title: Rapid Bioorthogonal Chemistry Turn-on through Enzymatic or Long Wavelength Photocatalytic Activation of Tetrazine Ligation.
abstract: Rapid bioorthogonal reactivity can be induced by controllable, catalytic stimuli using air as the oxidant. Methylene blue (4 μM) irradiated with red light (660 nm) catalyzes the rapid oxidation of a dihydrotetrazine to a tetrazine thereby turning on reactivity toward trans-cyclooctene dienophiles. Alternately, the aerial oxidation of dihydrotetrazines can be efficiently catalyzed by nanomolar levels of horseradish peroxidase under peroxide-free conditions. Selection of dihydrotetrazine/tetrazine pairs of sufficient kinetic stability in aerobic aqueous solutions is key to the success of these approaches. In this work, polymer fibers carrying latent dihydrotetrazines were catalytically activated and covalently modified by trans-cyclooctene conjugates of small molecules, peptides, and proteins. In addition to visualization with fluorophores, fibers conjugated to a cell adhesive peptide exhibited a dramatically increased ability to mediate contact guidance of cells.
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Han
authors.initials: H
authors.lastname: Zhang
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: William S
authors.initials: WS
authors.lastname: Trout
authors.affiliation: Department of Materials Science and Engineering, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Shuang
authors.initials: S
authors.lastname: Liu
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Gabriel A
authors.initials: GA
authors.lastname: Andrade
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Devin A
authors.initials: DA
authors.lastname: Hudson
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Samuel L
authors.initials: SL
authors.lastname: Scinto
authors.affiliation: Department of Materials Science and Engineering, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Kevin T
authors.initials: KT
authors.lastname: Dicker
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Yi
authors.initials: Y
authors.lastname: Li
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Nikifar
authors.initials: N
authors.lastname: Lazouski
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Joel
authors.initials: J
authors.lastname: Rosenthal
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Colin
authors.initials: C
authors.lastname: Thorpe
authors.affiliation: Department of Materials Science and Engineering, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Xinqiao
authors.initials: X
authors.lastname: Jia
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.|Department of Materials Science and Engineering, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Joseph M
authors.initials: JM
authors.lastname: Fox
mesh_terms: D000269:Adhesives; D002384:Catalysis; D004798:Enzymes / Q000737:chemistry; D006573:Heterocyclic Compounds, 1-Ring / Q000737:chemistry*; D006735:Horseradish Peroxidase / Q000737:chemistry; D007700:Kinetics; D008027:Light; D008751:Methylene Blue / Q000737:chemistry; D010084:Oxidation-Reduction; D055668:Photochemical Processes; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000269:Adhesives; D004798:Enzymes; D006573:Heterocyclic Compounds, 1-Ring; D006735:Horseradish Peroxidase; D008751:Methylene Blue