title: Photoinduced Bioorthogonal 1,3-Dipolar Poly-cycloaddition Promoted by Oxyanionic Substrates for Spatiotemporal Operation of Molecular Glues.
abstract: PGlue(PZ), a pyrazoline (PZ)-based fluorescent adhesive which can be generated spatiotemporally in living systems, was developed. Since PGlue(PZ) carries many guanidinium ion (Gu(+)) pendants, it strongly adheres to various oxyanionic substrates through a multivalent salt-bridge interaction. PGlue(PZ) is given by bioorthogonal photopolymerization of a Gu(+)-appended monomer (Glue(TZ)), bearing tetrazole (TZ) and olefinic termini. Upon exposure to UV light, Glue(TZ) transforms into a nitrileimine (NI) intermediate (Glue(NI)), which is eligible for 1,3-dipolar polycycloaddition. However, Glue(NI) in aqueous media can concomitantly be deactivated into Glue(WA) by the addition of water, and the polymerization hardly occurs unless Glue(NI) is concentrated. We found that, even under high dilution, Glue(NI) is concentrated on oxyanionic substrates to a sufficient level for the polymerization, so that their surfaces can be point-specifically functionalized with PGlue(PZ) by the use of a focused beam of UV light.
authors.affiliation: Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan).
authors.forename: Junichi
authors.initials: J
authors.lastname: Hatano
authors.affiliation: Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan). okuro@macro.t.u-tokyo.ac.jp.
authors.forename: Kou
authors.initials: K
authors.lastname: Okuro
authors.affiliation: Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan). aida@macro.t.u-tokyo.ac.jp.|RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan). aida@macro.t.u-tokyo.ac.jp.
authors.forename: Takuzo
authors.initials: T
authors.lastname: Aida
mesh_terms: D000269:Adhesives / Q000737:chemistry*; D000838:Anions / Q000737:chemistry; D003500:Cyclization; D061565:Cycloaddition Reaction; D019791:Guanidine / Q000737:chemistry*; D015394:Molecular Structure; D010316:Particle Size; D055668:Photochemical Processes; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry; D011720:Pyrazoles / Q000737:chemistry*; D013499:Surface Properties
chemical_list: D000269:Adhesives; D000838:Anions; D011108:Polymers; D011720:Pyrazoles; D019791:Guanidine
keywords: adhesives; bioorganic chemistry; noncovalent interactions; photochemistry; polymerization