Letter: Supermetallization of peptides and proteins with tetravalent metal Th(IV).

Supermetallization is the recently observed phenomenon of the formation of complex ions of peptide-metal in the gas phase when the peptide accepts an unexpectedly large number of metal atoms. It has been found that supermetallization takes place during electrospray ionization when charged droplets are evaporating at relatively high temperature (ca 400°C). In the present paper, we demonstrate supermetallized complexes of small protein ubiquitin and two peptides with Th(IV). We have observed complexes of ubiquitin with up to five thorium atoms, and attaching each Th(IV) requires the removal of four hydrogen atoms. To our knowledge, this is the first demonstration of gas-phase complexes of peptides and proteins with tetravalent metal atoms..