title: The design and synthesis of alanine-rich α-helical peptides constrained by an S,S-tetrazine photochemical trigger: a fragment union approach.
abstract: The design and synthesis of alanine-rich α-helical peptides constrained in a partially unfolded state by incorporation of the S,S-tetrazine phototrigger has been achieved, permitting, upon photochemical release, observation by 2D-IR spectroscopy of the subnanosecond conformational dynamics that govern the early steps associated with α-helix formation. Solid-phase peptide synthesis was employed to elaborate the requisite fragments, with full peptide construction via solution-phase fragment condensation. The fragment union tactic was also employed to construct (13)C═(18)O isotopically edited amides to permit direct observation of conformational motion at or near specific peptide bonds.
authors.affiliation: Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104, United States.
authors.forename: Joel R
authors.initials: JR
authors.lastname: Courter
authors.forename: Mohannad
authors.initials: M
authors.lastname: Abdo
authors.forename: Stephen P
authors.initials: SP
authors.lastname: Brown
authors.forename: Matthew J
authors.initials: MJ
authors.lastname: Tucker
authors.forename: Robin M
authors.initials: RM
authors.lastname: Hochstrasser
authors.forename: Amos B
authors.initials: AB
authors.lastname: Smith
mesh_terms: D000409:Alanine / Q000737:chemistry*; D015394:Molecular Structure; D010455:Peptides / Q000138:chemical synthesis* / Q000737:chemistry; D055668:Photochemical Processes; D013777:Tetrazoles / Q000737:chemistry*
chemical_list: D010455:Peptides; D013777:Tetrazoles; D000409:Alanine