Computational Modeling of Bromide and Chloride Catalyzed Formation of Sulfilimine Crosslinks
Professor Stan Zygmunt, Professor Haiying He
Arts and Sciences
A recent experimental study has demonstrated the essential connection between the concentration of ionic bromide (Br-) and the effective formation of sulfilimine crosslinks for assembly of collagen IV scaffolds in tissue development and architecture. In contrast, ionic chloride (Cl-) is shown to have a stronger preference for the formation of sulfoxide groups with at least 50,000 times less efficiency than Br- to catalyze the formation of sulfilimine crosslinks. In this work, we have carried out a comparison study of Br- and Cl- for sulfilimine and sulfoxide formation reactions using the density functional theory. The NC1 domains of collagen IV scaffolds are modeled by small clusters maintaining key functional groups at residues methionine 93 (Met93) and hydroxylysine 211 (Hyl211). We have searched for the minimum energy pathway for each reaction from a vast exploration of possible pathways in aqueous solution. Our results show qualitative agreement with experiment. The reaction mechanism and the different behavior of Br- and Cl- in catalyzing these reactions will be discussed.
Kim, Taegyun; Stan, Zygmunt Dr.; He, Haiying Dr.; and Morrissey, Christopher, "Computational Modeling of Bromide and Chloride Catalyzed Formation of Sulfilimine Crosslinks" (2015). Symposium on Undergraduate Research and Creative Expression (SOURCE). 590.