toma, H.E., (1996) Anal. Chim. Acta, 329, p. 91Araki, K., Angnes, L., Azevedo, C.M.B., Toma, H.E., (1995) J. Electroanal. Chem., 397, p. 205Zen, J.-M., Lai, Y.-Y., Ilangovan, G., Kumar, A.S., (2000) Electroanalysis, 12, p. 280Zen, J.-M., Kumar, A.S., Chang, M.-R., (2000) Electrochim. Acta, 45, p. 1691Berchmans, S., Gomathi, H., Rao, G.P., (1998) Sens. Actuators B, 50, p. 156Berchmans, S., Gomathi, H., Rao, G.P., (1995) J. Electroanal. Chem., 394, p. 267Casella, I.G., Desimoni, E., Salvi, A.M., (1991) Anal. Chim. Acta, 243, p. 61Casella, I.G., Cataldi, T.R.I., Salvi, A.M., Desimoni, E., (1993) Anal. Chem., 65, p. 3143Karyakin, A.A., Karyakina, E.E., (1999) Sens. Actuators B, 57, p. 268Itaya, K., Shoji, N., Uchida, I., (1984) J. Am. Chem. Soc., 106, p. 3423Karyakin, A.A., Karyakina, E.E., Gorton, L., (1996) Talanta, 43, p. 1597Cosnier, S., Innocent, C., Allien, L., Poitry, S., Tsacopoulos, M., (1997) Anal. Chem., 69, p. 968Belay, A., Ruzgas, T., Csösegi, E., Moges, G., Tessema, M., Solomon, T., Gorton, L., (1997) Anal. Chem., 69, p. 3471Villarta, R., Cunningham, D.D., Guilbault, G.G., (1991) Talanta, 38, p. 49Karyakin, A.A., Karyakina, E.E., Gorton, L., (1998) J. Electroanal. Chem., 456, p. 9

Tris (2,2′-bipyridil) Copper (ii) Chloride Complex: A Biomimetic Tyrosinase Catalyst In The Amperometric Sensor Construction

The use of tris (2,2′-bipyridil) copper (II) chloride complex, [Cu(bipy)3]Cl2·6H2O, as a biomimetic catalyst, is reported in the construction of an amperometric sensor for dopamine. The sensor was prepared modifying a glassy carbon electrode with a Nafion® membrane doped with the complex. The optimized conditions for the sensor response were obtained in 0.25 mol dm-3 Pipes buffer (pH 7.0) containing 150 μmol dm-3 H2O2, with an applied potential of -50 mV versus saturated calomel electrode (SCE). In these conditions, a linear response range between 9 and 230 μmol dm-3, with a sensitivity of 1.43 ± 0.01 nA dm3 μmol-1 cm-2 and a detection limit of 4.8 μmol dm-3 were observed for dopamine. The response time for this sensor was about 1 s, presenting the same response for at least 150 successive measurements, with a good repeatability (4.8%) expressed as relative standard deviation for n = 13. After its construction, this sensor can be used after 180 days without loss of sensitivity, kept at room temperature. The difference of the sensor response between four preparations was 4.2%. A detailed investigation about the sensor response for other eighteen phenolic compounds and five interfering species was performed. The sensor was applied for dopamine determination in pharmaceutical preparation with success. © 2002 Elsevier Science Ltd. All rights reserved.487855865Zhang, S., Zhao, H., John, R., (2001) Anal. Chim. Acta, 441, p. 95Cosnier, S., Fombon, J.J., Labbé, P., Limosin, D., (1999) Sens. Actuat. B, 59, p. 134Capannesi, C., Palchetti, I., Mascini, M., Parenti, A., (2000) Food Chem., 71, p. 553Nistor, C., Emnéus, J., Gorton, L., Ciucu, A., (1999) Anal. Chim. Acta, 387, p. 309Dantoni, P., Serrano, S.H.P., Brett, A.M.O., Gutz, I.G.R., (1998) Anal. Chim. Acta, 366, p. 137Hedenmo, M., Narváez, A., Domínguez, E., Katakis, I., (1997) J. Electroanal. 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Application Of (2,2′:6′,2″-terpyridyl) Copper(ii) Chloride Complex In Sensor Construction For Benzoyl Peroxide Determination In Pharmaceutical Samples

This work describes an alternative method for benzoyl peroxide (BP) determination in pharmaceutical samples, using an amperometric sensor based on a carbon paste modified with (2,2′:6′,2″-terpyridyl) copper(II) chloride complex [Cu(terpy)Cl]Cl·2H2O. The sensor presented the best response in 0.10moll-1 phosphate buffer solution (pH 7.0) applying a potential of -50mV versus SCE. In the optimized conditions the sensor showed a linear response range for BP from 0.9 to 5.0μgml -1. The response time for this sensor was 0.5s. The paste presented a stability of at least 6 months at room temperature. The precision of the measurements was 4.5%, expressed in term of relative standard deviation (R.S.D.) for n=5. A detailed study was carried out, in order to investigate the sensor response for some compounds contained in pharmaceutical formulations, such as carboxypolymethylene (carbopol® 940), triethanolamine, propyleneglycol, hydroxyethylcellulose (natrosol®), and no interference was observed with these compounds. The applicability of the sensor for BP determination was evaluated in pharmaceutical preparations, obtaining recovery averages of 98±1%. © 2003 Elsevier B.V. All rights reserved.49401/02/15199205Fares, H.M., Chatterjeeem, S., Hayward, M., (1996) Int. J. Pharmacol., 133, p. 215Valacchi, G., Rimbach, G., Saliou, C., Weber, S.U., Packer, L., (2001) Toxicology, 165, p. 225Babich, H., Zuckerbraun, H.L., Wurzburger, B.J., Rubin, Y.L., Borenfreud, E., Blau, L., (1996) Toxicology, 106, p. 187Terada, H., Sakabe, Y., (1985) J. Chromatogr., 346, p. 333Shintani, H., Tsuchiya, T., Hata, Y., Nakamura, A., (1993) J. Anal. Toxicol., 17, p. 73Shintani, H., (1995) J. Liquid Chromatogr., 18, p. 613Zaman, F., Beeser, A.E., Mitchell, J.C., Clarkson, Q., Elliot, J., Davis, A.F., Willson, R.J., (2001) Int. J. Pharmacol., 277, p. 133United States Pharmacopeia National Formulary XXI, US Pharmacopeial Convention, Rockville, MD, 1985, pp. 100-101Kleemann, A., Engel, J., (2001) Pharmaceutical Substances: Synthesis, Patents and Applications, Fourth Ed., pp. 210-211. , B. Kutscher, D. Reichert (Eds.), Thieme, StuttgartLunn, G., (2000) HPLC Methods for Pharmaceutical Analysis, pp. 677-678. , Wiley, New YorkMorgan, G., Burstall, F.H., (1937) J. Chem. Soc., 2, p. 1649Constable, E.C., (1986) Adv. Inorg. Radiochem., 30, p. 69Harris, C.M., Lockyer, T.N., (1970) Aust. J. Chem., 23, p. 673Somasundrum, M., Kirtikara, K., Tanticharoen, M., (1996) Anal. Chim. Acta, 319, p. 59Sotomayor, M.D.P.T., Tanaka, A.A., Kubota, L.T., (2003) Electrochim. Acta, 48, p. 855Oldham, C., (1968) Progr. Inorg. Chem., 10, p. 225Edwards, D.A., Richards, R., (1972) Inorg. Nucl. Chem. Lett., 8, p. 783Edwards, D.A., Richards, R., (1973) J. Chem. Soc., Dalton Trans., p. 2463Saphier, M., Burg, A., Sheps, S., Cohen, H., Meyerstein, D., (1999) J. Chem. Soc., Dalton Trans., p. 1845Bunting, J., Thong, K., (1970) Can. J. Chem., 48, p. 1654(1987) Analyst, 112, p. 199Sotomayor, M.D.P.T., Tanaka, A.A., Kubota, L.T., (2002) Anal. Chim. Acta, 455, p. 215Sotomayor, M.D.P.T., Tanaka, A.A., Kubota, L.T., (2002) J. Electroanal. Chem., 536, p. 7

Development Of An Amperometric Sensor Highly Selective For Dopamine And Analogous Compounds Determination Using Bis(2,2′-bipyridil) Copper(ii) Chloride Complex

The use of [Cu(bipy)2]Cl2·6H2O as a biomimetic catalyst in the construction of an amperometric sensor for dopamine determination is reported. The sensor was prepared modifying a glassy carbon electrode with a Nafion membrane doped with [Cu(bipy)2]Cl2·6H2O complex. The sensor presented a higher response in 0.25 mol L-1 phosphate buffer solution (pH 7.0), with an applied potential of - 50 mV (vs. SCE). In the optimized operational conditions, a linear response range between 35 and 240 μmol L-1, with a sensitivity of 2.02 ± 0.07 nA 1 μmoL-1 cm-2 and detection limit of 8.0 μmol L-1 were typically observed for the sensor. The response time presented for this sensor was 0.5 s, presenting the same response for at least 40 successive measurements, with good repeatability (3.0%) expressed as relative standard deviation for n = 6. The difference of the response between four sensor preparations was 4%. 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Ion Imprinted Polymers: Fundamentals, Preparation Strategies And Applications In Analytical Chemistry [polímeros Impressos Com íons: Fundamentos, Estratégias De Preparo E Aplicações Em Química Analítica]

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Development And Evaluation Of Gas Diffusion Electrodes (gde) For Generation Of H2o2 In Situ And Their Application In The Degradation Of Reactive Blue 19 Dye [desenvolvimento E Avaliação De Eletrodos De Difusão Gasosa (edg) Para Geração De H2o2 In Situ E Sua Aplicação Na Degradação Do Corante Reativo Azul 19]

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