Chiral Octahedral Cobalt(III) Complex Immobilized on Carboblack C as a Novel Robust and Readily Available Enantioselective Voltammetric Sensor for the Recognition of Tryptophan Enantiomers in Real Samples

Zilberg, R.A.; Teres, J.B.; Bulysheva, E.O.; Vakulin, I.V.; Mukhametdinov, G.R.; Khromova, O.V.; Panova, M.V.; Medvedev, M.G.; Maleev, V.I.; Larionov, V.A.

Авторы: Zilberg Rufina A., Teres Julia B., Bulysheva Elena O., Vakulin Ivan V., Mukhametdinov Genghiskhan R., Khromova Olga V., Panova Maria V., Medvedev Michael G., Maleev Victor I., Larionov Vladimir A.
Журнал: Electrochimica Acta
Том: 492
Год издания: 2024
Издательство: Elsevier BV
Местоположение издательства: Netherlands
Номер статьи: 144334
DOI: 10.1016/j.electacta.2024.144334
Аннотация: Enantioselective voltammetric sensors (EVSs) have significant interest in analytical and medicinalchemistry, as they allow for the express analysis and recognition of pharmacologically active components in drugs, as well as the establishment of the enantiopurity of compounds. The mostcommon methods of modifying the electrode surface are through molecular imprinting techniques and the addition of a non-electroactive chiral modifier to the electrode composition. By varyingthe structure and properties of the chiral modifier, the sensor can be designed to have the highest enantioselectivity for a chosen chiral analyte. In this study, we describe the development of a new type of EVS based on a Carboblack C paste electrode modified with a chiral octahedral cobalt(III) complex for use as a selective enantioselector. It was found that the EVS, prepared from enantiopure Co(III) complexes, can selectively recognize L- and D-tryptophan (Trp) in phosphate buffer solution (PBS) with pH = 6.86. The peak current ratio (iD/iL) between the two enantiomers reached 1.36, demonstrating the effectiveness of the sensor. The experimental results indicate a linear correlation between the peak currents of Trp enantiomers and their concentration in the range from 1.00·10-6to 5.00·10-4 М, leading to a detection limit of 2.42 µM and 3.30 µM for Dand L-Trp, respectively, when using chiral octahedral Co(III) complex with chloride counteranion. Next, the EVSs developed demonstrated practical applicability in measuring the concentration of Trp in pharmaceutical samples and human urine and blood plasma. An importantadvantage of these sensors is the difference in the oxidation potentials between Trp enantiomers(ΔEp=35 mV), which makes it possible to determine Trp enantiomers in their mixtures. Quantumchemical calculations and experimental data show that the octahedral Co(III) complex binds toone of the Trp enantiomers with a stronger affinity, thus increasing its concentration at theelectrode surface and promoting its oxidation. The easy preparation of the chiral Co(III) complexfrom inexpensive commercial materials, its high stability and insolubility in water make it apromising selector for the creation of efficient multifunctional EVSs for the analysis of variousaqueous solutions.
Добавил в систему: Ларионов Владимир Анатольевич

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Chiral Octahedral Cobalt(III) Complex Immobilized on Carboblack C as a Novel Robust and Readily Available Enantioselective Voltammetric Sensor for the Recognition of Tryptophan Enantiomers in Real Samplesстатья Исследовательская статья

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