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The aqueous zinc-sulfur battery holds promise for significant capacity and energy density with low cost and safe operation based on environmentally benign materials. However, it suffers from the sluggish kinetics of the conversion reaction. Here, we highlight the efficacy of molybdenum(IV) sulfide (MoS 2 ) to reduce the overpotential of S-ZnS conversion in aqueous electrolytes and study the discharge products formed at the solid-solid and solid-liquid interfaces using experimental and theoretical approaches. Specifically, the MoS 2 -catalyzed electrochemical conversion reaction is characterized via ex situ X-ray diffraction (XRD), transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS), Raman spectroscopy, synchrotron-based Mo K -edge X-ray absorption spectroscopy (XAS), and in situ synchrotron-based X-ray computed tomography (XCT). Additionally, operando synchrotron-based S K -edge XAS and X-ray fluorescence (XRF) maps are collected to determine the spatial evolution of sulfur-based species at the electrode-electrolyte interface. Coupling the operando S K -edge XAS data with the simulated spectra and fitting the data suggested a possible ZnS 2 intermediate phase.

Intense noise poses a threat to spiral ganglion neurons (SGNs) in the inner ear, often resulting in limited axonal regeneration during noise injury and leading to noise-induced hearing loss (NIHL). Here, we propose an ultrasound-triggered nitric oxide (NO) release to enhance the sprouting and regeneration of injured axons in SGNs. We developed hollow silicon nanoparticles to load nitrosylated N-acetylcysteine, producing HMSN-SNO, which effectively protects NO from external interferences. Utilizing low-intensity ultrasound stimulation with bone penetration, we achieve the controlled release of NO from HMSN-SNO within the cochlea. In mice with NIHL, a rapid and extensive loss of synaptic connections between hair cells and SGNs is observed within 24 h after exposure to excessive noise. However, this loss could be reversed with the combined treatment, resulting in a hearing functional recovery from 83.57 to 65.00 dB SPL. This positive outcome is attributed to the multifunctional effects of HMSN-SNO, wherein they scavenge reactive oxygen species (ROS) to reverse the pathological microenvironment and simultaneously upregulate the CREB/BDNF/EGR1 signaling pathway, thereby enhancing neuroplasticity and promoting the regeneration of neuronal axons. These findings underscore the potential of nanomedicine for neuroplasticity modulation, which holds promise for advancing both basic research and the further treatment of neurological diseases.

Short-wave infrared (SWIR) imaging systems offer remarkable advantages, such as enhanced resolution and contrast, compared to their optical counterparts. However, broader applications demand improvements in performance, notably the elimination of cryogenic temperature requirements and cost reduction in manufacturing processes. In this manuscript, we present a new development in SWIR photodetection, exploiting the potential of metal halide perovskite materials. Our work introduces a cost-effective and easily fabricated SWIR photodetector with an ultrabroad detection range from 900 to 2500 nm, a room-temperature responsivity of 1.57 × 10 2 A/W, and a specific detectivity of 4.18 × 10 10 Jones at 1310 nm. We then performed comprehensive static and time-resolved optical and electrical measurements under ambient conditions, complemented by extensive density functional theory simulations, validating the formation of heterojunctions within the intrinsic n -type and extrinsic p -type perovskite structures. The potential of our perovskite-based SWIR materials extends from photodetectors to photovoltaic cells and introduces a possibility for high SWIR responsivity at room temperature and atmospheric pressure, which promotes its economic efficiency., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Given the extensive role of lipids in cancer development, there is substantial clinical interest in developing therapies that target lipid metabolism. In this study, we identified one cyclometalated iridium complex ( Ir2 ) that exhibits potent antiproliferation activity in MIA PaCa-2 cells by regulating fatty acid metabolism and sphingolipid metabolism simultaneously. Ir2 also efficiently overcomes cisplatin resistance in vitro . Satisfyingly, the generated Ir2@F127 carriers, as a temperature-sensitiv e in situ gelling system of Ir2 , showed effective cancer treatment with minimal side effects in an in vivo xenograft study. To the best of our knowledge, Ir2 is the first reported cyclometalated iridium complex that exerts anticancer activity in MIA PaCa-2 cells by intervening in lipid metabolism, which provides an alternative pathway for the anticancer mechanism of cyclometalated iridium complexes.

The synergistic engineering of chemical complexity and crystal structures has been applied to Prussian blue analogue (PBA) cathodes in this work. More precisely, the high-entropy concept has been successfully introduced into two structure types of identical composition, namely, cubic and monoclinic. Through the utilization of a variety of complementary characterization techniques, a comprehensive investigation into the electrochemical behavior of the cubic and monoclinic PBAs has been conducted, providing nuanced insights. The implementation of the high-entropy concept exhibits crucial selectivity toward the intrinsic crystal structure. Specifically, while the overall cycling stability of both cathode systems is significantly improved, the synergistic interplay of crystal structure engineering and entropy proves particularly significant. After optimization, the cubic PBA demonstrates structural advantages, showcasing good reversibility, minimal capacity loss, high thermal stability, and unparalleled endurance even under harsh conditions (high specific current and temperature).

Thermal desorption (TD) of wipe-based samples was coupled with an in-line dielectric barrier discharge ionization (DBDI) source and rugged compact time-of-flight mass spectrometer (MS) for the detection of explosives, propellants, and postblast debris. The chromatography-free TD-DBDI-MS platform enabled rapid and sensitive detection of organic nitramine, nitrate ester, and nitroaromatic explosives as well as black powder and black powder substitute propellants. Parametric investigations characterized the response to TD temperature and optimized DBDI voltage, aerodynamically assisted entrainment, and fragmentation through in-source collision induced dissociation (isCID). Excess nitrate generated by the DBDI source yielded predominantly nitrate-adduct formation. Subnanogram sensitivities were demonstrated for all explosives investigated, except for nitroglycerin, specifically due to its volatility. Further, most analytes/explosives exhibited tens of picograms sensitivities. The platform also demonstrated the detection of propellant and military explosives from postblast debris. The TD-DBDI-MS system performed well without the need for aerodynamically assisted entrainment (and the associated rough pump), which along with requiring no additional gases (i.e., N 2 or He) or solvents, aid in potential field deployment. The ease of TD-DBDI attachment and removal added trace solid or liquid residue detection to the rugged mass spectrometer, designed primarily for the analysis of volatile organic and inorganic compounds.

Conical intersections (CIs) hold significant stake in manipulating and controlling photochemical reaction pathways of molecules at interfaces and surfaces by affecting molecular dynamics therein. Currently, there is no tool for characterizing CIs at interfaces and surfaces. To this end, we have developed phase-cycling interface-specific two-dimensional electronic spectroscopy (i2D-ES) and combined it with advanced computational modeling to explore nonadiabatic CI dynamics of molecules at the air/water interface. Specifically, we integrated the phase locked pump pulse pair with an interface-specific electronic probe to obtain the two-dimensional interface-specific responses. We demonstrate that the nonadiabatic transitions of an interface-active azo dye molecule that occur through the CIs at the interface have different kinetic pathways from those in the bulk water. Upon photoexcitation, two CIs are present: one from an intersection of an optically active S 2 state with a dark S 1 state and the other from the intersection of the progressed S 1 with the ground state S 0 . We find that the molecular conformations in the ground state are different for interfacial molecules. The interfacial molecules are intimately correlated with the locally populated excited state S 2 being farther away from the CI region. This leads to slower nonadiabatic dynamics at the interface than in bulk water. Moreover, we show that the nonadiabatic transition from the S 1 dark state to the ground state is significantly longer at the interface than that in the bulk, which is likely due to the orientationally restricted configuration of the excited state at the interface. Our findings suggest that orientational configurations of molecules manipulate reaction pathways at interfaces and surfaces.

Native chemical ligation (NCL) represents a cornerstone strategy in accessing synthetic peptides and proteins, remaining one of the most efficacious methodologies in this domain. The fundamental requisites for achieving a proficient NCL reaction involve chemoselective coupling between a C-terminal thioester peptide and a thiol-bearing N-terminal peptide. However, achieving coupling at sterically congested residues remains challenging. In addition, while most NCLs proceed without epimerization, β-branched (e.g., Ile, Thr, Val) and Pro-derived C-terminal thioesters react slowly and can be susceptible to significant epimerization and hydrolysis. Herein, we report an epimerization-free NCL reaction via β-lactone-mediated native chemical ligation which constructs sterically congested Thr residues. The constrained ring from the β-lactone allows rapid peptide ligation without detectable epimerization. The method has a broad side-chain tolerance and was applied to the preparation of cyclic peptides and polypeptidyl thioester, which could be difficult to obtained otherwise.

Ulva sp. is a type of green algae and is widely distributed in coastal areas around the world due to eutrophication. Effective utilization of Ulva sp. is expected for the establishment of carbon-neutral biochemical production. Microwave-assisted hydrothermal extraction is one of the most efficient ways of extracting highly functional polysaccharides called ulvan. Here, we demonstrate the importance of microwave frequency in enhancing ulvan extraction from Ulva meridionalis . We found that microwaves (2.45 GHz) selectively heat water solvent, while radio frequency (200 MHz) selectively heats ionic ulvan. Moreover, 2.45 GHz was more effective for extracting ulvan than 200 MHz. Then, we analyzed the conformational change in ulvan during microwave irradiation using in situ small-angle X-ray scattering. Microwaves initiated the loosening of ulvan bundles at temperatures lower than those of conventional heating. As a result, microwaves at 2.45 GHz selectively heat water and initiate ulvan structural change to enhance the extraction of ulvan from U. meridionalis ., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Secondary organic aerosol (SOA) from acid-driven reactive uptake of isoprene epoxydiols (IEPOX) contributes up to 40% of organic aerosol (OA) mass in fine particulate matter. Previous work showed that IEPOX substantially converts particulate inorganic sulfates to surface-active organosulfates (OSs). This decreases aerosol acidity and creates a viscous organic-rich shell that poses as a diffusion barrier, inhibiting additional reactive uptake of IEPOX. To account for this "self-limiting" effect, we developed a phase-separation box model to evaluate parameterizations of IEPOX reactive uptake against time-resolved chamber measurements of IEPOX-SOA tracers, including 2-methyltetrols (2-MT) and methyltetrol sulfates (MTS), at ~ 50% relative humidity. The phase-separation model was most sensitive to the mass accommodation coefficient, IEPOX diffusivity in the organic shell, and ratio of the third-order reaction rate constants forming 2-MT and MTS ( k M T / k M T S ). In particular, k M T / k M T S had to be lower than 0.1 to bring model predictions of 2-MT and MTS in closer agreement with chamber measurements; prior studies reported values larger than 0.71. The model-derived rate constants favor more particulate MTS formation due to 2-MT likely off-gassing at ambient-relevant OA loadings. Incorporating this parametrization into chemical transport models is expected to predict lower IEPOX-SOA mass and volatility due to the predominance of OSs.

Atmospheric nitrate, including nitric acid (HNO 3 ), particulate nitrate (pNO 3 ), and organic nitrate (RONO 2 ), is a key atmosphere component with implications for air quality, nutrient deposition, and climate. However, accurately representing atmospheric nitrate concentrations within atmospheric chemistry models is a persistent challenge. A contributing factor to this challenge is the intricate chemical transformations involving HNO 3 formation, which can be difficult for models to replicate. Here, we present a novel model framework that utilizes the oxygen stable isotope anomaly (Δ 17 O) to quantitatively depict ozone (O 3 ) involvement in precursor nitrogen oxides N O x = N O + N O 2 photochemical cycling and HNO 3 formation. This framework has been integrated into the US EPA Community Multiscale Air Quality (CMAQ) modeling system to facilitate a comprehensive assessment of NO x oxidation and HNO 3 formation. In application across the northeastern US, the model Δ 17 O compares well with recently conducted diurnal Δ 17 O(NO 2 ) and spatiotemporal Δ 17 O(HNO 3 ) observations, with a root mean square error between model and observations of 2.6 ‰ for Δ 17 O(HNO 3 ). The model indicates the major formation pathways of annual HNO 3 production within the northeastern US are NO+OH (46 %), N 2 O 5 hydrolysis (34 %), and organic nitrate hydrolysis (12 %). This model can evaluate NO x chemistry in CMAQ in future air quality and deposition studies involving reactive nitrogen.

We explore the potential of nanocrystals (a term used equivalently to nanoparticles) as building blocks for nanomaterials, and the current advances and open challenges for fundamental science developments and applications. Nanocrystal assemblies are inherently multiscale, and the generation of revolutionary material properties requires a precise understanding of the relationship between structure and function, the former being determined by classical effects and the latter often by quantum effects. With an emphasis on theory and computation, we discuss challenges that hamper current assembly strategies and to what extent nanocrystal assemblies represent thermodynamic equilibrium or kinetically trapped metastable states. We also examine dynamic effects and optimization of assembly protocols. Finally, we discuss promising material functions and examples of their realization with nanocrystal assemblies.

Traditional Li-ion intercalation chemistry into graphite anodes exclusively utilizes the cointercalation-free or cointercalation mechanism. The latter mechanism is based on ternary graphite intercalation compounds (t-GICs), where glyme solvents were explored and proved to deliver unsatisfactory cyclability in LIBs. Herein, we report a novel intercalation mechanism, that is, in situ synthesis of t-GIC in the tetrahydrofuran (THF) electrolyte via a spontaneous, controllable reaction between binary-GIC (b-GIC) and free THF molecules during initial graphite lithiation. The spontaneous transformation from b-GIC to t-GIC, which is different from conventional cointercalation chemistry, is characterized and quantified via operando synchrotron X-ray and electrochemical analyses. The resulting t-GIC chemistry obviates the necessity for complete Li-ion desolvation, facilitating rapid kinetics and synchronous charge/discharge of graphite particles, even under high current densities. Consequently, the graphite anode demonstrates unprecedented fast charging (1 min), dendrite-free low-temperature performance, and ultralong lifetimes exceeding 10 000 cycles. Full cells coupled with a layered cathode display remarkable cycling stability upon a 15 min charging and excellent rate capability even at -40 °C. Furthermore, our chemical strategies are shown to extend beyond Li-ion batteries to encompass Na-ion and K-ion batteries, underscoring their broad applicability. Our work contributes to the advancement of graphite intercalation chemistry and presents a low-cost, adaptable approach for achieving fast-charging and low-temperature batteries.

Carbon monoxide (CO) is a byproduct of the incomplete combustion of carbon-based fuels, such as wood, coal, gasoline, or natural gas. As incomplete combustion in a fire accident or in an engine, massively produced CO leads to a serious life threat because CO competes with oxygen (O 2 ) binding to hemoglobin and makes people suffer from hypoxia. Although there is hyperbaric O 2 therapy for patients with CO poisoning, the nanoscale mechanism of CO dissociation in the O 2 -rich environment is not completely understood. In this study, we construct the classical force field parameters compatible with the CHARMM for simulating the coordination interactions between hemoglobin, CO, and O 2 , and use the force field to reveal the impact of O 2 on the binding strength between hemoglobin and CO. Density functional theory and Car-Parrinello molecular dynamics simulations are used to obtain the bond energy and equilibrium geometry, and we used machine learning enabled via a feedforward neural network model to obtain the classical force field parameters. We used steered molecular dynamics simulations with a force field to characterize the mechanical strength of the hemoglobin-CO bond before rupture under different simulated O 2 -rich environments. The results show that as O 2 approaches the Fe 2+ of heme at a distance smaller than ∼2.8 Å, the coordination bond between CO and Fe 2+ is reduced to 50% bond strength in terms of the peak force observed in the rupture process. This weakening effect is also shown by the free energy landscape measured by our metadynamics simulation. Our work suggests that the O 2 -rich environment around the hemoglobin-CO bond effectively weakens the bonding, so that designing of O 2 delivery vector to the site is helpful for alleviating CO binding, which may shed light on de novo drug design for CO poisoning.

The observation of thioester-mediated acyl transfer processes in nature has inspired the development of novel protein synthesis and functionalization methodologies. The chemoselective transfer of an acyl group from S -to- N is the basis of several powerful ligation strategies. In this work, we sought to apply the reverse process, the transfer of an acyl group from N -to- S , as a method to convert stable chiral amides into more reactive thioesters. To this end, we developed a novel cysteine-derived oxazolidinone that serves as both a chiral imide auxiliary and an acyl transfer agent. This auxiliary combines the desirable features of rigid chiral imides as templates for asymmetric transformations with the synthetic applicability of thioesters. We demonstrate that the auxiliary can be applied in a range of highly selective asymmetric transformations. Subsequent intramolecular N -to- S acyl transfer of the chiral product and in situ trapping of the resulting thioester provides access to diverse carboxylic acid derivatives under mild conditions. The oxazolidinone thioester products can also be isolated and used in Pd-mediated transformations to furnish highly valuable chiral scaffolds, such as noncanonical amino acids, cyclic ketones, tetrahydropyrones, and dihydroquinolinones. Finally, we demonstrate that the oxazolidinone thioesters can also serve as a surrogate for SNAC-thioesters, enabling their seamless use as non-native substrates in biocatalytic transformations., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

A family of 4,4'- t Bu 2 -2,2'-bipyridine ( tBu bpy) ligands with substituents in either the 6-position, 4,4'- t Bu 2 -6-Me-bpy ( tBu bpy Me ), or 6 and 6'-positions, 4,4'- t Bu 2 -6,6'-R 2 -bpy ( tBu bpy R2 ; R = Me, i Pr, s Bu, Ph, or Mes), was synthesized. These ligands were used to prepare Ni complexes in the 0, I, and II oxidation states. We observed that the substituents in the 6 and 6'-positions of the tBu bpy ligand impact the properties of the Ni complexes. For example, bulkier substituents in the 6,6'-positions of tBu bpy better stabilized ( tBu bpy R2 )Ni I Cl species and resulted in cleaner reduction from ( tBu bpy R2 )Ni II Cl 2 . However, bulkier substituents hindered or prevented coordination of tBu bpy R2 ligands to Ni 0 (cod) 2 . In addition, by using complexes of the type ( tBu bpy Me )NiCl 2 and ( tBu bpy R2 )NiCl 2 as precatalysts for different XEC reactions, we demonstrated that the 6 or 6,6' substituents lead to major differences in catalytic performance. Specifically, while ( tBu bpy Me )Ni II Cl 2 is one of the most active catalysts reported to date for XEC and can facilitate XEC reactions at room temperature, lower turnover frequencies were observed for catalysts containing tBu bpy R2 ligands. A detailed study on the catalytic intermediates ( tBu bpy)Ni(Ar)I and ( tBu bpy Me2 )Ni(Ar)I revealed several factors that likely contributed to the differences in catalytic activity. For example, whereas complexes of the type ( tBu bpy)Ni(Ar)I are low spin and relatively stable, complexes of the type ( tBu bpy Me2 )Ni(Ar)I are high-spin and less stable. Further, ( tBu bpy Me2 )Ni(Ar)I captures primary and benzylic alkyl radicals more slowly than ( tBu bpy)Ni(Ar)I, consistent with the lower activity of the former in catalysis. Our findings will assist in the design of tailor-made ligands for Ni-catalyzed transformations., Competing Interests: Competing Financial Interests The authors declare no competing financial interests.

With the recent legalization of cannabis in multiple jurisdictions and widespread use as a medical treatment, there has been an increased focus on product safety and the potential impacts of contaminants on human health. One factor that has received little attention is the possible exposure to potentially hazardous levels of toxic elements from rolling (smoking) papers. The elemental composition of rolling papers is largely unregulated, with a minority of jurisdictions regulating papers only when they are part of a final cannabis product. This study reports the concentrations of 26 elements in commercially available rolling papers and estimates potential maximum exposures relative to USP232 and ICH Q3D dosages in pharmaceutical compounds. Exposure estimates indicate that the concentrations of several elements in some products, particularly Cu, Cr, and V, may present a potential hazard to frequent users. Several elements, including Ag, Ca, Ba, Cu, Ti, Cr, Sb, and possibly others, are likely present in elevated quantities in some papers due to product design and manufacturing processes. Our results further suggest that Cu-based pigments are used by a number of manufacturers and that regular use of these products might result in exposures as high as 4.5-11 times the maximum exposure limits. Further research to quantify the contribution of rolling papers to elemental exposure under realistic smoking conditions is warranted., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Spinal cord injury is a disease that causes severe damage to the central nervous system. Currently, there is no cure for spinal cord injury. Azithromycin is commonly used as an antibiotic, but it can also exert anti-inflammatory effects by down-regulating M1-type macrophage genes and up-regulating M2-type macrophage genes, which may make it effective for treating spinal cord injury. Bone mesenchymal stem cells possess tissue regenerative capabilities that may help promote the repair of the injured spinal cord. In this study, our objective was to explore the potential of promoting repair in the injured spinal cord by delivering bone mesenchymal stem cells that had internalized nanoparticles preloaded with azithromycin. To achieve this objective, we formulated azithromycin into nanoparticles along with a trans-activating transcriptional activator, which should enhance nanoparticle uptake by bone mesenchymal stem cells. These stem cells were then incorporated into an injectable hydrogel. The therapeutic effects of this formulation were analyzed in vitro using a mouse microglial cell line and a human neuroblastoma cell line, as well as in vivo using a rat model of spinal cord injury. The results showed that the formulation exhibited anti-inflammatory and neuroprotective effects in vitro as well as therapeutic effects in vivo . These results highlight the potential of a hydrogel containing bone mesenchymal stem cells preloaded with azithromycin and trans-activating transcriptional activator to mitigate spinal cord injury and promote tissue repair.

Interactions between the sigma 1 receptor agonist PRE-084 and various lipid monolayers, including dipalmitoylphosphatidylcholine (DPPC), DPP-ethanolamine (DPPE), DPP-glycerol (DPPG), DPP-serine (DPPS), palmitoylsphingomyelin (PSM), and cholesterol (Ch), were investigated to elucidate the effects of PRE-084 on membrane fluidity and stability. Their interactions with sigma 1 receptor agonists have potential implications for neuroprotection, antidepressant, analgesic, and cognitive enhancement effects. In this study, we observed that the presence of PRE-084 in the subphase led to increased fluidity in DPPC and DPPE monolayers, whereas decreasing fluidity was observed in DPPG, DPPS, and PSM monolayers. The interaction of PRE-084 with Ch monolayers was found to be distinct from its interaction with other lipids. Fluorescence microscopy images revealed changes in the size and shape of liquid-condensed domains in the presence of PRE-084, supporting the notion of altered membrane fluidity. Our findings provide new insights into the interaction of PRE-084 with lipid monolayers and its potential implications for biological and membrane science.

Herein, we report a three stranded coiled-coil (3SCC) de novo protein containing a type II copper center (CuT2) composed of 6-membered ring N-heterocycles. This design yields the most active homogenous copper nitrite reductase (CuNiR) mimic in water. We achieved this result by controlling three factors. First, previous studies with N δ and N ε -Methyl Histidine had indicated that a ligand providing pyridine-like electronic character to the copper site was superior to the more donating N δ for nitrite reduction. By substitution of the parent histidine with the non-coded amino acids pyridyl alanine (3'-Pyridine [3'Py] vs 4'-Pyridine [4'Py]), an authentic pyridine donor was employed without the complications of the coupling of both electronic and tautomeric effects of histidine or methylated histidine. Second, by changing the position of the nitrogen atom within the active site (4'-Pyridine vs. 3'Pyridine) a doubling of the enzyme's catalytic efficiency resulted. This effect was driven exclusivity by substrate binding to the copper site. Third, we replaced the leucine layer adjacent to the active site with an alanine, and the disparity between the 3'Py and 4'Py became more apparent. The decreased steric bulk minimally impacted the 3'Py derivative; however, the 4'Py K m decreased by an order of magnitude (600 mM to 50 mM), resulting in a 40-fold enhancement in the k cat / K m compared to the analogues histidine site and a 1500-fold improvement compared with the initially reported CuNiR catalyst of this family, TRIW-H. When combined with XANES/EXAFS data, the relaxing of the Cu(I) site to a more 2-coordinate Cu(I) like structure in the resting state increases the overall catalytic efficiency of nitrite reduction via the lowering of K m . This study illustrates how by combining advanced spectroscopic methods, detailed kinetic analysis, and a broad toolbox of amino acid side chain functionality, one can rationally design systems that optimize biomimetic catalysis., Competing Interests: The authors declare no competing financial interest.

The practically unlimited high-dimensional composition space of high-entropy materials (HEMs) has emerged as an exciting platform for functional material design and discovery. However, the identification of stable and synthesizable HEMs and robust design rules remains a daunting challenge. Here, we propose a mixed enthalpy-entropy descriptor (MEED) that enables highly efficient, robust, high-throughput prediction of synthesizable HEMs across vast chemical spaces from first-principles. The MEED is based on two parameters: the relative formation enthalpy with respect to the most stable competing compound and the spread of the point-defect formation energy spectrum. The former measures the relative synthesizability of an HEM to its most stable competing phase, going beyond the conventional thermodynamic understanding. The latter gauges the relative entropy forming ability of an HEM, entailing no sampling over numerous alloy configurations. By applying the MEED to two structurally distinct representative material systems (i.e., 3D rocksalt carbides and 2D layered sulfides), we not only successfully identify all experimentally reported HEMs within these systems but also reveal a cutoff criterion for assessing their relative synthesizability within each system. By the MEED, tens of new high-entropy carbides and 2D high-entropy sulfides are also predicted, which have the potential for a wide variety of applications such as coating in aerospace devices, energy conversion and storage, and flexible electronics.

Sodium-ion batteries (SIBs) have garnered significant attention due to their potential as an emerging energy storage solution. Tin sulfide (SnS) has emerged as a promising anode material for SIBs due to its impressive theoretical specific capacity of 1022 mA h g -1 and excellent electrical conductivity. However, its practical application has been hindered by issues such as large volume expansion, which adversely affects cycling stability and rate performance during the charge/discharge processes. In this study, a novel approach to address these issues by synthesizing the bean pod cube hollow metal-organic framework (MOF)-SnS x /NC@N-doped carbon nanofibers through a process involving electrospinning, PDA coating, and calcination. The Sn-MOF serves as a self-sacrificing template, facilitating the simultaneous dissociation of MOF and polymerization of dopamine, leading to the creation of hollow intermediates that retain tin components. Subsequent sulfidation results in the integration of the hollow MOF-SnS x /NC nanoparticles within 3D nitrogen-doped carbon nanofibers, forming the distinctive bean pod cube composite structure. This unique configuration effectively shortens the diffusion path and mitigates volume expansion for sodium ions, ultimately yielding an exceptional high rate performance of 130 mA h g -1 (10 A g -1 ) and an ultralong cycling performance of 328 mA h g -1 even after 3500 cycles (2 A g -1 ) as the anode for SIBs.

Voloxidation is a potential alternative reprocessing scheme for spent nuclear fuel that uses gas-solid reactions to minimize aqueous wastes and to separate volatile fission products from the desired actinide phase. The process uses NO 2 (g) as an oxidant for uranium dioxide (UO 2 ) fuel, ideally producing soluble uranium powders which can then be processed for full recycle. To continue development of the process flowsheet for voloxidation, ongoing examination of the process chemistry and associated process materials is required: discrepancies in the proposed chemical reactions that occur when spent nuclear fuel is exposed to NO 2 (g) atmospheres must be addressed. The objective of this work is to analyze the intermediate solid phases produced during voloxidation to support verification of the proposed NO 2 (g) voloxidation reaction mechanisms. This objective was achieved through using (1) powder X-ray diffraction and Raman spectroscopy to identify bulk uranium phases and (2) scanning electron microscopy to describe the morphology and microstructure of the powders at each reaction stage. The initial oxidation of UO 2 under NO 2 (g) reactions produced ε-UO 3 . Further exposure to NO 2 (g) did not nitrate the solid to produce uranyl nitrate, as reported in some literature. However, after the powder was hydrated with steam and then further exposed to NO 2 (g), some traces of uranyl nitrate hexahydrate were found. The results of this study suggest that surface hydration of powders plays a vital role in uranyl nitrate formation under voloxidation conditions and raises questions about the kinetics of the oxide-to-nitrate voloxidation conversion process. Future chemical and engineering design decisions for the voloxidation process may benefit from an improved understanding of these chemical mechanisms., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)