Electrospray ionization mass spectrometry of uniform and mixed monolayer nanoparticles: Au25[S(CH2)2Ph]18 and Au25[S(CH2)2Ph]18-x(SR)x.

New approaches to electrospray ionization mass spectrometry (ESI-MS)-with exact compositional assignments-of small (Au25) nanoparticles with uniform and mixed protecting organothiolate monolayers are described. The results expand the scope of analysis and reveal a rich chemistry of ionization behavior. ESI-MS of solutions of phenylethanethiolate monolayer-protected gold clusters (MPCs), Au25(SC2Ph)18, containing alkali metal acetate salts (MOAc) produce spectra in which, for Na+, K+, Rb+, and Cs+ acetates, the dominant species are MAu25(SC2Ph)182+ and M2Au25(SC2Ph)182+. Li+ acetates caused ligand loss. This method was extended to the analysis of Au25 MPCs with mixed monolayers, where thiophenolate (-SPh), hexanethiolate (-SC6), or biotinylated (-S-PEG-biotin) ligands had been introduced by ligand exchange. In negative-mode ESI-MS, no added reagents were needed in order to observe Au25(SC2Ph)18- and to analyze mixed monolayer Au25 MPCs prepared by ligand exchange with 4-mercaptobenzoic acid, HSPhCOOH, which gave spectra through deprotonation of the carboxylic acids. Adducts of tetraoctylammonium (Oct4N+) with -SPhCOO- sites were also observed. Mass spectrometry is the only method that has demonstrated capacity for measuring the exact distribution of ligand-exchange products. The possible origins of the different Au25 core charges (1-, 0, 1+, 2+) observed during electrospray ionization are discussed.