Characteristics of glutathione-capped ZnS nanocrystallites.

The titration of increasing equivalents of inorganic sulfide into preformed Zn-glutathione led to the appearance of UV/VIS spectral features attributable to ZnS nanocrystallites. Glutathione-ZnS complexes upon irradiation caused reduction of methylviologen confirming their semiconductor properties. Size-fractionation of glutathione-ZnS samples on a gel filtration column showed the formation of a range of complexes whose spectral properties were correlated with the sulfide content. The stoichiometry of Zn:glutathione increased from 1:2 to a maximum of about 7:1 as the sulfide/Zn ratios increase from 0 to approximately 1.0 in Zn-glutathione complex indicating up to 14-fold increase in the Zn-binding capacity of glutathione upon sulfide incorporation. Spectral characteristics of GSH-capped ZnS nanocrystallites were significantly influenced by pH and by the stoichiometry of Zn, sulfide and glutathione in the complex. Samples containing least glutathione and highest sulfide showed maximal luminescence at pH 6, whereas those with higher glutathione and lower sulfide content showed maximal luminescence at pH 11.