Electrochemical Study and Determination of All-trans-Retinol at Carbon Paste Electrode Modified by a Surfactant

U radu je cikličkom voltametrijom istražen mehanizam oksidacije trans-retinola (vitamina A1) i nekoliko njegovih estera u organskom otapalu, miješanoj otopini voda/organsko otapalo i vodenoj otopini. Proces oksidacije odvijao se u nekoliko ireverzibilnih koraka. Najveća gustoća elektrona u retinoidnoj molekuli delokaliziranih oko ugljikovih atoma vezanih s pet konjugiranih dvostrukih veza (C5-C14) pronađena je u dijelu molekule koji sudjeluje u oksidaciji. Najviši oksidacijski pik (na +0.8 V prema Ag/AgCl elektrodi) korišten je za određivanje retinola diferencijalnom pulsnom voltametrijom pomoću elektrode od ugljikove paste modificirane površinski aktivnom tvari (natrijev dodecil-sulfat). Rezultati pokazuju da je s dodatkom 30 % (po masi) natrijeva dodecil-sulfata dobivena optimalna osjetljivost elektrode i optimalan oblik voltamograma. U usporedbi s uobičajenom elektrodom od staklastog ugljika, elektroda od ugljikove paste modificirane pomoću natrijeva dodecil-sulfata bitno je pospješila elektroanalizu retinola. Linearan odziv modificirane elektrode od ugljikove paste bio je u rasponu od 1,5·10^−6–1,8·10^−4 M retinola s limitom detekcije 1,3·10^−6 M, dok je elektroda od staklastog ugljika imala linearni raspon 4,4·10^−6–7,0·10^−4 M i limit detekcije 4,6·10^−7 M.The oxidation mechanism of all-trans-retinol (vitamin A1) and its several esters in non-aqueous, aqueous organic mixture, and pure aqueous media was investigated by cyclic voltammetry. The oxidation occurred in several irreversible steps. The calculated highest density of electrons in retinoid molecules which are delocalized over carbon atoms of the five conjugated double bonds (C5-C14) was found in the part of the molecule involved in oxidation processes. The most sensitive oxidation peak (at +0.8 V vs. Ag/AgCl) was used for development of new direct voltammetric method based on differential pulse voltammetry for the determination of retinol at carbon paste electrode modified with surfactant sodium dodecyl sulfate (CPE/SDS). The results show that 30 % (by mass) of modifier SDS exhibited optimal sensitivity and shape of voltammograms. Compared to commonly used glassy carbon electrode (GCE), the CPE/SDS showed significant progress in the retinol electroanalysis. The linear ranges for retinol determination were 1.5·10^−6–1.8·10^−4 M for CPE/SDS and 4.4·10^−6–7.0·10^−4 M for GCE with the detection limits of 1.3·10^−6 and 4.6·10^−7 M, respectively