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Abstract: Polymerization-induced self-assembly (PISA) is widely recognized to be a powerful technique for the preparation of diblock copolymer nano-objects in various solvents. Herein a highly unusual non-aqueous emulsion polymerization formulation is reported. More specifically, the reversible addition–fragmentation chain transfer (RAFT) polymerization of N-(2-acryloyloxy)ethyl pyrrolidone (NAEP) is conducted in n-dodecane using a poly(stearyl methacrylate) (PSMA) precursor to produce sterically-stabilized spherical nanoparticles at 90 °C. This relatively high polymerization temperature was required to ensure sufficient background solubility for the highly polar NAEP monomer, which is immiscible with the non-polar continuous phase. A relatively long PSMA precursor (mean degree of polymerization, DP = 36) was required to ensure colloidal stability, which meant that only kinetically-trapped spheres could be obtained. Dynamic light scattering (DLS) studies indicated that the resulting PSMA36–PNAEPx (x = 60 to 500) spheres were relatively well-defined (DLS polydispersity <0.10) and the z-average diameter increased linearly with PNAEP DP up to 261 nm. Differential scanning calorimetry studies confirmed a relatively low glass transition temperature (Tg) for the core-forming PNAEP block, which hindered accurate sizing of the nanoparticles by TEM. However, introducing ethylene glycol diacrylate (EGDA) as a third block to covalently crosslink the nanoparticle cores enabled a spherical morphology to be identified by transmission electron microscopy studies. This assignment was confirmed by small angle X-ray scattering studies of the linear diblock copolymer nanoparticles. Finally, hydrophobic linear PSMA36–PNAEP70 spheres were evaluated as a putative Pickering emulsifier for n-dodecane–water mixtures. Unexpectedly, addition of an equal volume of water followed by high-shear homogenization always produced oil-in-water (o/w) emulsions, rather than water-in-oil (w/o) emulsions. Moreover, core-crosslinked PSMA36–PNAEP60–PEGDA10 spheres also produced o/w Pickering emulsions, suggesting that such Pickering emulsions must be formed by nanoparticle adsorption at the inner surface of the oil droplets. DLS studies of the continuous phase obtained after either creaming (o/w emulsion) or sedimentation (w/o emulsion) of the droplet phase were consistent with this interpretation. Furthermore, certain experimental conditions (e.g. ≥0.5% w/w copolymer concentration for linear PSMA36–PNAEPx nanoparticles, ≥0.1% w/w for core-crosslinked nanoparticles, or n-dodecane volume fractions ≤0.60) produced w/o/w double emulsions in a single step, as confirmed by fluorescence microscopy studies.

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Abstract: Reversible addition–fragmentation chain transfer (RAFT) mediated dispersion polymerisation in supercritical carbon dioxide (scCO2) is an efficient and green method for synthesising block copolymer microparticles with internal nanostructures. Here we report for the first time the synthesis of phase separated poly(methyl methacrylate-block-styrene-block-4-vinylpyridine) (PMMA-b-PS-b-P4VP) triblock terpolymer microparticles using a simple two-pot sequential synthesis procedure in scCO2, with high monomer conversions and no purification steps. The microparticles, produced directly and without further processing, show a complex internal nanostructure, appearing as a “lamellar with spheres” [L + S(II)] type morphology. The P4VP block is then exploited as a structure-directing agent for the fabrication of TiO2 microparticles. Through a simple and scalable sol–gel and calcination process we produce hollow TiO2 microparticles with a mesoporous outer shell. When directly compared to porous TiO2 particles fabricated using an equivalent PMMA-b-P4VP diblock copolymer, increased surface area and enhanced photocatalytic efficiencies are observed.

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Abstract: We have previously reported the synthesis of thermoresponsive poly(stearyl methacrylate)-poly(benzyl methacrylate) [PSMA-PBzMA] diblock copolymer vesicles in mineral oil via polymerisation-induced self-assembly (PISA). Such vesicles undergo a vesicle-to-worm transition on heating, which provides an interesting new oil-thickening mechanism (see M. J. Derry, et al., Angew. Chem., 2017, 56, 1746–1750). In the present study, we report an unexpected reduction in dispersion viscosity when heating vesicles of approximately the same composition above a certain critical temperature. Transmission electron microscopy (TEM) studies indicate rich thermoresponsive behavior, with vesicles present at 20 °C, worms being formed at 130 °C and spheres generated at 180 °C, indicating that a worm-to-sphere transition occurs after the initial vesicle-to-worm transition. Moreover, we have also prepared a series of new thermoresponsive diblock copolymer vesicles by RAFT dispersion copolymerization of n-butyl methacrylate (BuMA) with benzyl methacrylate (BzMA) using a poly(stearyl methacrylate) precursor in mineral oil. This model system was developed to examine whether statistical copolymerization of a suitable comonomer (BuMA) could be used to tune the critical onset temperature required for the vesicle-to-worm transition. Indeed, oscillatory rheology studies confirmed that targeting membrane-forming blocks containing up to 50 mol% BuMA lowered the critical onset temperature required to induce the vesicle-to-worm transition to 109 °C, compared to 167 °C for the reference PSMA14-PBzMA125 diblock copolymer. Variable temperature small-angle X-ray scattering (SAXS) experiments confirmed a vesicle-to-worm transition, with the vesicles initially present at 20 °C being converted into worms when heated above 130 °C. Furthermore, a substantial reduction in dispersion viscosity was again observed when heating above the critical onset temperature. TEM and shear-induced polarized light imaging (SIPLI) studies indicate that linear worms are no longer present at 160 °C and 170 °C respectively, suggesting a subsequent worm-to-sphere transition. The thermal transitions studied herein proved to be irreversible on cooling on normal experimental timescales (hours).

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Abstract: This research provides a thorough study of the mechanical response of PCL scaffolds and determines their deformation micromechanisms at different scales by a combination of experimental techniques (mechanical tests, scanning electron microscopy, wide angle X-ray diffraction and small-angle X-ray scattering). Scaffolds with different fibre orientation distribution functions were manufactured and subjected to tensile loading. The macromechanical properties were dictated the by the fibre deformation and interaction in terms of fibre straightening, rotation and stretching. The stiffness and the yield strength were directly proportional to the percentage of fibres oriented with the loading direction. The gradual deformation induced a progressive fibre rotation, uncurling and stretching, showing different impact at molecular level for each configuration. The fibres aligned with the loading direction presented a homogeneous plasticity with an inherent loss of the crystal phase, meanwhile the misaligned fibres exhibited a negligible loss of crystallinity due to a predominance of the fibre rotation. The fibre plasticity triggered the macromechanical yielding of the scaffold and for high levels of plastic deformation the fibres developed macromolecular fibrils and microvoids. These findings provide the fundamental observations to develop engineering tissues with highly tunable and tailored mechanical properties for site specific in vivo applications.

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Abstract: Poly(stearyl methacrylate)-poly(2-hydroxypropyl methacrylate) (PSMA-PHPMA) diblock copolymer nanoparticles are synthesized via reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA) in mineral oil at 90 °C. The relatively short PSMA precursor (mean degree of polymerization = 9) remains soluble in mineral oil, whereas the growing PHPMA block quickly becomes insoluble, resulting in polymerization-induced self-assembly (PISA). Relatively high HPMA monomer conversions (≥98%) were achieved within 70 min as confirmed by in situ 1H NMR spectroscopy studies, while gel permeation chromatography (GPC) analyses indicated high blocking efficiencies and relatively narrow molecular weight distributions (Mw/Mn ≤ 1.37) for all PISA syntheses. Depending on the precise synthesis conditions, this PISA formulation can produce diblock copolymer spheres, worms or vesicles; a pseudo-phase diagram has been constructed to enable reproducible targeting of each pure phase. Thus this is a rare example of the use of a commercially available polar monomer for PISA syntheses in non-polar media that offers access to the full range of copolymer morphologies. The resulting nanoparticles were characterized using dynamic light scattering (DLS), transmission electron microscopy (TEM), oscillatory rheology and small-angle X-ray scattering (SAXS). Interestingly, PSMA9-PHPMA70 worms undergo an unusual (partial) worm-to-vesicle transition at elevated temperature. Finally, PSMA9-PHPMA50 spheres were evaluated as putative Pickering emulsifiers. Using lower water volume fractions produced water-in-oil (w/o) emulsions after high shear homogenization, as expected. However, using higher water volume fractions, shear rates or copolymer concentrations favored the formation of w/o/w Pickering double emulsions.