Cu-Enhanced Efficient Förster Resonance Energy Transfer in PBSA Sunscreen-Associated Ternary Cu x Cd1- x S Quantum Dots

Abstract

Quantum dots (QDs) are semiconducting nanocrystals that exhibit size- and composition-dependent optical and electronic properties. Recently, Cu-based II-VI ternary Cu _x Cd_1-x S (CCS) QDs have emerged as a promising class of QDs as compared to their binary counterparts (CuS and CdS). Herein, a series of ternary CCS QDs are synthesized by changing the molar concentration of Cu²⁺ ions only keeping the 1:1 ratio of the stoichiometric mixture of Cd²⁺ and S^2-. These CCS QDs are attached to 2-phenylbenzimidazole-5-sulfonic acid (PBSA), an eminent UV-B filter widely used in many commercial sunscreen products to avoid skin erythema and DNA mutagenic photolesions. The photoinduced Förster resonance energy transfer (FRET) is investigated from PBSA to CCS QDs as a function of Cu concentration in CCS QDs using the steady-state photoluminescence and time-resolved photoluminescence measurements. A 2-fold increase in the magnitude of non-radiative energy transfer rate (K _T(r)) is observed as the molar concentration of Cu in CCS QDs increases from 2 to 10 mM. Our findings suggest that in PBSA-CCS QD dyads, the FRET occurrence from PBSA to QDs is dictated by the dynamic mode of photoluminescence (PL) quenching. The bimolecular PL quenching rate constants (k _q) estimated by Stern-Volmer's plots for PBSA-CCS QD dyads are of the order of 10¹⁰ M^-1 s^-1, which signifies that in the PBSA-CCS QD dyad FRET system, the process of PL quenching is entirely diffusion-controlled.