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Abstract: The precise control over the formation of complex nanostructures, e.g. polyoxometalates (POMs), at the sub-nanoscale is challenging but critical if non-covalent architectures are to be designed. Combining biologically-evolved systems with inorganic nanostructures could lead to sequence-mediated assembly. Herein, we exploit oligopeptides as multidentate structure-directing ligands via metal-coordination and hydrogen bonded interactions to modulate the self-assembly of POM superstructures. Six oligopeptides (GH, AH, SH, G2H, G4H and G5H) are incorporated into the cavities of Molybdenum Blue (MB) POM nanowheels. It is found that the helicity of the nanowheel can be readily switched (Δ to Λ) by simply altering the N-terminal amino acid on the peptide chain rather than their overall stereochemistry. We also reveal a delicate balance between the Mo-coordination and the hydrogen bonds found within the internal cavity of the inorganic nanowheels which results in the sequence mediated formation of two unprecedented asymmetrical nanowheel frameworks: {Mo122Ce5} and {Mo126Ce4}.

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Abstract: Large single-ion magnetic anisotropy is observed in lithium nitride doped with iron. The iron sites are two-coordinate, putting iron doped lithium nitride amongst a growing number of two coordinate transition metal single-ion magnets (SIMs). Uniquely, the relaxation times to magnetisation reversal are over two orders of magnitude longer in iron doped lithium nitride than other 3d-metal SIMs, and comparable with high-performance lanthanide-based SIMs. To understand the origin of these enhanced magnetic properties a detailed characterisation of electronic structure is presented. Access to dopant electronic structure calls for atomic specific techniques, hence a combination of detailed single-crystal X-ray absorption and emission spectroscopies are applied. Together K-edge, L2,3-edge and Kβ X-ray spectroscopies probe local geometry and electronic structure, identifying iron doped lithium nitride to be a prototype, solid-state SIM, clean of stoichiometric vacancies where Fe lattice sites are geometrically equivalent. Extended X-ray absorption fine structure and angular dependent single-crystal X-ray absorption near edge spectroscopy measurements determine FeI dopant ions to be linearly coordinated, occupying a D6h symmetry pocket. The dopant engages in strong 3dπ-bonding, resulting in an exceptionally short Fe–N bond length (1.873(7) Å) and rigorous linearity. It is proposed that this structure protects dopant sites from Renner–Teller vibronic coupling and pseudo Jahn–Teller distortions, enhancing magnetic properties with respect to molecular-based linear complexes. The Fe ligand field is quantified by L2,3-edge XAS from which the energy reduction of 3dz2 due to strong 4s mixing is deduced. Quantification of magnetic anisotropy barriers in low concentration dopant sites is inhibited by many established methods, including far-infrared and neutron scattering. We deduce variable temperature L3-edge XAS can be applied to quantify the J = 7/2 magnetic anisotropy barrier, 34.80 meV (∼280 cm−1), that corresponds with Orbach relaxation via the first excited, MJ = ±5/2 doublet. The results demonstrate that dopant sites within solid-state host lattices could offer a viable alternative to rare-earth bulk magnets and high-performance SIMs, where the host matrix can be tailored to impose high symmetry and control lattice induced relaxation effects.

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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: A three-dimensional FeII4L6 parallelogram was prepared from ferrocene-containing ditopic ligands. The steric preference of the bulky ferrocene cores towards meridional vertex coordination brought about this new structure type, in which the ferrocene units adopt three distinct conformations. The structure possesses two distinct, bowl-like cavities that host anionic guests. Oxidation of the ferrocene FeII to ferrocenium FeIII causes rotation of the ferrocene hinges, converting the structure to an FeII1L1+ species with release of anionic guests, even though the average charge per iron increases in a way that would ordinarily increase guest binding strength. The degrees of freedom exhibited by these new structures – derived from the different configurations of the three ligands surrounding a meridional FeII center and the rotation of ferrocene cores – thus underpin their ability to reconfigure and eject guests upon oxidation.

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Abstract: Small-angle X-ray scattering (SAXS) is used to characterize the in situ formation of diblock copolymer spheres, worms and vesicles during reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate at 70 °C using a poly(glycerol monomethacrylate) steric stabilizer. 1H NMR spectroscopy indicates more than 99% HPMA conversion within 80 min, while transmission electron microscopy and dynamic light scattering studies are consistent with the final morphology being pure vesicles. Analysis of time-resolved SAXS patterns for this prototypical polymerization-induced self-assembly (PISA) formulation enables the evolution in copolymer morphology, particle diameter, mean aggregation number, solvent volume fraction, surface density of copolymer chains and their mean inter-chain separation distance at the nanoparticle surface to be monitored. Furthermore, the change in vesicle diameter and membrane thickness during the final stages of polymerization supports an ‘inward growth’ mechanism.