We are interested in exploring the controlled synthesis and self-assembly of well-defined functionalised polymers into novel materials capable of behaving as catalytic nanoreactors or nanosized delivery vehicles. These constructs are proposed to utilise their confined hydrophobic core environment as pockets to do specific chemistry in particular catalysis reactions. To date, the majority of our work has utilised the unique stabilised core-shell morphology of functional spherical polymeric nanostructures as supports for catalytically active functionality. We have developed methods to incorporate a range of catalytically active functionality into the polymeric constructs including;
2. Dimethylaminopyridine, DMAP
3. McMillan catalyst
4. Pd pincer complexes
A number of these nanoreactor systems show enhanced activity and selectivity compared to the unsupported catalyst and highlight the ability to influence the catalytic potential of a functional group through tuning its local environment within a polymeric micelle. Of significant interest is the design of functional micelles which have been tailored to respond to external stimuli such as temperature, light or pH to allow for improved catalyst recycling, recovery or controlled release.
Some of this research has been conducted in collaboration with out industry partners from AWE, Unilever and BP. Funding was also received from the EPSRC through the award of a career acceleration fellowship to ROR.
Recyclable l-Proline Functional Nanoreactors with Temperature-Tuned Activity Based on CoreShell Nanogels, A. Lu, D. Moatsou, I. Hands-Portman, D.A. Longbottom, R.K. O'Reilly, ACS Macro Letters, 2014, 3, 1235-1239, DOI: 10.1021/mz500704y
Studying the activity of the MacMillan catalyst embedded within hydrophobic crosslinked polymeric nanostructures, B. Moore, D. Moatsou, A. Lu, R.K. O'Reilly, Polymer Chemistry, 2014, 3487-3494, DOI:10.1039/C3PY01734F.
Thermoresponsive polymer-supported L-proline micelle catalysts for the direct asymmetric aldol reaction in water, H.A. Zayas, A. Lu, D. Valade, F. Amir, Z. Jia, R.K.O'Reilly and M. Monterio, ACS Macro Letters, 2013, 2, 327;
Immobilization of MacMillan Catalyst via Controlled Radical Polymerization: Catalytic Activity and Reuse, B. L. Moore, A. Lu, D.A. Longbottom and R. K. O’Reilly, Polymer Chemistry, 2013, 4, 2304 - 2312.DOI: 10.1039/C3PY21125H
Tuning the Catalytic Activity of L-Proline Functionalized Hydrophobic Nanogel Particles in Water, A. Lu, D. Moatsou, D.A. Longbottom and R.K. O'Reilly, Chem. Sci. 2013, 4, 965-969. DOI: 10.1039/C2SC21300A