Complementary light scattering and synchrotron small-angle X-ray scattering studies of the micelle-to-unimer transition of polysulfobetaines.

AB and ABA di- and triblock copolymers where A is the hydrophilic poly(oligoethylene glycol methacrylate) (POEGMA) block and B is a thermo-responsive sulfobetaine block [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (PDMAPS) were synthesised by aqueous RAFT polymerisation with narrow dispersity (DM ≤ 1.22), as judged by aqueous SEC analysis. The di- and triblock copolymers self-assembled in salt-free water to form micelles with a PDMAPS core and the self-assembly of these polymers was explored by SLS and TEM analysis. The micelles were shown, by DLS analysis, to undergo a micelle-to-unimer transition at a critical temperature, which was dependent upon the length of the POEGMA block. Increasing the length of the third, POEGMA, block decreased the temperature at which the micelle-to-unimer transition occurred as a result of the increased hydrophilicity of the polymer. The dissociation of the micelles was further studied by SLS and synchrotron SAXS. SAXS analysis revealed that the micelle dissociation began at temperatures below that indicated by DLS analysis and that both micelles and unimers coexist. This highlights the importance of using multiple complementary techniques in the analysis of self-assembled structures. In addition the micelle-to-unimer morphology transition was employed to encapsulate and release a hydrophobic dye, Nile Red, as shown by fluorescence spectroscopy.

Exploiting the tetrazine-norbornene reaction for single polymer chain collapse.

Single chain polymer nanoparticles (SCNPs) have been formed using polystyrenes decorated with pendent norbornenes and a bifunctional tetrazine crosslinker. Characterisation by size exclusion chromatography and (1)H NMR gives evidence for the formation of SCNPs by the tetrazine-norbornene reaction, whilst light scattering, neutron scattering, transmission electron microscopy and atomic force microscopy show that discrete well-defined nanoparticles are formed and their size in solution calculated.

Recyclable l-Proline Functional Nanoreactors with Temperature-Tuned Activity Based on Core-Shell Nanogels.

Recyclable core-shell (CS) nanogels based on l-proline-containing hydrophobic cores with a thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) shell have been synthesized via a seeded precipitation polymerization process. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were used to verify the successful addition of the shell and investigate the thermoresponsive properties of the nanostructures. The catalytic activity of the nanogels was assessed in a model asymmetric aldol reaction, where an enhancement was observed with increasing temperature, attributed to the hydrophobic nature of the PNIPAM shell. However, when a nanogel was synthesized with core-shell morphology based on a gradient of cross-linking density in the corona (GS), a dramatic drop in activity was observed at elevated temperatures: the collapse of the outer, lightly cross-linked, "corona" polymer chains appears to block access to the catalytic core. High activity and enantioselectivity were maintained in a number of recovery and reuse cycles, highlighting the recycling potential of these catalytic nanostructures.

Structural characterization of amphiphilic homopolymer micelles using light scattering, SANS, and cryo-TEM.

We report the aqueous solution self-assembly of a series of poly(N-isopropylacrylamide) (PNIPAM) polymers end-functionalized with a hydrophobic sulfur-carbon-sulfur (SCS) pincer ligand. Although the hydrophobic ligand accounted for <5 wt% of the overall homopolymer mass, the polymers self-assembled into well-defined spherical micelles in aqueous solution, and these micelles are potential precursors to solution-assembled nanoreactors for small molecule catalysis applications. The micelle structural details were investigated using light scattering, cryogenic transmission electron microscopy (cryo-TEM), and small angle neutron scattering (SANS). Radial density profiles extracted from the cryo-TEM micrographs suggested that the PNIPAM chains formed a diffuse corona with a radially decreasing corona density profile and provided valuable a priori information about the micelle structure for SANS data modeling. SANS analysis indicated a similar profile in which the corona surrounded a small hydrophobic core containing the pincer ligand. The similarity between the SANS and cryo-TEM results demonstrated that detailed information about the micelle density profile can be obtained directly from cryo-TEM and highlighted the complementary use of scattering and cryo-TEM in the structural characterization of solution-assemblies, such as the SCS pincer-functionalized homopolymers described here.

Catalytic Y-tailed amphiphilic homopolymers - aqueous nanoreactors for high activity, low loading SCS pincer catalysts.

A new amphiphilic homopolymer bearing an SCS pincer palladium complex has been synthesized by reversible addition fragmentation chain transfer polymerization. The amphiphile has been shown to form spherical and worm-like micelles in water by cryogenic transmission electron microscopy and small angle neutron scattering. Segregation of reactive components within the palladium containing core results in increased catalytic activity of the pincer compound compared to small molecule analogues. This allows carbon-carbon bond forming reactions to be performed in water with reduced catalyst loadings and enhanced activity.

Advances in nanoreactor technology using polymeric nanostructures.

Site isolation, compartmentalization and substrate specificity are a few of the characteristics responsible for the catalytic efficiency demonstrated by enzymes in natural systems. In efforts to mimic these highly efficient systems, research has been directed towards macromolecular chemistry. Robust polymer assemblies can create a favorable and isolated environment around the catalytic site allowing specific and sometimes incompatible reactions to take place within this protected reaction pocket. Further exploring the use of 'smart' polymers, control over both the catalytic activity and substrate specificity is achieved. In addition, polymeric systems provide the opportunity for recycling of the active catalysts, further enhancing the advantages of polymer supported catalytic systems.

Thermoresponsive Polymer-Supported l-Proline Micelle Catalysts for the Direct Asymmetric Aldol Reaction in Water.

l-Proline moieties bound to a thermoresponsive polymer nanoreactor efficiently directed the asymmetric aldol reaction in water with excellent yields and enantioselectivity (ee). The reactions were efficient at higher temperatures in direct contrast to the low yields and ee values found when the reaction was carried out in a DMF/water mixture due to the location of the l-proline moieties within the hydrophobic pocket inside the core of the nanoreactors. This ideal environment formed for catalysis allows control over the water content as well as enhancing interactions between the carboxylic acid of l-proline and the aldehyde substrate. The nanoreactors were disassembled to fully water-soluble polymers by lowering the temperature to below the lower critical solution temperature (LCST) of the polymer, resulting in precipitation of the product in near pure form. The product was isolated by centrifugation and the polymer/water solution reused in additional catalytic cycles by heating the polymer above its LCST and thus reforming the nanoreactors. Although a small decrease in yield after five cycles was observed, the selectivity (anti/syn ratio and ee) remained high.

Effect of Complementary Nucleobase Interactions on the Copolymer Composition of RAFT Copolymerizations.

Methacryloyl-type monomers containing adenine and thymine have been successfully synthesized with good yields. The homopolymerization and copolymerization of these two new functional monomers were carried out using RAFT polymerization. The reactivity ratios of monomer pairs were measured and calculated using a nonlinear least-squares (NLLS) method, and the results confirmed that the monomer reactivities were dependent on the solvent used for polymerization. The presence and absence of hydrogen bonding affected the resultant copolymer composition where moderate alternating copolymers had a tendency to be formed in CHCl3, while in DMF, statistical copolymers were formed. Furthermore, the glass transition temperatures of the copolymers were investigated, and the self-assembly of block copolymers made in solvents with different polarity were studied.

Aldol reactions catalyzed by L-proline functionalized polymeric nanoreactors in water.

The use of functional core-shell micelles as asymmetric catalytic nanoreactors for organic reactions in water is presented. An unprecedented increase in rate of reaction was achieved, which is proposed to be associated with the ability of the nanostructures to effectively concentrate the reagents in the catalytically active micelle core.

L-Proline Functionalized Polymers Prepared by RAFT Polymerization and Their Assemblies as Supported Organocatalysts.

We have prepared a range of well-defined copolymers of styrene and L-proline functionalized styrene (5-11 kDa) using reversible addition-fragmentation chain transfer (RAFT) polymerization techniques and explored their use in supported catalysis. Upon deprotection of the L-proline functionalities, the solution self-assembly of these copolymers was investigated in mixed solvent systems. The resulting assemblies were characterized by dynamic light scattering, transmission electron microscopy (on graphene oxide substrates, along with cryo-TEM and tomography), and scanning electron microscopy. The application of these functional assemblies as supported catalysts for the aldol condensation reaction was explored using cyclohexanone and 4-nitrobenzaldehyde. The rate and selectivity of solution catalysis in our self-assembled system were comparable to those of L-proline, and a significant advantage of our system was that the polymer support could be utilized at lower catalyst loadings with comparable activity and also could be recycled a number of times while maintaining activity and selectivity.

The pyrolysis of (-)-(S)-nicotine: racemization and decomposition.

The pyrolytic behaviour of (-)-(S)-nicotine in methanol was investigated using on-line pyrolysis GC/MS to establish whether racemization to the R(+) antipode occurs and to identify other products of pyrolysis. The conditions used included pyrolysing the sample for 15 seconds in an atmosphere of 9% oxygen in nitrogen (275 ml/min total flow) across the temperature range of 200 degrees C-1000 degrees C. A chiral Cyclodex-B analytical column (30 m x 0.25 mm i.d. x 0.25 microm film thickness) was used to separate the enantiomers of nicotine, although the two enantiomer peaks were not baseline resolved. The results of the experiment shows that there is no increase in (+)-(R)-nicotine levels across a wide temperature range. This suggests that the elevated levels of (+)-R-nicotine observed in tobacco smoke (compared to tobacco leaf material) are not due to the pyrolytic auto-racemization of (-)-(S)-nicotine but are a result of more complex interactions between (-)-(S)-nicotine and other smoke components. The pyrolysis of isotopically labelled nicotine established that nicotine undergoes thermal decomposition to beta-nicotyrine which in turn may decompose to other products.