Metal(IV) phosphonates are a type of organic-inorganic coordination polymer material with promise for a variety of applications including catalysis, sorption, separations, proton exchange and energy storage. The extent of phosphonate coordination to the metal(IV) can vary in these materials, which has substantial implications on their functionality. This study demonstrates how the choice of tetravalent metal, the type of metal(IV) precursor, synthesis duration and synthesis temperature can all be used to control phosphonate availability, which was characterised via solid-state NMR of eight different amorphous metal(IV) phosphonate sorbents. It was found that Zr chloride (compared to Zr propoxide and Zr tert-butoxide) was the most effective Zr precursor for inducing a greater extent of phosphonate coordination. Increasing reaction time also increased phosphonate coordination, but increasing synthesis temperature had the largest impact. Changing the metal(IV) from Zr to Ti resulted in a substantially reduced reactivity with the phosphonate group. Sorbents prepared with Ti resulted in lower ligand content, a high proportion of free phosphonate environments, formation of anatase and even crystallisation of unreacted 2,6-bis(1,2,3-triazol1-ethanephosphonate)pyridine ligand, for which a novel crystal structure was identified. This work also reveals a novel means of assessing phosphonate availability using x-ray absorption spectroscopy (XAS), which opens new avenues for studying metal phosphonate materials given XAS is not restricted to the rigid measurement conditions of solid-state NMR.

Cathode-solid electrolyte (SE) interfacial instability poses a major challenge for achieving stable and high-power operations in all-solid-state batteries, which promise superior energy density, thermal stability, and safety over the current Li-ion technology. For technologically important Ni-rich NMCs (LiNixMnyCozO2 or NMCxyz; x/y/z: Ni/Mn/Co stoichiometry) paired with sulfide SEs, redox-mediated instability of the SE is often blamed for rapid cathode deterioration. Here, in-depth spectroscopic and electrochemical analyses of Ni-rich NMCs with a promising sulfide SE reveal hitherto unrecognized electrochemical isolation of active NMC particles driven by rapid interfacial degradations, sparking accelerated capacity fading and poor thermal stability. Introducing a functionalized conductive carbon into the cathode suppresses sulfide SE degradation into reactive polysulfides that drive NMC deterioration. Consequently, NMC622 and NMC811-based cells display high active material utilization, enhanced stability, attractive rate capability and thermal resilience - illustrated by 1C (1C: 160 mA g-1) capacity of ∼150 mAh g-1, 5C rate retention of 95% after 500 cycles with high active loading (≥12 mg cm-2), and an average Coulombic efficiency of 99.8% even for high-temperature cycling. This study uncovers a critical performance degradation pathway in a key cathode-SE pairing and presents a scalable strategy for its in situ regulation, enabling significant performance gains.

The treatment and remediation of sulphate-bearing nuclear wastes is challenging as the presence of sulphur limits available wasteform options for their stabilisation. This study is the first to demonstrate successful Hot-Isostatic Pressing (HIP) consolidation of wasteforms specifically designed for sulphur-rich nuclear wastes. Two optimised glass-ceramic formulations were produced with 10.3-11.5 wt% of SO3 (14-16 wt% Li2SO4) waste loading. Characterisation showed a targeted glass matrix containing dispersed BaSO4 and minor secondary phases. HIPed samples exhibited up to 76% higher density and 92% lower porosity than sintered samples. NMR revealed a predominantly amorphous, highly polymerised silicate-aluminate network, with durability primarily influenced by the balance between network formers and depolymerising species. Chemical durability testing showed these candidate wasteforms met or exceeded performance criteria for similar Low Activity Waste wasteforms. The stainless-steel canister-wasteform interaction zone did not produce additional phases compared to the bulk wasteform nor had any detrimental impact on the HIP canister properties.

Anti-inflammatory colchicine therapy has emerged as a new era for atherosclerotic cardiovascular diseases. However, the therapeutic benefit of colchicine has not been clearly defined. Herein, we present a double coordination-driven approach to fabricate a stable metal-organic nano-assembly of colchicine (COL-TA-Zn) by uniting the tropolone ring of colchicine (COL), phenolic groups of tannic acid (TA), and Zn 2+ ions. This design leverages the antioxidant and anti-inflammatory properties of COL and TA to create a nanoscale platform capable of scavenging radicals and modulating inflammatory pathways. Through robust Zn 2+ coordination, the resulting COL-TA-Zn nanocomplexes exhibit enhanced stability under physiological conditions, ensuring efficient delivery and sustained bioactivity. In vitro assays confirm suppression of foam cell formation and multiple inflammatory mediators, suggesting significant potential for managing atherosclerosis by targeting both oxidative stress and inflammation. Intravenous administration of COL-TA-Zn in Apoe − / − mice significantly reduces atherosclerotic plaque area, MMP-9, TNF-α, and reactive oxygen species (ROS) levels, thereby illustrating its superior anti-atherosclerotic efficacy compared to COL alone. These findings highlight the promise of the dual coordination-driven nanoplatform in cardiovascular disease treatment.

Recent advances in membranes based on 2-dimensional (2D) materials have enabled precise control over angstrom-scale pores, providing a unique platform for studying diverse mass transport mechanisms. In this work, we systematically investigate the transport of solvent vapors through 2D channels made of graphene oxide (GO) laminates with precisely controlled oxygen content. Using in-situ chemical reduction of GO with vitamin C, we fabricated reduced GO membranes (VRGMs) with oxygen content systematically decreased from 31.6 % (pristine GO) to 24.0 % (VRGM-maximum reduction). Vapor permeability measurements showed a distinct correlation between oxygen functional groups and solvent transport behaviour. Specifically, non-polar hexane exhibits 114 % of enhanced permeance through the reduced membranes with larger graphitic domains, while the permeance of water decreases by 55 %. With the support of density functional theory (DFT) simulations, we modelled the hydrogen-bond and dispersion complexes between the solvents and GO and calculated the complexation energies. The simulation results suggest that polar molecules interact with the oxygen functional groups of GO via a hydrogen-bond network, supporting in-plane transport. In contrast, van der Waals forces drive the transport of low-polarity solvents along the graphitic domains of the 2D channel in reduced GO membranes. Our findings provide potential strategies for future design of organic solvent nanofiltration membranes.

Plastic waste has become a critical challenge threatening our environment and survival. There has been a growing demand for recycling methods to process waste into clean virgin-like material. However, one of the key challenges limiting recyclability is the difficulty in accurately identifying different types of plastics in post-consumer kerbside waste. Commercial sorting of collected waste relies primarily on near infrared technology, which is associated with significant limitations. Herein, we compared a range of analytical techniques to identify different post-consumer plastic waste samples. With the finding that 13C solid state NMR can precisely identify different polyolefins, we explored the possibility of employing 13C solid state NMR for quantification of plastics from mixed waste samples, which can be quite difficult to quantitate using other standard techniques. Our results demonstrate that 13C solid-state NMR is highly efficient in the quantification of polyolefins from different controlled mixtures. For identification, DSC and NMR are methods of choice with the most clear differences between different polymers, with the exception of different polyethylene subtypes being more suitable for NMR analysis.

This study aims to investigate crystallization of strontium-substituted hydroxyapatite upon sintering. A study of mechanochemically-synthesized hydroxyapatite (HAp), doped with strontium at varying levels from 0 to 20 % is presented. The Sr-doped HAp powders were obtained by a mechanochemical method, followed by sintering at 1000 degrees C. The sintered samples were characterized using a complimentary set of SEM-EDX, XRD, FTIR, Raman, and solid-state NMR techniques. The FTIR spectra of the sintered samples showed a decreasing nu OH vibrational bands with increasing Sr content. This conflict is resolved by multinuclear solid-state NMR which conclusively demonstrates presence of OH-in all samples, and that the strontium doping does not influence the OH-concentration. Sr doping is demonstrated to not be random, with evidence of clustering, but without phase segregation even at the higher Sr loadings. The structural transformations of HAp revealed herein have significant implications in ongoing development of hydroxyapatite based systems, in monitoring the degree of hydroxylation, phase structure and concomitant effects on crystallinity and bioactivity.

The practical realization of lithium metal batteries (LMBs)-long hailed for their high theoretical energy density-continues to be impeded by the persistent challenge of lithium dendrite formation, which compromises safety and cycling stability. In this study, we introduce 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TPP) as an electrolyte additive to suppress dendritic lithium growth. The porphyrin additive forms an in situ lithium-TPP complex at the Li metal interface, which facilitates the interfacial charge transfer and homogenizes the Li+ flux, thereby stabilizing the lithium metal deposition. Symmetric cells incorporating 20 mM TPP in a commercial electrolyte, with a thin polymeric separator that offers minimal resistance to dendritic penetration, exhibit stable cycling for over 1000 h at 0.5 mA cm(-2) without short-circuiting and stable voltage response under increasing current, significantly outperforming the reference cell without the TPP-containing electrolyte, which suffers rapid short-circuit failure. Scanning electron microscopy reveals a compact lithium morphology with the TPP-modified electrolyte, while operando solid-state Li-7 NMR spectroscopy during symmetric Li-cell cycling confirms the suppression of dendrite formation. Full cells using Li4Ti5O12 cathodes demonstrate 90% capacity retention over 150 cycles, with a Coulombic efficiency of 99.9%. These results highlight the potential of porphyrin-based additives in enabling safe and long-lasting lithium metal batteries, and may inspire broader exploration of molecular complexes as a dynamic interphase in next-generation energy storage systems.

Metal phosphonates show promise for recovery of valuable lanthanide (Ln) elements from acidic waste streams due to their selectivity, high capacity, fast kinetics and chemical stability. To optimise these properties, a balance is needed between free phosphonate groups available to bind Ln and P-O-metal linkages to provide stability. This work demonstrates how astute choice of metal precursors can be used to control the phosphonate structure and maximise both sorption and stability. Relative to single metal zirconium phosphonate, mixed metal zirconium titanium phosphonate sorbents had more free phosphonate groups and greater porosity, increasing Ln capacity by 30 % and the kinetic rate constant by 90 %. Acid stability was also improved upon Ti inclusion. Use of metal propoxide and tert-butoxide precursors were also compared, revealing different reactivities with Zr versus Ti. Specifically, the tert-butoxide precursor increased P-O-Zr linkages and acid stability with Zr, but increased formation of leachable P-O-Na-2 groups in the presence of Ti that decreased acid stability. The optimised zirconium titanium phosphonate sorbent used metal propoxide precursors and a Zr:Ti molar ratio of 1:1 to achieve (1) selectivity for Ln over Co, Sr and Cs, (2) sorption capacity of approximately 70 mg Eu/g, (3) fast kinetics with > 99 % sorption in 10 min and (4) retention of 60 % sorption capacity after contact with 5 M nitric acid. The enhanced chemical stability, capacity and kinetics achieved via incorporating Ti drastically improves the practicality of these sorbents for Ln recovery from acidic leachates of magnets, phosphors and other wastes.

Halide solid electrolytes (SEs), like Li3InCl6, are promising for high-energy all-solid-state lithium batteries (ASSLBs) due to their high ionic conductivity and compatibility with high-voltage cathodes. Although solvent-mediated synthesis offers a scalable route to phase-pure Li3InCl6, a lack of understanding of critical synthetic parameters, specifically crystallization kinetics, generally yields SE materials with inferior properties. This study systematically investigates the influence of evaporative crystallization temperature and environment on the phase purity, microstructure, defect chemistry of Li3InCl6 SE, and how these factors collectively impact its transport properties and electrochemical performance. It is revealed that slow crystallization under ambient conditions and moderate temperatures (20-60 °C) yields phase-pure Li3InCl6 with the highest ionic conductivity ever reported for the water-mediated route -3.97 mS cm-1 with carbon contact and 2.98 mS cm-1 without. In contrast, high temperature and non-ambient processing introduce structural defects, increase grain-boundary impedance, and promote impurity incorporation, leading to a significant drop in conductivity. Full cells incorporating the optimized Li3InCl6 deliver high capacity even at a low 20 °C, along with excellent stability (>95%) at high areal loading, supported by low and stable cathode interfacial impedance. This work addresses a critical knowledge gap in solvent-mediated synthesis of halide SEs, providing broadly applicable insights for designing phase-pure, high-conductivity materials for next-generation ASSLBs.

Here, we review the processes involved in producing and assessing the quality of recombinant spider silk proteins (spidroins) and the challenges associated with their synthesis and spinning into robust fibres. We provide an overview of the techniques used to produce the proteins, from gene synthesis to expression in various host organisms. Evidence suggests that the N- and C-terminal regions of spidroins are of utmost importance for fibre assembly and the repetitive domains are responsible for the unique mechanical properties in both native and recombinant versions of spider silks. We describe the role of liquid–liquid phase separation (LLPS) in spidroin assembly and its importance in subsequent fibre formation. Recent developments in recombinant spidroin production and co-expression strategies for improving yield and scalability are highlighted. Techniques such as mass photometry and size exclusion chromatography (SEC) for analysing protein purity and assembly behaviour are thereupon detailed. Finally, we address the role that predictive computational methods play in the future of designing novel and high-performing materials inspired by spidroins.

Deuterium labelling of the non-labile protium atoms in starch granules has been achieved for the first time, by growing genetically modified yeast on deuterated media. Mass spectrometry of the glucose monomers from digested starch showed 44 % average deuteration of the non-labile protium when grown on partially deuterated raffinose (with average deuteration 48 %); yielding starch with 26 % average overall deuteration. Non-labile deuteration was also demonstrated using D2O solvent in the culture medium. Solid-state NMR revealed that deuteration was not evenly distributed across the monomer, being highest at the C6 carbon and lowest at the C1 carbon. SANS revealed two structural features at q = 0.05 & Aring;- 1 and 0.4 & Aring;- 1, the first corresponding to a lamellar repeat of approximately 12-13 nm while the latter is consistent with B-type crystalline polymer packing. Furthermore, solvent contrast variation SANS analysis yielded a contrast match point of 66 mol% D2O indicative of approximately 30-35 % average deuteration of the bulk granules, consistent with mass spectroscopy. When coupled with the more traditional process of exchange of labile protium in the hydroxyl groups by D2O solvent exchange, the biosynthesis of highly deuterated starch opens new opportunities for neutron scattering experiments involving multicomponent starch-based systems.

Sodium borohydride (NaBH4) has been found to display superionic Na+ conductivity upon partial oxidation. Herein, by controlling the hydrolysis of NaBH4 and by thermally stabilizing the oxide phase formed, i.e., NaB(OH)(4), Na+ ionic conductivity increased from similar to 10(-10) S cm(-1) for unmodified NaBH4 to 2.2 x 10(-5) S cm(-1) at room temperature and 2.6 x 10(-3) S cm(-1) at 75 degrees C for hydrolyzed NaBH4. More remarkably, this approach allowed for a comprehensive multidimensional (Na-1H)-Na-23 and (B-1H)-B-11 solid-state NMR analysis and determination of the interplay between pristine alpha-NaBH4 and NaB(OH)(4) in leading to high Na+ ionic conductivity. Not only NMR analysis confirmed that the superionic behavior observed in partially hydrolyzed NaBH4 was the result of Na+ hopping, but 2D NMR also revealed that the hopping mechanism was the result of the formation of a highly defective structure at the alpha-NaBH4/NaB(OH)(4) interface, leading to high Na+ conductivity. Given the simplicity of the oxidation process reported here, this finding opens novel and facile methodologies for the development of promising solid-state electrolytes for sodium-based batteries.

Defect engineering in metal oxides is an effective approach for improving advanced oxidation processes. Herein, we report that regulating the defect types present on SnO2 enables deconvolution of their distinct effects on organic oxidation. Nitrogen annealing created E-delta' center and non-bridging oxygen hole center (NBOHC) defects, while optimum hydrogenation introduced oxygen vacancies, significantly enhancing catalytic oxidation performance. Based on spectroscopic analysis, extended hydrogenation times passivated NBOHCs and formed new types of defects, such as electrons trapped in oxygen vacancies, which are less catalytically active in comparison with NBOHCs. DFT indicated that oxygen vacancies lower the energy barrier for oxygen activation as well as activation of the C-H bonds in formic acid, corroborating the experimental results of enhanced catalytic activity in samples with optimized defect concentrations. The current work advances understanding of the roles different defects play in enhancing organic oxidation in the ongoing search for efficient materials for oxidation reactions.

We report a durable COF nanocoating on living cells, resistant to various stressors, enhancing cell survival under extreme conditions and enabling yeast fermentation, making it a dependable microorganism protection platform.

Gallium (Ga), a low-melting-point liquid metal with soft, metallic, and biocompatible properties, offers many possibilities. However, the potential of composites that integrate Ga with biomacromolecules, combining their biocompatibility, elasticity, and conductivity, has not been thoroughly explored, which is a gap for advancing these composites in various applications. In parallel and independently, protein self-assembled l.,;3bhnanofibrils have attracted great interest as building blocks for functional biomaterials. Here, composites of Ga droplets and nanofibrils are presented, self-assembled from plant proteins of soy protein isolate (SPI). It is evidenced that in these composites self-assembled SPI nanofibrils can effectively reduce the oxidation of Ga droplets. It is observed that the composites of beta-sheet nanofibrils and Ga droplets offer mechanical properties similar to only fibrils-based films. Films of 32 wt% Ga in SPI showed enhanced electrical conductivity and well-structured nanofibrils with multifunctional potential in gas-sensing and electronically controlled antibacterial applications. It is illustrated that the 32 wt% Ga in SPI composite offered the best sensing performance for a diatomic molecule, CO, and electro-stimulation of this composite effectively reduced bacterial growth. The Ga in SPI composite, combining the advantages of protein nanofibrils and Ga droplets, offers great potential in future biomedical applications. Composites of gallium (Ga) droplets and nanofibrils from plant-based soy protein isolate (SPI) are presented. Nanofibrils reduce the oxidation of the surface of Ga droplets, sintering them. The SPI-Ga composite films are electrically conductive organic-inorganic hybrids. These composites offer multifunctional capabilities for gas-sensing and electronically controlled antibacterial applications. image

Organic redox-active materials are promising electrode candidates for the next generation of rechargeable batteries owing to their versatile redox chemistry, sustainability, and potential low cost. Here, we present polydiphenylamine as a moderately high-voltage (1.25 V vs. Zn) and highly reversible organic cathode for aqueous zinc batteries. As revealed by cyclic voltammetry and spectroscopic analysis, the chemical oxidation-derived diphenylamine dimer electrochemically transforms into a cross-linked polymeric material during the first electrochemical oxidation (charge), which then operates by pdoping/dedoping redox of the amine center and a pseudocapacitor-like solid-state charge storage mechanism during the subsequent discharge-charge cycles. With an 80 wt% active loading, the polymer cathode delivers a specific capacity of 138 mAh/g at 100 mA/g, with 73% retention over 1000 cycles at a 99.8% Coulombic efficiency. Excellent rate capability is evidenced by 87 mAh/g capacity at 400 mA/g and highly stable cycling of over 1200 cycles under variable current rates. Facile one-step synthesis, fast charge storage kinetics, and attractive electrochemical performance establish polydiphenylamine as a notable organic cathode candidate for aqueous zinc batteries. (c) 2024 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

Composite zeolites, specifically ZSM-5/AlPO4-5 ([E]-Z5/Al5, [B]-Z5/Al5 and [H]-Z5/Al5), were prepared using tri-substituted imidazolium bromide ionic liquids (ILs). The ILs used were 1-ethyl-2,3-dimethylimidazolium bromide ([EMMIM]Br), 1-butyl-2,3-dimethylimidazolium bromide ([BMMIM]Br) and 1-hexyl-2,3-dimethylimidazolium bromide ([HMMIM]Br). The structure, morphology and acidity of the composite zeolites were analyzed using various techniques, such as X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), Fourier transform infrared spectroscopy (FT-IR), N2 isothermal adsorption-desorption, thermogravimetric analysis (TGA), temperature-programmed desorption of ammonia (NH3-TPD) and nuclear magnetic resonance spectroscopy (NMR). The catalysts obtained demonstrate outstanding performance in the methanol-to-olefin (MTO) reaction, with a catalytic lifetime extended by approximately tenfold and an approximately 10 % increase in the yield of light carbon olefins compared to the traditional hydrothermal Z5/Al5 catalyst. There is a strong relationship between the selectivity and stability of the MTO reaction with the optimized grain size and catalyst acidity.

Quasi-solid-state dual-ion batteries (QSS-DIBs), which represent an emerging part of clean decarbonization technologies, enable sustainable energy storage with metal-free anion-intercalation graphite cathodes. However, the feasibility of QSS-DIBs is constrained by the low areal capacity (<0.2 mA h cm(-2)) and rapid performance decay of the graphite cathode. In this report, an anion conductive polymer (ACP) coating layer is introduced to stabilize the cathode-electrolyte interface for durable and high-areal-performance QSS-DIBs. The solvated ACP layer made from metatungstate-doped polyaniline can confine the solvent, which minimizes side reactions on cathodes and promises an exceptional lifespan with 94% capacity retention after 2000 cycles. Most importantly, the ACP accelerates the efficient anion delivery on a high-loading graphite cathode and unlocks a record areal capacity of 1.78 mA h cm(-2) in QSS-DIBs. Finally, the ACP-Gr design promotes both the performance and eco-friendliness of graphite cathodes in QSS-DIBs.