title: (Ultra)fast catalyst-free macromolecular conjugation in aqueous environment at ambient temperature.
abstract: Tailor-made water-soluble macromolecules, including a glycopolymer, obtained by living/controlled RAFT-mediated polymerization are demonstrated to react in water with diene-functionalized poly(ethylene glycol)s without pre- or post-functionalization steps or the need for a catalyst at ambient temperature. As previously observed in organic solvents, hetero-Diels-Alder (HDA) conjugations reached quantitative conversion within minutes when cyclopentadienyl moieties were involved. However, while catalysts and elevated temperatures were previously necessary for open-chain diene conjugation, additive-free HDA cycloadditions occur in water within a few hours at ambient temperature. Experimental evidence for efficient conjugations is provided via unambiguous ESI-MS, UV/vis, NMR, and SEC data.
authors.affiliation: Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie and Centre for Functional Nanostructures, Karlsruhe Institute of Technology, Engesserstrasse 18, 76128 Karlsruhe, Germany.
authors.forename: Mathias
authors.initials: M
authors.lastname: Glassner
authors.forename: Guillaume
authors.initials: G
authors.lastname: Delaittre
authors.forename: Michael
authors.initials: M
authors.lastname: Kaupp
authors.forename: James P
authors.initials: JP
authors.lastname: Blinco
authors.forename: Christopher
authors.initials: C
authors.lastname: Barner-Kowollik
mesh_terms: D000466:Alkadienes / Q000138:chemical synthesis / Q000737:chemistry*; D003500:Cyclization; D011092:Polyethylene Glycols / Q000138:chemical synthesis / Q000737:chemistry*; D011102:Polyhydroxyethyl Methacrylate / Q000031:analogs & derivatives / Q000138:chemical synthesis / Q000737:chemistry; D058105:Polymerization; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry*; D011134:Polysaccharides / Q000138:chemical synthesis / Q000737:chemistry; D013696:Temperature; D014867:Water / Q000737:chemistry*
chemical_list: D000466:Alkadienes; D011108:Polymers; D011134:Polysaccharides; D014867:Water; D011102:Polyhydroxyethyl Methacrylate; C023037:poly(2-hydroxyethyl acrylate); D011092:Polyethylene Glycols