Elucidating the Mechanism of Copper-Induced Photoluminescence Quenching in 2-Phenylbenzimidazole-5-Sulfonic Acid.

To explore the possible impact of 2-Phenylbenzimidazole-5-sulfonic acid (PBSA) on the function of a sunscreen, in this work we investigate the binding of copper metal ions (Cu2+) to PBSA. Due to the existence of an intrinsic interaction phenomenon between Cu2+ ions and PBSA molecules, the photoluminescence (PL) quenching arises owing to the charge transfer from PBSA to Cu2+ ions. The mechanism of fluorescence quenching is probed experimentally following excitation at 306 nm by evaluating various quenching parameters with the help of the Stern-Volmer plot. Through the assessment of the values of the Stern-Volmer constant ( K SV = 45.2 M - 1 ) and bimolecular quenching rate constant ( k q = 0.77 × 10 10 M - 1 . s - 1 ), it is deduced that the dynamic mode of PL quenching is operative between PBSA and Cu2+ ions. We evaluate the number of binding sites (n = 1) that advocate the presence of a single binding site in PBSA for Cu2+ ions. The numerical value of standard Gibbs free energy change, Δ G o ~ -27.485 kJ.mol-1 implies the spontaneous binding between Cu2+ ions and PBSA molecules. The results obtained give an insight into the mechanism of metal-induced PL quenching of water soluble PBSA sunscreen.

Elucidating the Size-dependent FRET Efficiency in Interfacially Engineered Quantum Dots Attached to PBSA Sunscreen.

Applying sunscreen on human skin provides photoprotection against the harmful ultraviolet (UV) radiation of the sun. Sunscreen absorbs UV radiations and dissipates the absorbed energy through various radiative and nonradiative pathways. The attachment of functionalized quantum dots (QDs) to the sunscreen component is a novel idea to enhance the absorption cross-section of UV radiations. Therefore, the attachment of the sunscreen component to the ligand functionalized biocompatible QDs and the absorbed energy transfer from sunscreen to the QDs could work as a model system to overall improve the efficiency of the sunscreen. This study elucidates the mechanism of size-dependent Förster resonance energy transfer (FRET) efficiency and its rate between 2-phenylbenzimidazole-5-sulfonic acid (PBSA) and mercaptoacetic acid (MAA) functionalized CdS QDs. In the PBSA-QDs dyad, the PBSA (donor) dissipates UV-absorbed energy to the CdS QDs (acceptor). Following excitation at 306 nm, the steady-state photoluminescence (SSPL) and time-resolved photoluminescence (TRPL) techniques measurements demonstrate that both the nonradiative energy transfer efficiency and rate are QDs size-dependent in addition to donor-acceptor distance, and suggest that bigger sized-QDs result in an increase of the FRET efficiency.