Model Calculations Relevant to Disulfide Bond Cleavage via Electron Capture Influenced by Positively Charged Groups

Abstract

Ab initio electronic structure calculations are used to explore the effect of nonneighboring positively charged groups on the ability of low-energy (<1 eV) electrons to directly attach to S−S σ bonds in disulfides to effect bond cleavage. It is shown that, although direct vertical attachment to the σ* orbital of an S−S σ bond is endothermic, the stabilizing Coulomb potential produced in the region of the S−S bond by one or more distant positive groups can render the S−S σ* anion state electronically stable. This stabilization, in turn, can make near vertical electron attachment exothermic. The focus of these model studies is to elucidate a proposed mechanism for bond rupture that may, in addition to other mechanisms, be operative in electron capture dissociation (ECD) experiments. The importance of these findings lies in the fact that a more complete understanding of how ECD takes place will allow workers to better interpret ECD fragmentation patterns observed in mass spectrometric studies of proteins and polypeptides.