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Photoinduced Bioorthogonal 1,3‐Dipolar Poly‐cycloaddition Promoted by Oxyanionic Substrates for Spatiotemporal Operation of Molecular Glues
Author(s) -
Hatano Junichi,
Okuro Kou,
Aida Takuzo
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201507987
Subject(s) - glue , chemistry , tetrazole , polymerization , monomer , bioorthogonal chemistry , polymer chemistry , methacrylate , photopolymer , photochemistry , covalent bond , aqueous solution , polymer , stereochemistry , organic chemistry , materials science , click chemistry , composite material
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.