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Transformation of Thioester‐Initiated Star Polymers into Linear Arms via Native Chemical Ligation
Author(s) -
Aksakal Suzan,
Aksakal Resat,
Becer Caglar Remzi
Publication year - 2019
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.201900247
Subject(s) - thioester , polymerization , polymer , polymer chemistry , native chemical ligation , chemistry , molar mass distribution , chain transfer , radical polymerization , end group , materials science , organic chemistry , enzyme , cysteine
The synthesis of a new class of Cu‐mediated polymerization initiators with thioester functionality is demonstrated and their polymerization kinetics via single‐electron transfer living radical polymerization is reported. From periodic sampling, it is found that thioester‐ or ester‐based initiators can be employed interchangeably, resulting in very similar polymerization rates. Furthermore, a multifunctional thioester initiator is employed for the preparation of a well‐defined four‐arm star‐shaped polymer. It is further shown that the full dissociation of the star polymer into linear arms via native chemical ligation can easily be followed via size exclusion chromatography, as a result of the change in hydrodynamic volume. Finally, the obtained linear polymers are characterized via matrix‐assisted laser desorption/ionization–time of flight mass spectrometry and found to be in good agreement with the expected molecular weight distribution that confirms the successful transformation.