An ultrasensitive photoelectrochemical sensor with layer-by-layer assembly of chiral multifarene[3,2,1] and g-C3N4 quantum dots for enantiorecognition towards thyroxine

Abstract

A photoelectrochemical sensor was developed with stepwise decoration of g-C 3 N 4 quantum dots and chiral multifarene[3,2,1] to achieve the ultrasensitive enantiorecognition for L -thyroxine. • A facile method for preparation of g-C 3 N 4 quantum dots was discovered. • A photoelectrochemical sensor built with g-C 3 N 4 QDs and chiral macrocycle was developed. • The ultrasensitive enantiorecognition for thyroxine was reached with the proposed photoelectrochemical sensor. With a facile preparation for graphitic carbon nitride quantum dots (g-C 3 N 4 QDs), an ultrasensitive photoelectrochemical (PEC) sensor was developed with the supramolecular affinity of chiral multifarene[3,2,1] (CMF) to a hormone drug, thyroxine (T 4 ), for efficient identification of thyroxine enantiomers. In the principle that g-C 3 N 4 QDs was employed to achieve the photocurrent response and the macrocyclic compound served as the supramolecular enantiorecognition for thyroxine, the photoelectrochemical electrode was constructed by layer-by-layer assembly of g-C 3 N 4 QDs and CMF on the surface of ITO (ITO-g-C 3 N 4 -CMF QDs). The proposed PEC sensor produced the limits of detection low to 67 pM towards L -T 4 and 85 pM towards D -T 4 in a concentration range from 0.1 nM to 10 nM, which was superior to the values in pioneering reports with colorimetric or electrochemical methods. With good stability, reproducibility, repeatability anti-interference ability, and acceptable recoveries, the proposed PEC sensor was employed for quantitative determination of L/D -T 4 in water, human serum and commercial tablet.