Application of a biomimetic sensor based on iron phthalocyanine chloride: 4-methylbenzylidene-camphor detection

Abstract

A construção e a aplicação de um sensor biomimético para a determinação de 4-metilbenzilideno cânfora (4-MBC), um protetor de radiação ultravioleta (UV), são descritas. O sensor foi preparado pela modificação de um eletrodo de pasta de carbono com um complexo de cloreto de ferro(III) com ftalocianina, FePcCl. As medidas amperométricas conduzidas com o sensor, sob um potencial aplicado de 0,0 V vs. Ag|AgCl em uma mistura de tetraidrofurano e 0,1 mol L -1 H 2 SO 4 (30:70 em volume), mostraram uma resposta linear no intervalo de 1,8×10 -4 to 9,0×10 -4 mol L -1 . Uma investigação detalhada da seletividade da resposta frente a outros nove filtros UV também foi realizada. Um mecanismo de resposta do sensor foi proposto e os resultados para a quantificação de 4-MBC em protetores solares comerciais e em águas de piscinas e de rios são apresentados.The construction and application of a biomimetic sensor for determination of 4-methylbenzylidene camphor (4-MBC), an ultraviolet (UV) radiation protector, are described. The sensor was prepared by modifying a carbon paste electrode with iron(III) phthalocyanine chloride (FePcCl). Amperometric measurements carried out with the sensor under an applied potential of 0.0 V vs. Ag|AgCl in a mixture of tetrahydrofuran and 0.1 mol L -1 H 2 SO 4 solution (30:70 volume ratio) showed a linear response range from 1.8×10 -4 to 9.0×10 -4 mol L -1 . A detailed selectivity investigation for other nine UV filters was also performed. A sensor response mechanism was proposed and the results for 4-MBC quantification in commercial sunscreens and in water from swimming pools and rivers are presented.Keywords: iron phthalocyanine, amperometric sensor, methylbenzylidene camphor IntroductionChemical ultraviolet (UV) filters have been introduced in 1889, when an acidified quinine sulfate solution was used to block UV radiation, 1 and thereafter sunscreen has become an everyday cosmetic with continuously increasing use.The positive effect exerted by UV filters is to block the UV light radiation damage from sunlight, sunlamps and in tanning parlours; moreover, they have color protective abilities and therefore may prevent premature fading of hair color and damage to hair cuticle. On the other hand, it has been recently reported that commonly used chemical UV filters may cause endocrine disrupting effects in both aquatic and terrestrial animals, as well as in human skin cells. [1][2][3][4] In addition, five of the most commonly UV filters used in cosmetic formulations, i.e., oxybenzone, octyl methoxycinnamate (OMC), homosalate, p-aminobenzoic acid (PABA), octyldimethyl-PABA (ODP), and 4-methylbenzylidene camphor (4-MBC), exhibited oestrogenic effects in MCF-7 (Michigan Application of a Biomimetic Sensor Based on Iron Phthalocyanine Chloride J. Braz. Chem. Soc. 1378 Cancer Foundation-7) breast cancer cells. Furthermore, oxybenzone, 4-MBC and OMC were confirmed to be oestrogenic by classical in vivo uterotrophic assays with rats dosed in the feed. For the most potent oestrogenic UV filter 4-MBC, the eff...

Electroanalytical determination of bumetanide employing a biomimetic sensor for detection of doping in sports

“…All the chemicals used were of analytical or HPLC grade. Copper(II) 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecauoro 29H,31H-phthalocyanine [CuPc], bumetanide, mineral oil and graphite powder were purchased from Sigma-Aldrich.…”

“…The graph obtained by plotting the current of the oxidation peak of square wave voltammograms versus the concentration including saturated amounts of the analyte should be similar to that of an enzymatic biosensor, since the complex used had a structure similar to that of the P450 hemeenzymes. In the case of the biosensor based on redox enzymes, the current signal initially increases linearly with the concentration of the substrate ([S]), and then, as [S] is further increased, the enzyme becomes saturated, and the current signal reaches a maximum value 23,27 producing a graph with a hyperbolic prole. A biomimetic sensor, just as ours, should therefore produce the same graphic, which means the sensor response follows a pseudo-Michaelis-Menten kinetics, which is expected, since our catalyst is based on the structure of the active site of a redox enzyme.…”

“…18 In addition, the degradation of xenobiotics such as drugs, pesticides and endocrine disruptors is possible through hydroxylation, oxidation or reduction reactions. 18,19 Materials derived from the phthalocyanines and porphyrins of iron and other metals have been successfully used in the construction of biomimetic chemical sensors for analytical use, [20][21][22][23][24] since these compounds mimic the chemical structure of the P450 active site (iron protoporphyrin IX).…”

Analytical development of a binuclear oxo-manganese complex bio-inspired on oxidase enzyme for doping control analysis of acetazolamide

“…The biomimetic properties of the sensor were reflected in a response plot that showed a hyperbolic profile for acetazolamide concentrations between 1.00 Â 10 À 6 mol L À 1 and 1.00 Â 10 À 5 mol L À 1 (Supplementary material). In such cases, the reaction rate increases with increasing substrate concentration and must asymptotically approach the saturation rate that is directly proportional to the total biomimetic material concentration (Boni et al, 2010;Ruy et al, 2014). Similarly, for concentrations higher than 5.00 Â 10 À 6 mol L À 1 , the proposed bio-inspired sensor showed marked deviation from linearity, which could be attributed to the maximum saturation of the electrocatalytic sites on the electrode surface.…”

Cobalt phthalocyanine as a biomimetic catalyst in the amperometric quantification of dipyrone using FIA

“…Biomimetic sensors are more sensitive, compared to enzymatic biosensors, due to a smaller diffusion barrier and greater electron transfer between the biomimetic complex and the analyte [6,7]. This new and increasingly popular class of sensors has been used for the identification and quantification of various drugs [13][14][15][16][17], and has also been coupled to flow systems [18,19].…”