TY - JOUR

T1 - Electrochemistry and electrochemical assessment of host–guest complexation of substituted pillar[m]arene[n]quinones

AU - Shamagsumova, R. V.

AU - Kulikova, T. N.

AU - Porfireva, A. V.

AU - Shurpik, D. N.

AU - Stoikov, I. I.

AU - Rogov, A. M.

AU - Stoikov, D. I.

AU - Evtugyn, G. A.

N1 - Financial support of Russian Science Foundation (grant No 22-13-00070, https://rscf.ru/en/project/22-13-00070 ) is gratefully acknowledged.

PY - 2023/6/1

Y1 - 2023/6/1

N2 - Electrochemical behavior of pillar[n]arene[m]quinone (n + m = 5, n = 2–4) has been for the first time investigated in aqueous media on the glassy carbon electrode. All the compounds studied showed quasi-reversible redox conversion to hydroquinone derivatives. The reaction was not complicated with ionization of hydroxy groups or by the formation of intramolecular hydrogen bonds. In the whole pH region tested (2.0 – 9.0) the stoichiometry of electron and hydrogen ions transfer was found the same (1:1). The peak currents changed with no respect of the number of quinone units in the macrocycle molecule and were probably more affected by steric factors and self-aggregation confirmed by scanning electron microscopy. Adsorption of the macrocycles on the electrode covered with carbon black resulted in remarkable improvement of the conditions of electron exchange and of the peak currents on voltammograms. Screening of possible guest molecules showed that among amino acids, tyrosine formed complexes with pillarquinones both in solution and on the electrode interface. Complexation resulted in decrease of the peak currents on voltammograms due to steric hindrance of electric wiring. This made it possible to determine 5–100 µM tyrosine in the solution and 1–100 µM tyrosine with pillar[3]arene[2]quinone adsorbed in the carbon black layer. No interferences were established in normal human serum and Ringer-Locke’s solution. The approach to supramolecular detection of small molecules by intrinsic redox activity of the macrocyclic hosts can be extended to other analytes by modification of the macrocyclic components of the reaction.

AB - Electrochemical behavior of pillar[n]arene[m]quinone (n + m = 5, n = 2–4) has been for the first time investigated in aqueous media on the glassy carbon electrode. All the compounds studied showed quasi-reversible redox conversion to hydroquinone derivatives. The reaction was not complicated with ionization of hydroxy groups or by the formation of intramolecular hydrogen bonds. In the whole pH region tested (2.0 – 9.0) the stoichiometry of electron and hydrogen ions transfer was found the same (1:1). The peak currents changed with no respect of the number of quinone units in the macrocycle molecule and were probably more affected by steric factors and self-aggregation confirmed by scanning electron microscopy. Adsorption of the macrocycles on the electrode covered with carbon black resulted in remarkable improvement of the conditions of electron exchange and of the peak currents on voltammograms. Screening of possible guest molecules showed that among amino acids, tyrosine formed complexes with pillarquinones both in solution and on the electrode interface. Complexation resulted in decrease of the peak currents on voltammograms due to steric hindrance of electric wiring. This made it possible to determine 5–100 µM tyrosine in the solution and 1–100 µM tyrosine with pillar[3]arene[2]quinone adsorbed in the carbon black layer. No interferences were established in normal human serum and Ringer-Locke’s solution. The approach to supramolecular detection of small molecules by intrinsic redox activity of the macrocyclic hosts can be extended to other analytes by modification of the macrocyclic components of the reaction.

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U2 - 10.1016/j.jelechem.2023.117444

DO - 10.1016/j.jelechem.2023.117444

M3 - Article

VL - 938

JO - Journal of Electroanalytical Chemistry

JF - Journal of Electroanalytical Chemistry

SN - 1572-6657

M1 - 117444

ER -