title: Photodissociation of non-covalent peptide-crown ether complexes.
abstract: Highly chromogenic 18-crown-6-dipyrrolylquinoxaline coordinates primary amines of peptides, forming non-covalent complexes that can be transferred to the gas-phase by electrospray ionization. The appended chromogenic crown ether facilitates efficient energy transfer to the peptide upon ultraviolet irradiation in the gas phase, resulting in diagnostic peptide fragmentation. Collisional-activated dissociation and infrared multiphoton dissociation of these non-covalent complexes result only in their disassembly with the charge retained on either the peptide or crown ether, yielding no sequence ions. Upon UV photon absorption the intermolecular energy transfer is facilitated by the fast activation timescale of ultraviolet photodissociation (<10 ns) and by the collectively strong hydrogen bonding between the crown ether and peptide, thus allowing effective transfer of energy to the peptide moiety before disruption of the intermolecular hydrogen bonds.
authors: Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712, USA.
authors: Jeffrey J
authors: JJ
authors: Wilson
authors: Gregory J
authors: GJ
authors: Kirkovits
authors: Jonathan L
authors: JL
authors: Sessler
authors: Jennifer S
authors: JS
authors: Brodbelt
mesh_terms: D000588:Amines / Q000737:chemistry; D043844:Crown Ethers / Q000737:chemistry*; D006860:Hydrogen Bonding; D010455:Peptides / Q000737:chemistry*; D010777:Photochemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D014466:Ultraviolet Rays
chemical_list: D000588:Amines; D043844:Crown Ethers; D010455:Peptides