Julie A. Watts

Asymmetric functionalisation of polyoxometalates with tailored functionality yields stimuli-responsive, redox-active molecules that can form soft assemblies or graft onto nano- and macroscale surfaces.

We report the divergent assembly of polyproline helices into two types of metallo-peptide nanoparticles. In this report we also show that the primary sequence is crucial to ensure a controlled and desired assembly.

The field of peptide based supramolecular biomaterials is fast evolving. These types of constructs have been shown to find applications in the fields of bioimaging, drug delivery and scaffolds for chemical reactions. However, the community typically focuses on the use of two specific class of structured peptides: alpha-helices and beta-sheets, clearly neglecting a unique peptide secondary structure: the polyproline helix. Herein, we report the first design, synthesis and characterization of polyproline based metallo-peptide nanoparticles. We demonstrate that rationally engineered polyproline helices can assemble in a divergent manner, into two types of nanoparticles. We also demonstrate that the primary sequence of the functionalised polyproline peptide, is crucial to ensure a controlled assembly. This work clearly demonstrates that polyproline helices can be a powerful tool to achieve supramolecular assemblies of complex and responsive bioinspired nanomaterials.

The 3D architecture of RNAs governs their molecular interactions, chemical reactions, and biological functions. However, a large number of RNAs and their protein complexes remain poorly understood due to the limitations of conventional structural biology techniques in deciphering their complex structures and dynamic interactions. To address this limitation, we have benchmarked an integrated approach that combines cryogenic OrbiSIMS, a state-of-the-art solid-state mass spectrometry technique, with computational methods for modelling RNA structures at atomic resolution with enhanced precision. Furthermore, using 7SK RNP as a test case, we have successfully determined the full 3D structure of a native RNA in its apo, native and disease-remodelled states, which offers insights into the structural interactions and plasticity of the 7SK complex within these states. Overall, our study establishes cryo-OrbiSIMS as a valuable tool in the field of RNA structural biology as it enables the study of challenging, native RNA systems.

Access to asymmetrically functionalized polyoxometalates is a grand challenge as it could lead to new molecular nanomaterials with multiple or modular functionality. Now, a simple one‐pot synthetic approach to the isolation of an asymmetrically functionalized organic–inorganic hybrid Wells–Dawson polyoxometalate in good yield is presented. The cluster bears two organophosphonate moieties with contrasting physical properties: a chelating metal‐binding group, and a long aliphatic chain that facilitates solvent‐dependent self‐assembly into soft nanostructures. The orthogonal properties of the modular system are effectively demonstrated by controlled assembly of POM‐based redox‐active nanoparticles. This simple, high‐yielding synthetic method is a promising new approach to the preparation of multi‐functional hybrid metal oxide clusters, supermolecular systems, and soft‐nanomaterials.

Access to asymmetrically functionalized polyoxometalates is a grand challenge as it could lead to new molecular nanomaterials with multiple or modular functionality. Now, a simple one‐pot synthetic approach to the isolation of an asymmetrically functionalized organic–inorganic hybrid Wells–Dawson polyoxometalate in good yield is presented. The cluster bears two organophosphonate moieties with contrasting physical properties: a chelating metal‐binding group, and a long aliphatic chain that facilitates solvent‐dependent self‐assembly into soft nanostructures. The orthogonal properties of the modular system are effectively demonstrated by controlled assembly of POM‐based redox‐active nanoparticles. This simple, high‐yielding synthetic method is a promising new approach to the preparation of multi‐functional hybrid metal oxide clusters, supermolecular systems, and soft‐nanomaterials.

Double-chain redox-active surfactants based on hybrid polyoxometalates show solvent-dependent assembly into nanoscale micellar architectures. These organic–inorganic hybrid amphiphiles, of the general formula K₆[P₂W₁₇O₆₁(POC₆H₄O(C_nH_2n+1))₂], were prepared with varying aliphatic chain lengths (n = 10, 12, 14, 16, 18 and 20) and display different multi-electron redox behaviours in their molecular and supramolecular forms. Furthermore, modification of the length of the hydrophobic tail is an effective strategy for controlling the stability and electronic properties of the supramolecular nanostructures.