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Naked and Self‐Clickable Propargylic‐Decorated Single‐Chain Nanoparticle Precursors via Redox‐Initiated RAFT Polymerization
Author(s) -
SanchezSanchez Ana,
AsenjoSanz Isabel,
Buruaga Lorea,
Pomposo José A.
Publication year - 2012
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201200180
Subject(s) - polymerization , dispersity , polymer chemistry , monomer , click chemistry , raft , nanoparticle , chain transfer , chemistry , alkyne , copolymer , reversible addition−fragmentation chain transfer polymerization , redox , materials science , nanotechnology , radical polymerization , catalysis , organic chemistry , polymer
Protection of acetylenic monomers is a common practice to avoid parasitic side reactions during polymerization. Herein, we report that redox‐initiated RAFT polymerization allows the direct, room temperature synthesis of a variety of single‐chain nanoparticle precursors (displaying narrow molecular weight dispersity, $\overline{M}_{\rm w}$ / $\overline{M}_{\rm n}$ = 1.12 –1.37 up to $\overline{M}_{\rm w}$ = 100 kDa) containing well‐defined amounts of naked, unprotected acetylenic functional groups available for rapid and quantitative intrachain cross‐linking via metal‐catalyzed carbon–carbon coupling (i.e., C–C “click” chemistry). To illustrate the useful “self‐clickable” character of the new unprotected acetylenic precursors, single‐chain nanoparticles have been prepared for the first time in a facile and highly efficient manner by copper‐catalyzed alkyne homocoupling (i.e., Glaser–Hay coupling) at room temperature under normal air atmosphere.