We present first results on triazolium-based ionic liquids (ILs) as a novel class of non-derivatising solvents for cellulose. Despite their chemical similarity to imidazolium cations, the 1,2,3-triazolium cation lacks the isolated ring proton, leading to reduced formation of N-heterocyclic carbenes (NHCs), and therefore to lower reactivity and less unwanted side reactions. We synthesised six ILs based on 1,2,3-triazolium and 1,2,4-triazolium cations. The acetates are room temperature ionic liquids (RTILs) and dissolve a similar amount of cellulose as the corresponding imidazolium salt. From NMR spectroscopy of the solution, we rule out polymer degradation. The cellulose solubility rises with increasing anion basicity, while being almost independent of the cation. We perform molecular dynamics simulations and compute enthalpies of solvation, which quantitatively fit the experimental solubilities. Trajectory analysis reveals strong hydrogen bonds between acetate anions and cellulose hydroxyl groups, while the cations do not form strong hydrogen bonds to cellulose. Thus, the simulations provide an atomistic explanation of our experimental observations.
Synthetic polymers incorporating fluorine segments or blocks are highly interesting for biomedical and pharmaceutical research due to the singular biological activity imparted by the fluorinated moieties. However, rather demanding traditional living polymerization techniques required to obtain well-defined block copolymers had typically been a major hurdle for a faster development of the field. Recently, block copolymers and telechelic polymers comprising segments with different chemical affinities, therefore termed as “polyphilic”, have become easily accessible, thanks to alternative controlled radical polymerization techniques. They can be applied alone or in conjunction with novel quantitative post-polymerization reactions which allow to “click” additional segments via functional groups. Triphilic polymers exhibit a rich variety of morphologies in solvents selective for one of the blocks including multicompartment micelles, which forecasts innovative pharmaceutical applications as for example vehicles of nanometre size for the simultaneous delivery of incompatible drug components to cells. In this highlight we focus on our recent contributions, current trends and perspectives regarding triphilic block copolymers and telechelic polymers formed exclusively from hydrophilic, lipophilic and fluorophilic building blocks.
8 July 2008 in Macromolecular Rapid Communications