title: Transimination of quinone imines: a mechanism for embedding exogenous redox activity into the nucleosome.
abstract: Aminophenols can redox cycle through the corresponding quinone imines to generate ROS. The electrophilic quinone imine intermediate can react with protein thiols as a mechanism of immobilization in vivo. Here, we describe the previously unkown transimination of a quinone imine by lysine as an alternative anchoring mechanism. The redox properties of the condensation product remain largely unchanged because the only structural change to the redox nucleus is the addition of an alkyl substituent to the imine nitrogen. Transimination enables targeting of histone proteins since histones are lysine-rich but nearly devoid of cysteines. Consequently, quinone imines can be embedded in the nucleosome and may be expected to produce ROS in maximal proximity to the genome.
authors.affiliation: Department of Biological Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Wenjie
authors.initials: W
authors.lastname: Ye
authors.forename: Uthpala I
authors.initials: UI
authors.lastname: Seneviratne
authors.forename: Ming-Wei
authors.initials: MW
authors.lastname: Chao
authors.forename: Kodihalli C
authors.initials: KC
authors.lastname: Ravindra
authors.forename: Gerald N
authors.initials: GN
authors.lastname: Wogan
authors.forename: Steven R
authors.initials: SR
authors.lastname: Tannenbaum
authors.forename: Paul L
authors.initials: PL
authors.lastname: Skipper
mesh_terms: D000818:Animals; D016466:CHO Cells; D006224:Cricetinae; D003412:Cricetulus; D006657:Histones / Q000378:metabolism*; D007097:Imines / Q000378:metabolism*; D008239:Lysine / Q000378:metabolism; D009707:Nucleosomes / Q000378:metabolism*; D010084:Oxidation-Reduction; D011809:Quinones / Q000378:metabolism*
chemical_list: D006657:Histones; D007097:Imines; D009707:Nucleosomes; D011809:Quinones; D008239:Lysine