Adsorption of l-Cysteine and Cysteamine on Zinc Oxide Nanoparticles

The reaction of l-cysteine and cysteamine hydrochloride with zinc oxide nanoparticles (ZnO NPs), by stirring excess reactant with the NPs in ethanol, has been studied by thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Raman spectroscopy. l-Cysteine adsorption occurs via the thiol functional group, and there is no evidence for bonding via the carboxylic acid or amine functionalities. However, Raman spectroscopy and XPS reveal some protonated thiol, suggesting unbound l-cysteine is also present, as confirmed by XRD that shows the presence of l-cysteine crystallites. In the case of cysteamine/ZnO, TGA indicates that a large fraction of the sample is organic, and Raman spectroscopy reveals a dramatic shift in the C-S stretch from 796 cm^-1 for unreacted cysteamine to 837 cm^-1 for the reacted cysteamine. It is postulated that the acidic and chelating nature of the reaction causes dissolution of some Zn²⁺ ions that form a Zn(II) coordination complex with cysteamine. These studies have implications for biomolecular applications in which ZnO nanoparticles are used for biosensors, bioimaging, and drug delivery.