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Abstract: Graphene oxide (GO) forms a well-aligned lyotropic liquid crystal (LC) phase in aqueous dispersions at relatively low concentrations. Under a remarkably wide range of shear rates, we report hitherto unobserved shear-induced polarized light image patterns, a Maltese cross combined with shear banding, recorded in real time and in situ during rheological measurements. This is shown to be a result of elastic flow instabilities that manifest as a helical flow in alternating bands of left- and right-handed helices, arising from a combination of shear flow and Taylor-type vortex flow. The instability is observed for LCs formed from large aspect ratio GO particles owing to their unique viscoelastic properties, but not for smaller aspect ratio particles. This phenomenon coincides with rheopecty and anomalous small-angle X-ray scattering patterns under shear flow, which confirm the instabilities. The results presented here could lead to advanced control over macroscopic periodic alignment in technologically relevant dispersions of two-dimensional material particles.

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Abstract: Polyetheretherketone (PEEK)/polyetherimide (PEI) blends (50/50, v/v) keeping the crystal phase of PEEK have been manufactured by alternate PEEK/PEI layer stacking. This strategy avoided the complete miscibility of both polymers, keeping layers of PEEK and PEI unmixed along the sample thickness, as well as promoting the formation of a smooth interfacial layer where PEEK and PEI were mixed. The properties of this interface after processing at molten state and different times was studied by DSC, DMA, and X-Ray synchrotron. These techniques allowed monitoring the evolution of glass transition, where isolated Tg’s for both pristine polymers were observed even after long processing time. PEEK crystallinity slightly decreased during manufacturing, whereas PEEK crystal parameters did not vary. These observations show that, although the interface—the zone where both polymers are mixed—grew, layers with pristine polymers remained even after prolonged processing time. The preservation of the PEEK crystallinity was also observed in the mechanical properties of the multilayer PEEK/PEI films, which were compared with pristine PEEK and PEI films. Multilayer samples processed for shorter times rendered higher young modulus, tensile strength, and strain at break.

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Abstract: Controlling the assembly and disassembly of nanoscale protein cages for the capture and internalization of protein or non-proteinaceous components is fundamentally important to a diverse range of bionanotechnological applications. Here, we study the reversible, pressure-induced dissociation of a natural protein nanocage, E. coli bacterioferritin (Bfr), using synchrotron radiation small-angle X-ray scattering (SAXS) and circular dichroism (CD). We demonstrate that hydrostatic pressures of 450 MPa are sufficient to completely dissociate the Bfr 24-mer into protein dimers, and the reversibility and kinetics of the reassembly process can be controlled by selecting appropriate buffer conditions. We also demonstrate that the heme B prosthetic group present at the subunit dimer interface influences the stability and pressure lability of the cage, despite its location being discrete from the interdimer interface that is key to cage assembly. This indicates a major cage-stabilizing role for heme within this family of ferritins.

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Abstract: In this work we experimentally investigate solvent and temperature induced conformational transitions of proteins and examine the role of ion–protein interactions in determining the conformational preferences of avidin, a homotetrameric glycoprotein, in choline-based ionic liquid (IL) solutions. Avidin was modified by surface cationisation and the addition of anionic surfactants, and the structural, thermal, and conformational stabilities of native and modified avidin were examined using dynamic light scattering, differential scanning calorimetry, and thermogravimetric analysis experiments. The protein-surfactant nanoconjugates showed higher thermostability behaviour compared to unmodified avidin, demonstrating distinct conformational ensembles. Small-angle X-ray scattering data showed that with increasing IL concentration, avidin became more compact, interpreted in the context of molecular confinement. To experimentally determine the detailed effects of IL on the energy landscape of avidin, differential scanning fluorimetry and variable temperature circular dichroism spectroscopy were performed. We show that different IL solutions can influence avidin conformation and thermal stability, and we provide insight into the effects of ILs on the folding pathways and thermodynamics of proteins. To further study the effects of ILs on avidin binding and correlate thermostability with conformational heterogeneity, we conducted a binding study. We found the ILs examined inhibited ligand binding in native avidin while enhancing binding in the modified protein, indicating ILs can influence the conformational stability of the distinct proteins differently. Significantly, this work presents a systematic strategy to explore protein conformational space and experimentally detect and characterise ‘invisible’ rare conformations using ILs.

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Abstract: The rational synthesis of epoxy-functional diblock copolymer nano-objects has been achieved via RAFT aqueous emulsion polymerisation of glycidyl methacrylate (GlyMA; aqueous solubility ∼22 g dm−3 at 50 °C) by utilising relatively mild conditions (pH 7, 50 °C) to preserve the epoxy groups. High monomer conversions were achieved within 1 h when using a poly(glycerol monomethacrylate) chain transfer agent with a mean degree of polymerisation (DP) of 28, with GPC analysis indicating relatively narrow molecular weight distributions (Mw/Mn < 1.40) when targeting PGlyMA DPs up to 80. A phase diagram was constructed to identify the synthesis conditions required to access pure spheres, worms or vesicles. Transmission electron microscopy, dynamic light scattering and small-angle X-ray scattering (SAXS) studies indicated the formation of well-defined worms and vesicles when targeting relatively long PGlyMA blocks. These epoxy-functional nano-objects were derivatised via epoxy-thiol chemistry by reaction with L-cysteine in aqueous solution. Finally, an in situ SAXS study was conducted during the RAFT aqueous emulsion polymerisation of GlyMA at 50 °C to examine the nucleation and size evolution of PGMA48-PGlyMA100 diblock copolymer spheres using a bespoke stirrable reaction cell.