Controlled radical polymerization, which provides exquisite tuning of macromolecular size, structure, composition and architecture, with experimental convenience, has become one of the most indispensible tools for polymer chemists. Its emergence in the mid-1990s has greatly advanced the fields of nanoscience and nanotechnology, by providing ready access to complex polymers that serve as building blocks for functional nanostructures with predictable parameters such as the size, morphology, regioselective placement of functionalities, etc. This exceptional polymerization control is due to reversible termination events that mediate the radical concentration and reactivity. The living character of this type of polymerization provides an ability to produce polymers with controlled molecular weight and narrow molecular weight distribution, and, moreover, to chain extend with different monomers and obtain multi-block copolymers. Nitroxide-mediated radical polymerization (NMP) is one of these controlled radical polymerizations that also includes atom transfer radical polymerization (ATRP), and reversible addition-fragmentation chain transfer (RAFT) polymerization. NMP stands out due to its simplicity: the polymerization is thermally initiated in the absence of an external radical source or a metal catalyst. As illustrated in Scheme 1, NMP involves a combination of radical initiator (Ι), monomer (M) and nitroxide radical (R), for trapping of intermediate radical species. For instance, the thermally-promoted homolysis of benzoyl peroxide (Aldrich Prod. No. 179981) produces radicals that are capable of initiating the polymerization of styrene monomer. Propagation proceeds to produce polymer chains, while reversible termination events, involving reactions with nitroxide radicals to afford thermally labile alkoxyamines, mediate the availability of the reactive radical species and, thereby, provide control over the polymerization. It is important that the stable nitroxide radicals are capable of the reversible termination reactions, but do not initiate polymerizations. - See more at: http://www.sigmaaldrich.com/technical-documents/articles/material-matters/block-copolymer-synthesis.html#sthash.I4Cswj8a.dpuf