Quantum dot (QD) fluorescence is effectively quenched at low concentration by nitroxides bearing amine or carboxylic acid ligands. The association constants and fluorescence quenching of CdSe QDs with these derivatized nitroxides have been examined using electron paramagnetic resonance (EPR) and fluorescence spectroscopy. The EPR spectra in the non-protic solvent toluene are extremely sensitive to intermolecular and intramolecular hydrogen bonding of the functionalized nitroxides. Fluorescence measurements show that quenching of QD luminescence is nonlinear, with a strong dependence on the distance between the radical and the QD. The quenched fluorescence is restored when the surface-bound nitroxides are converted to hydroxylamines by mild reducing agents, or trapped by carbon radicals to form alkoxyamines. EPR studies indicate that photoreduction of the nitroxide occurs in toluene solution upon photoexcitation at 365 nm. However, photolysis in benzene solution gives no photoreduction, suggesting that photoreduction in toluene is independent of the quenching mechanism. The fluorescence quenching of QDs by nitroxide binding is a reversible process.

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A method to visually detect minute amounts of urushiol, the toxic catechol from poison oak, poison ivy, and poison sumac, has been developed utilizing the reaction of a profluorescent nitroxide with the B-n-butylcatecholboronate ester formed in situ from urushiol and B-n-butylboronic acid. The resulting N-alkoxyamine is strongly fluorescent upon illumination with a fluorescent lamp, allowing the location of the toxic urushiol contamination to be visualized. This methodology constitutes the groundwork for the future development of a spray to detect urushiol to avoid contact dermatitis, as well as to detect catecholamines for biomedical applications.