A new one pot synthetic method has been developed for preparing amphiphilic block copolymers. The method makes use of episulfide anionic polymerization for generating symmetric or asymmetric tri- or multiblock copolymers with living mechanism. Important features of the method are (a) the use of in situ generated thiolates, which ensures reproducibility in the initiator concentration; (b) the mild character of the reactive species; therefore, also sensitive bioactive groups could be easily incorporated into the polymer structure; (c) the tolerance to impurities in the reagents and the one pot character, which allow the use of the method also by operators with limited skills in organic synthesis.

Sulfur(II)-containing polymers (polysulfides) combine flexible synthetic and processing techniques with a unique responsiveness to oxidants. Here, the polysulfide oxidative sensitivity is put into the biological context of the development of new anti-inflammatory therapies - the development of new anti-inflammatory methodologies, adopted interactions and the minimisation of foreign-body reactions - through the review of 50 years of research on polysulfide synthetic methodologies. Attention is paid to the identification of the most flexible and robust preparative techniques.

In episulfide polymerisation, the exchange between thiols and disulfides results in a chain transfer, which may compromise the control over molecular weight and molecular weight distribution. Self‐assemblable polysulfide structures have found promising applications as bionanomaterials (responsive nanoparticles or vesicles, surface films, etc.), but the necessary precise molecular control may indeed be jeopardised by the presence of disulfides. We here discuss in depth the role of disulfides as chain transfer agents and present some robust solutions, aiming at minimising the presence of disulfides and optimising synthetic procedures.

Episulfide polymerization offers a number of features that are uncommon in other ring‐opening anionic mechanisms. Besides the negligible sensitivity to water, the most distinctive and novel one is likely to be the role of disulfides, which may act both at the levels of chain transfer and end‐capping, producing polymers that feature both terminal and internal disulfides. In this article, we have qualitatively studied the kinetics of chain transfer and measured the thiolate–disulfide exchange equilibrium constants. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2233–2249, 2008