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Intermediate-range solvent templating and counterion behaviour at charged carbon nanotube surfaces

The ordering of ions and solvent molecules around nanostructures is of profound fundamental importance, from understanding biological processes to the manipulation of nanomaterials to optimizing electrochemical devices. Classical models commonly used to describe these systems treat the solvent simplistically, an approach that endures, in part, due to the extreme difficulty of attaining experimental measurements that challenge this approximation. Here we perform total neutron scattering experiments on model systems—concentrated amide solutions of negatively charged carbon nanotubes and sodium counterions—and measure remarkably complex intermediate-range molecular solvent ordering. The charged surface orders the solvents up to 40 Å, even beyond its dense concentric solvation shells. Notably, the molecular orientation of solvent in direct contact with the nanotube surface itself is distinct, lying near-parallel and not interacting with desolvated sodium counterions. In contrast, beyond this layer the ordering of solvent is perpendicular to the surface. Our results underscore the critical importance of multibody interactions in solvated nanoscale systems and charged surfaces, highlighting competing ion/surface solvation effects.

Site-specific activation of the proton pump inhibitor rabeprazole by tetrathiolate zinc centres

Proton pump inhibitors have become top-selling drugs worldwide. Serendipitously discovered as prodrugs that are activated by protonation in acidic environments, proton pump inhibitors inhibit stomach acid secretion by covalently modifying the gastric proton pump. Despite their widespread use, alternative activation mechanisms and potential target proteins in non-acidic environments remain poorly understood. Employing a chemoproteomic approach, we found that the proton pump inhibitor rabeprazole selectively forms covalent conjugates with zinc-binding proteins. Focusing on DENR, a protein with a C4 zinc cluster (that is, zinc coordinated by four cysteines), we show that rabeprazole is activated by the zinc ion and subsequently conjugated to zinc-coordinating cysteines. Our results suggest that drug binding, activation and conjugation take place rapidly within the zinc coordination sphere. Finally, we provide evidence that other proton pump inhibitors can be activated in the same way. We conclude that zinc acts as a Lewis acid, obviating the need for low pH, to promote the activation and conjugation of proton pump inhibitors in non-acidic environments.

Direct observation of Mn-ion dissolution from LiMn2O4 lithium battery cathode to electrolyte

The degradation of lithium-ion batteries has become a concerning issue. One problem is metal ion dissolution from the cathode material, such as Mn2+ dissolution from spinel-type LiMn2O4 (LMO). However, direct observation of the dissolution process has yet to be reported. Here, we establish in-situ 1H nuclear magnetic resonance imaging (MRI) measurement as an efficient technique to observe Mn2+ dissolution from a model lithium battery with LMO as the cathode. We observe an increase in the MRI signal intensity near the cathode, confirming the dissolution of Mn2+ from the cathode to the electrolyte. Moreover, we show that Mn2+ dissolution from LMO can be suppressed using an appropriate choice of electrolytes. We believe the method developed here can answer the long-time unanswered question of when, where, and how the metal ion dissolution occurs in the lithium-ion battery electrode and can be extended to other electrochemical systems.

Revealing the molecular interplay of coverage, wettability, and capacitive response at the Pt(111)-water solution interface under bias

While electrified interfaces are crucial for electrocatalysis and corrosion, their molecular morphology remains largely unknown. Through highly realistic ab initio molecular dynamics simulations of the Pt(111)-water solution interface in reducing conditions, we reveal a deep interconnection among electrode coverage, wettability, capacitive response, and catalytic activity. We identify computationally the experimentally hypothesised states for adsorbed hydrogen on Pt, HUPD and HOPD, revealing their role in governing interfacial water reorientation and hydrogen evolution. The transition between these two H states with increasing potential, induces a shift from a hydrophobic to a hydrophilic interface and correlates with a change in the primary electrode screening mechanism. This results in a slope change in differential capacitance, marking the onset of the experimentally observed peak around the potential of zero charge. Our work produces crucial insights for advancing electrocatalytic energy conversion, developing deep understanding of electrified interfaces.

Improving lithium-sulfur battery performance using a polysaccharide binder derived from red algae

Li-S batteries are a promising energy storage technology due to their high theoretical capacity, but they suffer from issues such as poor cycle stability and capacity loss over time. Here, we investigate the impact of carrageenan, a polysaccharide binder derived from red algae, on the performance of Li-S batteries. Electrode slurries are prepared without the toxic solvent N-methyl-2-pyrrolidone, using only water as a solvent and dispersant, making the process potentially scalable and cost-effective. With the optimal amount of carrageenan, we observe a capacity retention of 69.1% at 4 C after 1000 charge-discharge cycles. Carrageenan-based electrodes deliver 30% higher capacity than those made with the industry-standard polyvinylidene fluoride binder. X-ray photoelectron spectroscopy analysis confirms the chemical binding of carrageenan to the sulfur active material, and transmission X-ray absorption spectroscopy reveals that carrageenan effectively traps shorter-chain lithium polysulfides, improving the overall battery performance.

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