A new electroanalytical procedure was developed for the determination of Benzophenone-3 (BENZO) in commercial sunscreen as the active ingredient. The procedure is based on the use of electrochemical methods as cyclic and square-wave voltammetry, with boron-doped diamond (BDD) electrodes. The reduction of BENZO in Britton-Robinson buffer (0.1 mol●L<sup>–1</sup>) using this type of electrode gives rise to one irreversible peak in –1.30 V (versus Ag/AgCl) in presence of cationic surfactant cetyltrimethylammonium bromide (CTABr). The proposed electrochemical method was successfully applied to the analysis of commercially available pharmaceutical preparations.
KeywordsBoron-Doped DiamondBenzophenone-3 BENZO and Square-Wave Voltammetry
H. Gonzalez, A. Abrot, O. Larko and A. M. Wennberg, “Percutaneous Absorption of the Sunscreen Benzophenone-3 after Repeated Whole-Body Applications, with and without Ultraviolet Irradiation,” British Journal of Dermatology, Vol. 154, No. 2, 2006, pp .337-340.
T. Suzuki, S. Kitamura, R. Khota, K. Sugihara, N. Fujimoto and S. Ohta, “Estrogenic and Antiandrogenic Activities of 17 Benzophenone Derivatives Used as UV Stabilizers and Sunscreens,” Toxicology and Applied Pharmacology, Vol. 203, No. 1, 2005, pp. 9-17. doi:10.1016/j.taap.2004.07.005
C. G. Daughton, “Environmental Stewardship and Drugs as Pollutants,” Lancet, Vol. 360, No. 9339, 2002, pp. 1035-1036. doi:10.1016/S0140-6736(02)11176-7
M. E. Balmer, H. R. Buser, M. D. Muller and T. Poiger, “Occurrence of Some Organic UV Filters in Wastewater, in Surface Waters, and in Fish from Swiss Lakes,” Environmental Science & Technology, Vol. 39, No. 4, 2005, pp. 953-962. doi:10.1021/es040055r
G. A. Loraine and M. E. Pettigrove, “Seasonal Variations in Concentrations of Pharmaceuticals and Personal Care Products in Drinking Water and Reclaimed Wastewater in Southern California,” Environmental Science & Technology, Vol. 40, No. 3, 2006, pp. 687-695. doi:10.1021/es051380x
S. C. Rastogi and G. H. Jensen, “Identification of UV Filters in Sunscreen Products by High-Performance Liquid Chromatography-Diode Array Detection,” Journal of Chromatography A, Vol. 828, No. 1-2, 1998, pp. 311-316. doi:10.1016/S0021-9673(98)00784-5
V. Vanquerp, C. Rodriguez, C. Coiffard, L. J. M. Coiffard and Y. D. Roeck-Holtzhauer, “High-Performance Liquid Chromatographic Method for the Comparison of the Photostability of Five Sunscreen Agents,” Journal of Chromatography A, Vol. 832, No. 1-2, 1999, pp. 273-277. doi:10.1016/S0021-9673(98)00928-5
A. Chisvert, M. C. Pascual-Marti and A. Salvador, “Determination of UV-Filters in Sunscreens by HPLC,” Fresenius Journal of Analytical Chemistry, Vol. 369, No. 7-8, 2001, pp. 638-641. doi:10.1007/s002160100701
T. Felix, B. J. Hall and J. S. Brodbelt, “Determination of Benzophenone-3 and Metabolites in Water and Human Urine by Solid-Phase Microextraction and Quadrupole Ion Trap GC-MS,” Analytica Chimica Acta, Vol. 371, No. 2-3, 1998, pp. 195-203. doi:10.1016/S0003-2670(98)00293-1
V. Lorena, C. Alberto, C. Antonio, P. Elefteria, L. Alexei, A. Fernando, J. Karen, A. H. James and M. Frank, “Chemically Surface-Modified Carbon Nanoparticle Carrier for Phenolic Pollutants: Extraction and Electrochemical Determination of Benzophenone-3 and Triclosan,” Analytica Chimica Acta, Vol. 616, No. 1, 2008, pp. 28-35. doi:10.1016/j.aca.2008.04.011
A. O. Razak, A. A. Gazy and A. M. Wahbi, “Polarographic Determination of Phenytoin and Benzophenone (as Impurity) in Pharmaceutical Preparations,” Journal Pharmaceutical and Biomedical Analysis, Vol. 28, No. 3-4, 2002, pp. 613-619. doi:10.1016/S0731-7085(01)00669-0
J. C. Cardoso, B. M. L. Armondes, J. B. G. Júnior and V. S. Ferreira, “Simultaneous Electrochemical Determination of Three Sunscreens Using Cetyltrimethylammonium Bromide,” Colloids and Surfaces B: Biointerfaces, Vol. 63, No. 1, 2008, pp. 34-40. doi:10.1016/j.colsurfb.2007.11.001
A. J. Wain, J. D. Wadhawan and R. G. Compton, “Electrochemical Studies of Vitamin K1 Microdroplets: Electrocatalytic Hydrogen Evolution,” Chemical Physics And Physical Chemistry, Vol. 4, No. 9, 2003, pp. 974-982.
J. M. Gong and X. Q. Lin, “Electrochemical Determination of Serotonin and the Competitive Adsorption with Dopamine at 5,5-Ditetradecyl-2-(2-trimethylammonioethyl)-1,3-dioxane Bromide Lipid Film Modified by Glassy Carbon Electrode,” Anaytica Sciences, Vol. 20, No. 6, 2004, pp. 905-909. doi:10.2116/analsci.20.905
H. B. Suffredini, S. A. S. Machado and L. A. Avaca, “The Water Decomposition Reaction on Boron-Doped Diamond Electrode,” Journal Brazilian Chemical Society, Vol. 15, No. 1, 2004, pp. 16-21. doi:10.1590/S0103-50532004000100004
R. Bellagamba, P. A. Michaud, C. Comninellis and N. Vatistas, “Electro-Combustion of Polyacrylates with BoronDoped Diamond Anodes,” Electrochemistry Communication, Vol. 4, No. 2, 2002, pp. 171-176. doi:10.1016/S1388-2481(01)00302-2
J. S. Foord and C. H. Goeting, “Electrochemically Controlled Modification of CVD Diamond Surfaces,” Diamond and Related Materials, Vol. 13, No. 4-8, 2004, pp. 1054-1058. doi:10.1016/j.diamond.2003.12.016
M. C. Granger and G. M. Swain, “The Influence of Surface Interactions on the Reversibility of Ferri/Ferrocyanide at Boron-Doped Diamond Thin-Film Electrodes,” Journal of the Electrochemical Society, Vol. 146, No. 12, 1999, pp. 4551-4558. doi:10.1149/1.1392673
I. Duo, C. Lévy-Clément, A. Fujishima and C. Comninellis, “Electron Transfer Kinetics on Boron-Doped Diamond Part I: Influence of Anodic Treatment,” Journal of Applied Electrochemistry, Vol. 34, No. 9, 2004, pp. 935-943. doi:10.1023/B:JACH.0000040525.76264.16
H. B. Suffredini, V. A. Pedrosa, L. Codognoto, S. A. S. Machado, R. C. Rocha-Filho and L. A. Avaca, “Enhanced Electrochemical Response of Boron-Doped Diamond Electrodes Brought on by a Cathodic Surface Pre-Treatment,” Electrochimica Acta, Vol. 49, No. 22-23, 2004, pp. 4021-4026. doi:10.1016/j.electacta.2004.01.082
G. R. Salazar-Banda, L. S. Andrade, P. A. P. Nascente, P. S. Pizani, R. C. Rocha-Filho and L. A. Avaca, “On the Changing Electrochemical Behaviour of Boron-Doped Diamond Surfaces with Time after Cathodic Pre-Treatments,” Electrochimica Acta, Vol. 51, No. 22, 2006, pp. 4612-4619. doi:10.1016/j.electacta.2005.12.039
M. S. Saha, T. Furuta and Y. Nishiki, “Conversion of Carbon Dioxide to Peroxycarbonate at Boron-Doped Diamond Electrode,” Electrochemistry Communication, Vol. 6, No. 2, 2004, pp. 201-204. doi:10.1016/j.elecom.2003.11.014
J. Iniesta, P. A. Michaud, M. Panizza and C. Comninellis, “Electrochemical Oxidation of 3-Methylpyridine at a Boron-Doped Diamond Electrode: Application to Electroorganic Synthesis and Wastewater Treatment,” Electrochemistry Communication, Vol. 3, No. 7, 2001, pp. 346- 351. doi:10.1016/S1388-2481(01)00174-6
J. W. Strojek, M. C. Granger, T. Dallas, M. W. Holtz and G. M. Swain, “Enhanced Signal-to-Background Ratios in Voltammetric Measurements Made at Diamond Thin-Film Electrochemical Interfaces,” Analytical Chemistry, Vol. 68, No. 13, 1996, pp. 2031-2037. doi:10.1021/ac9506847
M. Hupert, A. Muck, J. Wang, J. Stotter, Z. Cvackova, S. Haymond, Y. Show and G. M. Swain, “Conductive Diamond Thin-Films in Electrochemistry,” Diamond and Related Materials, Vol. 12, No. 10-11, 2003, pp. 1940-1949. doi:10.1016/S0925-9635(03)00260-7
Y. Yano, D. A. Tryk, K. Hashimoto and A. Fujishima, “Electrochemical Behavior of Highly Conductive Boron-Doped Diamond Electrodes for Oxygen Reduction in Alkaline Solution,” Journal of the Electrochemical Society, Vol. 145, No. 6, 1998, pp. 1870-1876. doi:10.1149/1.1838569
N. Vinokur, B. Miller, Y. Avyigal and R. Kalisk, “Electrochemical Behavior of Boron-Doped Diamond Electrodes,” Journal of the Electrochemical Society, Vol. 143, No. 10, 1996, pp. L238-L240. doi:10.1149/1.1837157
T. N. Rao, Y. Yagi, T. Miwa, D. A. Tryk and A. Fujishima, “Electrochemical Oxidation of NADH at Highly Boron-Doped Diamond Electrodes,” Analytical Chemistry, Vol. 71, No. 13, 1999, pp. 2506-2511. doi:10.1021/ac981376m
E. Popa, H. Notsu, T. Miwa, D. A. Tryk and A. Fujishima, “Selective Electrochemical Detection of Dopamine in the Presence of Ascorbic Acid at Anodized Diamond Thin Film Electrodes,” Electrochemistry and Solid-State Letters, Vol. 2, No. 1, 1999, pp. 49-51. doi:10.1149/1.1390730
J. Iniesta, P. A. Michaud, M. Panizza, C. Cerisola, A. Aldaz and C. Comniniellis, “Electrochemical Oxidation of Phenol at Boron-Doped Diamond Electrode,” Electrochimica Acta, Vol. 46, No. 23, 2001, pp. 3573-3578. doi:10.1016/S0013-4686(01)00630-2
M. C. Granger, J. S. Xu, J.W. Strojek and G. M. Swain, “Polycrystalline Diamond Electrodes: Basic Properties and Applications as Amperometric Detectors in Flow Injection Analysis and Liquid Chromatography,” Analytica Chimica Acta, Vol. 397, No. 1-3, 1999, pp. 145-161. doi:10.1016/S0003-2670(99)00400-6
V. A. Pedrosa, L. Codognoto and L. A. Avaca, “Electro-analytical Determination of 4-Nitrophenol by Square Wave Voltammetry on Diamond Electrodes,” Journal of the Brazilian Chemical Society, Vol. 14, No. 4, 2003, pp. 530-535. doi:10.1590/S0103-50532003000400007
V. A. Pedrosa, L. Codognoto and L. A. Avaca, “Is the Boron-Doped Diamond Electrode a Suitable Substitute for Mercury in Pesticide Analyses? A Comparative Study of 4-Nitrophenol Quantification in Pure and Natural Waters,” Journal of Electroanalytical Chemistry, Vol. 573, 2004, pp. 11-18.
V. A. Pedrosa, H. B. Suffredini, L. Codognoto, S. T. Tanimoto, S. A. S. Machado and L. A. Avaca, “Carbon Surfaces for Electrochemical Applications. A Comparative Study,” Analytical Letters, Vol. 38, 2005, pp. 1115-1125.
L. Codognoto, S. A. S. Machado and L. A. Avaca, “Square Wave Voltammetry on Boron-doped Diamond Electrodes for Analytical Determination,” Diamond and Related Materials, Vol. 11, No. 9, 2002. pp. 1670-1675. doi:10.1016/S0925-9635(02)00134-6
G. W. Muna, N. Tasheva and G. M. Swain “Electro-Oxidation and Amperometric Detection of Chlorinated Phenols at Boron-Doped Diamond Electrodes: A Comparison of Microcrystalline and Nanocrystalline Thin Films,” Environmental Science & Technology, Vol. 38, No. 13, 2004, pp. 3674-3682. doi:10.1021/es034656e
C. E. Banks, M. E. Hyde, P. Tomcik, R. Jacobs and R. G. Comptom, “Cadmium Detection via Boron-Doped Diamond Electrodes: Surfactant Inhibited Stripping Voltammetry,” Talanta, Vol. 62, No. 2, 2004, pp.279-286. doi:10.1016/j.talanta.2003.07.008
J. Iniesta, P. A. Michaud, M. Panizza and C. Comninellis, “Electrochemical Oxidation of 3-Methylpyridine at a Boron-Doped Diamond Electrode: Application to Electroorganic Synthesis and Wastewater Treatment,” Electrochemistry Communication, Vol. 3, No. 7, 2001, pp. 346-351. doi:10.1016/S1388-2481(01)00174-6
P. A. Michaud, E. Mahé, W. Haenni, A. Perret and C. Comninellis, “Preparation of Peroxodisulfuric Acid Using Boron-Doped Diamond Thin Film Electrode,” Electrochemistry and Solid-State Letters, Vol. 3, No. 2, 2000, pp. 77-79. doi:10.1149/1.1390963
R. T. S. Oliveira, G. R. Salazar-Banda, M. C. Santos, M. L. Calegaro, D. W. Miwa, S. A. S. Machado and L. A. Avaca, “Electrochemical Oxidation of Benzene on Boron-Doped Diamond Electrodes,” Chemosphere, Vol. 66, No. 11, 2007, pp. 2152-2158. doi:10.1016/j.chemosphere.2006.09.024
E. Brillas, B. Boye, I. Sires, J. A. Garrido, R. M. Rodriguez, C. Arias, P. L. Cabot and C. Comninellis, “Electrochemical Destruction of Chlorophenoxy Herbicides by Anodic Oxidation and Electro-Fenton Using a Boron-Doped Diamond Electrode,” Electrochimica Acta, Vol. 49, No. 25, 2004, pp. 4487-4496. doi:10.1016/j.electacta.2004.05.006
J. F. Zhi, H. B. Wang, T. Nakashima, T. N. Rao and A. Fujishima, “Electrochemical Incineration of Organic Pollutants on Boron-Doped Diamond Electrode. Evidence for Direct Electrochemical Oxidation Pathway,” Journal of Physical Chemistry B, Vol. 107, No. 48, 2003, pp. 13389-13395. doi:10.1021/jp030279g
R. Bellagamba, P. A. Michaud, C. Comninellis and N. Vatistas, “Electro-Combustion of Polyacrylates with Boron-Doped Diamond Anodes,” Electrochemistry Communication, Vol. 4, No. 2, 2002, pp. 171-176. doi:10.1016/S1388-2481(01)00302-2
F. Montilla, E. Morallon, I. Duo, C. Comninellis and J. L. Vazquez, “Platinum Particles Deposited on Synthetic Boron-Doped Diamond Surfaces. Application to Methanol Oxidation,” Electrochimica Acta, Vol. 48, No. 25-26, 2003, pp. 3891-3897. doi:10.1016/S0013-4686(03)00526-7
G. R. Salazar-Banda, H. B. Suffredini and L. A. Avaca, “Improved Stability of PtOx Sol-Gel Modified Diamond Electrodes Covered with a Nafion Film,” Journal of the Brazilian Chemical Society, Vol. 16, No. 5, 2005, pp. 903-906. doi:10.1590/S0103-50532005000600003
H. B. Suffredini, G.R. Salazar-Banda, S. T. Tanimoto, M. L. Calegaro, S. A. S. Machado and L. A. Avaca, “AFM Studies and Electrochemical Characterization of Boron-Doped Diamond Surfaces Modified with Metal Oxides by the Sol-Gel Method,” Journal of the Brazilian Chemical Society, Vol. 17, No. 2, 2006, pp. 257-264. doi:10.1590/S0103-50532006000200007
C. Terashima, T. N. Rao, B. V. Sarada, Y. Kubota and A. Fujishima, “Direct Electrochemical Oxidation of Disulfides at Anodically Pretreated Boron-Doped Diamond Electrodes,” Analytical Chemistry, Vol. 75, No. 7, 2003, pp. 1564-1572. doi:10.1021/ac020583q
T. N. Rao, T. A. Ivandini, C. Terashima, B. V. Sarada and A. Fujishima, “Applications of Bare and Modified Diamond Electrodes in Electroanalysis,” New Diamond Frontier Carbon Technology, Vol. 13, 2003, pp.79-88.
R. T. S. Oliveira, G. R. Salazar-Banda, S. C. Oliveira, V. S. Ferreira and L. A. Avaca, “Electroanalytical Determination of Lidocaine in Pharmaceutical Preparations Using Boron-Doped Diamond Electrodes,” Electroanalysis, Vol. 19, No. 11, 2007, pp. 1189-1194. doi:10.1002/elan.200603840
R. T. S. Oliveira, G. R. Salazar-Banda, S. A. S. Machado and L. A. Avaca, “Electroanalytical Determination of N-Nitrosamines in Aqueous Solution Using a Boron-Doped Diamond Electrode,” Electroanalysis, Vol. 20, No. 4, 2008, pp. 396-401. doi:10.1002/elan.200704055
G. Pastor-Moreno and D. J. Riley, “The Influence of Surface Preparation on the Electrochemistry of Boron-Doped Diamond: A Study of the Reduction of 1,4-Benzoquinone in Acetonitrile,” Electrochemistry Communication, Vol. 4, No. 2, 2002, pp. 218-221. doi:10.1002/elan.200704055
A. Arranz, L. Dolara, S. F. Bet?no, J. M. Moreda, A. Cid and J. F. Arranz, “Electroanalytical Study and Square Wave Voltammetric Techniques for the Determination of β-Blocker Timolol at the Mercury Electrode,” Analytica Chimica Acta, Vol. 389, No. 1-3, 1999, pp. 225-232. doi:10.1016/S0003-2670(99)00214-7
M. Lovri?, K. ?ebojka and W. Murray, “Adsorption Effects in Square-Wave Voltammetry of Totally Irreversible Redox Reactions,” Electrochimica Acta, Vol. 33, No. 6, 1988, pp. 739-744. doi:10.1016/S0013-4686(98)80002-9
M. Lovri? and K. ?ebojka, “Square-Wave Voltammetry of an Adsorbed Reactant,” Journal of Electronalytical Chemistry and Interfacial Electrochemistry, Vol. 248, No. 2, 1988, pp. 239-253. doi:10.1016/0022-0728(88)85089-7
R. Q. Thompson, M. Porter, C. Stuver, H. B. Halsall, W. R. Heineman, E. Buckley and M. R. Smyth, “Zeptomole Detection Limit for Alkaline Phosphatase Using 4-Aminophenyl-Phosphate, Amperometric Detection, and an Optimal Buffer System,” Analytica Chimica Acta, Vol. 271, No. 2, 1993, pp. 223-229. doi:10.1016/0003-2670(93)80049-Q
L. A. Currie, “International Recommendations Offered on Analytical Detection and Quantification Concepts and Nomenclature,” Analytica Chimica Acta, Vol. 391, No. 2, 1999, p. 103. doi:10.1016/S0003-2670(99)00103-8
J. Mocak, A. M. Bond, S. Mitchell and G. Scollary, “A Statistical Overview of Standard (IUPAC and ACS) and New Procedures for Determining the Limits of Detection and Quanti?cation: Application to Voltammetric and Stripping Techniques,” Pure and Applied Chemistry, Vol. 69, No. 2, 1997, pp. 297-328. doi:10.1351/pac199769020297