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Published on: April 10, 2012
(Ultra)fast catalyst-free macromolecular conjugation in aqueous environment at ambient temperature
Mathias Glassner1, Guillaume Delaittre, Michael Kaupp
1Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie and Centre for Functional Nanostructures, Karlsruhe Institute of Technology, Engesserstrasse 18, 76128 Karlsruhe, Germany.
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.
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