Catalytic polymeric nanoreactors: more than a solid supported catalyst

Abstract

Polymeric nanostructures can be synthesized where the catalytic motif is covalently attached within the core domain and protected from the environment by a polymeric shell. Such nanoreactors can be easily recycled, and have shown unique properties when catalyzing reactions under pseudohomogeneous conditions. Many examples of how these catalytic nanostructures can act as nanosized reaction vessels have been reported in the literature. This prospective will focus on the exclusive features observed for these catalytic systems and highlight their potential as enzyme mimics, as well as the importance of further studies to unveil their full potential.

Tuneable enhancement of the salt and thermal stability of polymeric micelles by cyclized amphiphiles

“…To exploit the topology effects, micellar catalysis38 of a halogen exchange reaction (Finkelstein reaction) in water was conducted. A water-insoluble substrate, 1-(bromoacetyl)pyrene (41 mg, 0.13 mmol), was suspended in an aqueous NaCl solution (10 ml) in the presence of either a linear or cyclic amphiphile (0.12 mM, 1.2 μmol, 0.92 mol% of the substrate), as well as in the absence of them to produce 1-(chloroacetyl)pyrene.…”

Coordination Chemistry inside Polymeric Nanoreactors: Metal Migration and Cross-Exchange in Amphiphilic Core-Shell Polymer Latexes

“…These experiments were carried out by mixing together, after core swelling with toluene, equimolar amounts of metal-free and fully-metal-loaded TPP@CCM particles. Even though the metal does not change the coordination environment when moving from one nanoreactor to another, these experiments gave unambiguous information on the rate of metal migration because of the rapid self-exchange process taking place within 50% loaded particles; see Equation (1). Hence, while the fully-loaded particles show a 31 P resonance as a doublet at δ 47.5 (J PRh = 175 Hz) and the metal-free particles show a single resonance at δ´6.6, the fully-exchanged (50% loaded) final sample has a silent 31 P NMR spectrum, because the rate of the interparticle degenerative exchange of Equation (1) gives signal coalescence at room temperature [43].…”

“…The current report expands on the investigation of the metal migration process by addressing the following variations: (i) migration of the [Rh(acac)(CO)] fragment for the nanogel (TPP@NG) particles and comparison with TPP@CCM to assess the role of the polymer architecture on the particle interpenetration process; (ii) metal cross-exchange between differently-functionalized polymers, using both the CCM and the NG particles, to remove the rapid intraparticle ligand exchange of Equation (1). The cross-exchange uses TPP and BMOPPP as ligands and [Rh(acac)(CO)] and [RhCl(COD)] (COD = η 4 -1,5-cyclooctadiene) as metal fragments.…”

Block copolymer synthesis by controlled/living radical polymerisation in heterogeneous systems

“…81, 157, 177, 178, 217 117 The use of block copolymer particles as functional materials is a field still in its infancy, but has been gathering interest over the last 5 years and could broaden the overall scope of block copolymer applications by orders of magnitude. Amphiphilic block copolymer particles synthesised by CLRP have already been investigated in drug delivery, 255,256 sensors, 257 Pickering emulsifiers, 258 gels for cell growth 259 and coatings, 260 and these nano-objects could further impact on diverse fields including nanoreactors, 261 theranostics, 262 and the controlled synthesis of inorganic NPs. 263,264 Larger block copolymer particles (i.e.…”