Electrospray Gold Standards of Molecular Mass 32- to 52-kDa: Charging Patterns of the Ubiquitous Virus-like Clusters, I - 197Au144-5(SR)60, R = 8 Variants, in Native [HPLC]-ESI-MS

Abstract

Faradays legendary Molecules of Gold have stimulated intense interest (over 165 years) but have only recently begun to yield their secrets to modern methods of chemical analysis. Here(in), we demonstrate how striking charging patterns emerge directly from native electrospray of large, gold-rich molecules that were generated by reduction of various (8) small gold(I)thiolate complexes [-RS-Au(I)-SR-], followed by extensive thermochemical processing to enrich the most robust forms. In each case (R), electrospray ionization of a picomolar solution yields a characteristic series of abundant, highly resolved peaks at related (m/z)-ratios, that can be used to deduce charges {z e+} and hence a distinct molecular mass, {MR}. A plot of {MR} versus thiolate-mass {mL} yields a straight line with slope 60.0 (the ligand count) and an intercept of 28,364-Da, the mass of 144 Au-atoms. i.e., a unique molecular composition {197Au144(SR)60}. This formula agrees with the unique chiral-icosahedral structure-model, c@12@42@60@(30,60), the Pd145(CO)60-structure, that features a massively-compact globular Au114-core (~1.6-nm) and an intrinsically chiral (I) outer shell (~2.0-nm) with 12 distinct ligand types of 5-fold equivalence], denoted by Martin et al. as virus-like on the basis of its resemblance of icosahedral-virus capsids.