Browse Articles

Influence of Halide Substitution on Local and Average Structure, Lattice Dynamics, and Transport Properties in Cu6PS5X Argyrodites

Abstract Halide-substituted argyrodite materials have attracted increasing attention for energy applications since compositional tuning provides an effective strategy to modulate their structure and transport characteristics. While Li+-based halide argyrodites have been extensively studied, a unified composition-resolved understanding of Cu+-based halide argyrodites that integrates phase evolution, local structure, lattice dynamics, and electronic and ionic transport remain limited. In this work, we investigate Cu6PS5X (X = Cl, Br, I, Cl0.5Br0.5, Cl0.5I0.5, and Br0.5I0.5) within a combined experimental and computational framework. All compositions adopt an average cubic F4̅3m structure at room temperature, while local structural analysis reveals deviations from cubic symmetry consistent with a monoclinic Cc model involving PS43– tetrahedral tilting. 31P MAS NMR spectroscopy corroborates this local symmetry breaking through multiple distinct phosphorus environments arising from relative tetrahedral orientation rather than S2–/X– site disorder. Halide substitution modifies the Cu+ conductivity through changes in the activation energy and the Arrhenius pre-exponential factor, following the Meyer–Neldel behavior, with additional contributions from variations in jump distances and migration pathways. Direction-projected phonon density of states analysis identifies low-frequency Cu+ vibrational components along the crystallographic migration pathways. Analysis of the Meyer–Neldel slope further suggests phonon assisted ion hopping involving multiphonon excitation of low-frequency Cu+ vibrational modes. Together, these findings offer insight into structure–property relationships in Cu6PS5X and suggest that, alongside the migration energy landscape, the vibrational energy scale, thermal population, and directionality of mobile ion modes should be considered when interpreting ion transport, thereby providing a vibrational perspective for the design of solid-state ion conductors.

Genomic profiling identifies actionable DNA-repair defects in a new cervical cancer model

Abstract Genetic profiling of a new HPV-negative cervical cancer model identified pathogenic variants in genes implicated in oncogenic signaling, cell cycle regulation, and DNA damage repair pathways, including homologous recombination, non-homologous end-joining, and mismatch repair. Deficiencies in BRCA 2, RAD51 and MLH1 were among these actionable targets. The newly described cervical cancer model revealed sensitivity towards the PARP inhibitor olaparib, which was further augmented upon combination with platinum-based chemotherapeutics. In contrast, BRCA1/2 -proficient cervical cancer cells exhibited greater resistance to these strategies. This study highlights the potential of in-depth genetic analysis to identify genetic susceptibilities to guide personalized medicine approaches.

Understanding Electrochemical Alcohol Hydrogenolysis Enabled by Carbonyl Reduction in Lignocellulosic Biomass-Derived Aromatic Oxygenates

Abstract Molecules derived from lignocellulosic biomass are oxygenates with multiple oxygen-containing functional groups, such as hydroxyl and carbonyl groups. Therefore, the ability to selectively reduce a specific oxygenate group is essential for the reductive upgrading of such molecules. Previous studies on electrochemical biomass conversion have shown that alcohol hydrogenolysis, which involves cleavage of the σ(C–Oalcohol) bond, is extremely challenging for furfural and 5-hydroxymethylfurfural (HMF) derivatives, including furfuryl alcohol, 5-methylfurfuryl alcohol (MFA), and 2,5-bis(hydroxymethyl)furan (BHMF). In contrast, HMF itself undergoes alcohol hydrogenolysis relatively easily in acidic aqueous media. Considering that the only structural difference between HMF and BHMF or MFA is the presence of a carbonyl group, this observation raises the question of whether the carbonyl group in HMF facilitates alcohol hydrogenolysis. In this study, we designed systematic experiments to provide a coherent explanation of when and how a carbonyl group enables hydrogenolysis of a copresent alcohol group. Specifically, we show that alcohol hydrogenolysis in HMF proceeds via reduction of the carbonyl group to a ketyl radical, followed by a spin-center shift (SCS) through extended π conjugation. We also elucidate the effect of pH on the selectivity between carbonyl hydrogenation and alcohol hydrogenolysis, both of which share the ketyl radical intermediate. This mechanistic understanding enhances our ability to predict and control alcohol hydrogenolysis in the reductive upgrading of biomass-derived oxygenates.

Mechanical and electrical characteristics and pressure-sensitive response measurements of alkali-activated mortar containing conductive fillers

Facile Fabrication of Redox-Active Covalent Organic Frameworks via Reductive <i>N</i> -methylation

Abstract Redox-active covalent organic frameworks (COFs) are promising materials for electronics, sensing, and catalysis. However, their synthesis is hampered by the scarcity of redox-active monomers and the difficulty of functionalizing as-synthesized frameworks without compromising crystallinity. Here, we introduce a reductive N-methylation strategy that enables the universal and mild conversion of imine-linked COFs into crystalline tertiary amine-linked frameworks (NMe-COFs). The method preserves structural order while imparting strong electron-donating and redox-responsive properties. Among the NMe-COFs, COF-300-NMe exhibits an 11-fold increase in iodine uptake with a distinct gate-opening adsorption profile─a behavior that computational studies attribute to enhanced framework flexibility and raised electronic energy levels. Furthermore, incorporation of the electron acceptor 7,7,8,8-tetracyanoquinodimethane into COF-300-NMe yields a charge-transfer complex exhibiting distinct spin signatures. This work establishes a versatile postsynthetic linkage conversion strategy, paving the way toward stimuli-responsive soft COFs and purely organic spin-active materials.

Semaglutide and COVID-19 mortality risk

Abstract Semaglutide, a glucagon-like peptide-1 (GLP-1) receptor agonist, is used to treat type 2 diabetes and manage weight in individuals with obesity or who are overweight. Semaglutide was found to reduce COVID-19-related mortality risk in a secondary analysis of the Semaglutide Effects on Cardiovascular Outcomes in People with Overweight or Obesity (SELECT) trial. We previously demonstrated that diabetes and obesity are associated with higher risks of COVID-19-related mortality in the general population. Using this existing cohort, we found that semaglutide use was associated with a significant 49% reduction in the risk of COVID-19-related death. Diabetes and obesity were linked to higher mortality risk, but an E-value of 3.31 suggests that unmeasured confounders would need to be strong to negate the observed association. These findings suggest that further investigation is warranted into the potential role of semaglutide in reducing risks associated with other causes of death.

In Situ Unveiling of the Coupling Mechanism of Intercalation-Conversion Processes at the Nanoscale in Lithium–Ion/Lithium–Oxygen Hybrid Batteries

Abstract With the rapid growth in energy demand, designing a novel hybrid battery system has become increasingly important. It is critical to reveal the coupling mechanisms of intercalation-conversion hybrid cathodes and provide an in-depth understanding of structure-performance relationships for the electrochemical energy storage devices with high energy density. In this study, a hybrid cathode that combines intercalation-type LiNixCoyMn1-x-yO2 (NCM) with conversion-type oxygen (O2) is proposed. Using in situ electrochemical atomic force microscopy (EC-AFM), we elucidate that the overlithiation of the NCM cathode enhances electronic conductivity and exposes abundant active sites during discharge, thereby inducing the formation of Li2O2. Electrochemical tests demonstrate that the contributions of intercalation and conversion reactions to capacity are rate-dependent, with lower rates favoring the intercalation-dominated electrochemical process. Further scanning transmission electron microscopy characterization indicates that, during prolonged cycling, oxygen vacancies in the NCM intercalation-type cathode serve as preferential sites for the conversion-type Li–O2 intermediates, significantly enhancing the cycling stability of the battery. Ultimately, by optimizing the mass ratio between the intercalation and conversion cathodes, an enhanced cycle stability is achieved. This study offers valuable insights into modulating battery performance through multimechanism reactions in hybrid battery systems.

Feasibility of a novel wearable magnetic sensor device for swallowing assessment compared with videofluoroscopic swallowing study

Multidomain Relaxation Dispersion NMR Resolves an Intermediate-Gated Binding Pathway for Selective Recognition of Linear Diubiquitin by HOIL-1L

Abstract Molecular recognition is governed not only by the structural complementarity of the final complex, but by the kinetic pathway through which it forms. Polyubiquitin chains, in which sequence-identical domains are covalently linked yet must be discriminated by dedicated receptors to encode distinct cellular signals, exemplify this challenge. For NMR relaxation dispersion studies of such systems, spectral overlap between identical domains prevents conventional uniform isotope labeling from resolving the per-domain exchange contributions. Here we show, using domain-selective 15N labeling combined with R2 relaxation dispersion, that the binding of linear (Met1-linked) diubiquitin to HOIL-1L NZF proceeds through an apparent three-state pathway as detected by relaxation dispersion, in which rapid ligand-dependent pre-equilibration populates a conformationally preorganized intermediate that is selectively captured by NZF in a slower, chain-type-selective step. This kinetic hierarchy offers a mechanistic basis for understanding the discrimination between linear and Lys63-linked ubiquitin chains that static structures alone cannot reveal. This strategy should be broadly applicable to multidomain recognition systems─including epigenetic reader complexes and multivalent signaling adaptors─where the pathway between known structural end points remains hidden.

The prediction of Aedes mosquito abundance using remote sensing and machine learning in Harris County, Texas

Magnetohydrodynamic Williamson fluid flow in ureteral tubes with heat and mass transfer in electromagnetic therapy: numerical and artificial neural network analysis

Arraying Shape-Persistent Molecular Alkynyl Trap into Highly Porous and Robust Zirconium Metal–Organic Framework for Propyne Capture and Propyne/Propylene Separation

Abstract Adsorptive separation of propyne/propylene (C3H4/C3H6) using porous adsorbents offers a promising route toward energy-efficient production of polymer-grade C3H6. Currently, the prevailing adsorbents are ultramicroporous metal–organic frameworks (MOFs) that feature narrow channels and/or consist of inorganic anion pillars, which often lead to limited C3H4 uptake capacity and high isosteric enthalpy of adsorption. We report herein a highly porous and robust zirconium metal–organic framework, termed SJTU-520. This MOF incorporates shape-persistent molecular arrays in three-dimensional space derived from cyclotetrabenzoin, which function as selective sites for the preferential entrapment of C3H4 over C3H6, thus enabling high C3H4 capture capacity, record high C3H4/C3H6 uptake ratio at 1 bar and 298 K, and efficient C3H4/C3H6 separation at ambient conditions. Compared with the cyclotetrabenzoin and tetraacetate cyclotetrabenzoin-based supramolecular organic crystals, SJTU-520 exhibits significantly higher surface area (3650 m2/g versus 42 and 570 m2/g), leading to a C3H4 uptake boost by 6.1-fold and 3.7-fold at 298 K and 1 bar, without any compromise of the C3H4/C3H6 selectivity. The efficient C3H4/C3H6 separation was validated by extensive breakthrough experiments under various conditions with great recyclability and high productivity of polymer-grade C3H6 from a 10/90 C3H4/C3H6 mixture. Computational simulations revealed that the four benzene walls of the cyclotetrabenzoin macrocycle in SJTU-520 formed equidistant π–π interactions with the C≡C triple bond of encapsulated C3H4 molecule. This work illustrates a general and powerful strategy─the reticulation of intrinsically functional organic scaffolds into highly porous frameworks─toward creating bespoke materials with precisely tailored functionalities and enhanced properties.

Engineered nitrogen enriched magnetic biochar for enhanced adsorption of rhodamine 6G: a comparative study

Dedioxygenative Phosphonylation of Carboxylic Acids

Abstract Dedioxygenative transformations of carboxylic acids are faced with the significant challenges in efficiently breaking multiple C–O bonds and achieving broad applicability across diverse carboxylic acids, thereby hampering the development and application of this field. In this work, through the cooperation of multiple catalysts, we realized a dedioxygenative phosphonylation of carboxylic acids that is applicable to both aliphatic and aromatic substrates, showing good scope and functional-group tolerance. This protocol also demonstrates promising performance in the late-stage modification of complex molecules. Meanwhile, it establishes a formal deoxygenative coupling approach that enables rapid access to alkenes from carboxylic acids and aldehydes or alcohols. Mechanistic studies reveal distinct activation modes for different C–O bonds and further highlight a carbon-retentive transformation pattern of carboxylic acids, complementing conventional carbon-deletion decarboxylative phosphonylation based on redox-active esters or other strategies.

Unstable trunk core strength training improves shooting performance and holding stability in elite 10 m air pistol athletes: a pilot randomized controlled trial

Origins of Reactivity in SAM-Utilizing Ribozyme SAMURI-Catalyzed RNA Alkylation

Abstract Unlocking the design principles of programmable RNA catalysts capable of site-specific chemical modification is critical for expanding the functional and therapeutic potential of RNA. The SAM analogue-utilizing ribozyme (SAMURI) enables site-specific RNA alkylation using either S-adenosylmethionine (SAM) or the synthetic cofactor propargylic Se-2,6-diaminopurinribosyl-selenomethionineamide (ProSeDMA), yet the molecular determinants of its reactivity remain incompletely understood. Here, we combined molecular dynamics, 3D-RISM solvation analysis, alchemical free energy calculations, quantum pKa shift predictions, and ab initio QM/MM free energy simulations to characterize the conformational and electronic factors that govern catalysis. Simulations show that, although the global fold of SAMURI remains stable in solution, the formation of catalytically competent near-attack configurations is rare, indicating that the observed rate depends on access to a minor fraction of these reactive conformations (freact). A putative Mg2+ binding site between the SAM carboxylate and the G30 phosphate, together with a hydrogen bond between the cofactor α-amine and U8:O2, enriches freact. QM/MM simulations support an SN2-like alkyl transfer mechanism and show that ProSeDMA reacts more readily than SAM primarily due to its more favorable electronic leaving group properties that enhance the intrinsic rate (kint). Atomic substitutions at A52 that tune the N3 pKa enhance nucleophilicity, further lower the activation barrier, and increase kint. Together, these results show that SAMURI catalysis is governed by a combination of conformational preorganization and electronic effects, providing a framework to guide the design of new programmable RNA alkyltransferases.

Development and validation of the comprehensive mentalizing questionnaire

High-Pressure Investigation of the I–N System: Discovery of the Nitric Ozonide [N3]3– (“Ozonitride”) Species and Multicenter Bonding in Iodine Frameworks

Abstract Despite binary nitrides being heavily investigated at high pressures in the past decade, nitrogen halides are still a terra incognita at pressures exceeding 1 bar. Due to the unique chemistry of halogens, they are fertile grounds for the discovery of novel nitrogen species. Here, we report the high-pressure investigation of the I–N system up to 120 GPa using laser-heated diamond anvil cells and the synthesis of the first two thermodynamically stable binary iodine–nitrogen compounds, I4(N2)3 and I2(N2)(N3), formed from 81 and 95 GPa, respectively. Their crystal structures were solved and refined through synchrotron single-crystal X-ray diffraction measurements. I4(N2)3 is comprised of a layered polymeric iodine framework of hexagonal iodine units and infinite linear iodine chains─both evidenced to feature multicenter bonding─along with N2 dimers. In contrast, I2(N2)(N3) exhibits corrugated and distorted I6 layers along with N2 dimers as well as a hitherto unknown nitrogen species, [N3]3–. This anion is both isosteric and isoelectronic with ozone (O3), leading to its designation as a nitric ozonide (or “ozonitride” for simplicity). The stability domain of each compound is investigated, and their bulk modulus determined. Accompanying density functional theory calculations provide further insight into the crystal chemistry, stability regime, and physical properties of the two iodine–nitrogen compounds.

A loser-augmented duelist algorithm for cloud data center energy consumption minimization

Supramolecular Predisposition Promotes Intramolecular Heavy-Atom Effects for Self-Sensitized Oxidation

Abstract Supramolecular confinement is widely used to control molecular architecture, but its use to direct excited-state reaction pathways remains underexplored. This limitation is particularly evident for spin-forbidden processes such as intersystem crossing (ISC), which are difficult to regulate through supramolecular design. The heavy-atom effect, although central to promoting ISC, is typically regarded as an intrinsic substituent property rather than a geometry-dependent supramolecular parameter. Here we show that macrocycle-directed supramolecular predisposition can deliberately enforce intramolecular heavy-atom effects to activate latent spin-forbidden transitions, enabling efficient self-sensitized oxidation. Encapsulation of a flexible aldehyde- and bromine-substituted guest within cucurbit[8]uril (CB[8]) enforces a folded geometry that juxtaposes the heavy atom and reactive aldehyde, as established by solution studies and single-crystal analysis. Under white-light irradiation, this predisposed complex undergoes selective oxidation of the aldehyde to the corresponding carboxylic acid. Control experiments varying heavy-atom identity, cavity size, and guest binding modes define CB[8]-enforced spatial juxtaposition as the critical structural requirement, while scavenger and EPR studies support triplet-oxygen energy transfer to generate singlet oxygen as the operative pathway. Preferential binding of CB[8] to the substrate over the product mitigates product inhibition and allows catalytic turnover under substoichiometric host loadings. These results show that macrocyclic encapsulation does more than statically stabilize a host−guest complex: it transforms spatial geometry into a structurally gated switch for spin-forbidden pathways, establishing supramolecular predisposition as a versatile design principle for developing switchable photocatalysts and conformationally responsive smart materials.