One of the most significant advances with NMP was the isolation of an alkoxyamine that could act as a unimolecular agent, providing both the reactive, initiating radical and the stable, mediating nitroxide radical. Initially, nitroxides were employed as additives to reversibly terminate polymer chains initiated by a separate radical source. By using TEMPO to trap a styrenyl radical initiated by benzoyl peroxide (as shown by structure A of Scheme 1), Hawker demonstrated an ability to tune the molecular weight, define the end groups, and extend to block copolymers, while maintaining narrow molecular weight distributions. He later developed a universal initiator, which has received broad application in laboratories around the world. A key limitation to the use of this universal initiator remained the challenge of its synthesis. With it now being offered commercially by Aldrich Materials Science, it is expected that NMP will experience a renewed vigor of investigation. With our interest in the construction of nanoscopic objects via the selfassembly of amphiphilic block copolymers in water, we have used the universal initiator (Aldrich Prod. No. 700703), in the presence of less than 5 equivalent percent of the corresponding nitroxide (added to assist with capping the propagating chain ends during polymerization), to prepare an amphiphilic diblock copolymer precursor, poly(tert-butyl acrylate)-b-poly(4-acetoxystyrene) with a controlled molecular weight and a narrow molecular weight distribution (Scheme 2). - See more at: http://www.sigmaaldrich.com/technical-documents/articles/material-matters/block-copolymer-synthesis.html#sthash.I4Cswj8a.dpuf