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Monitoring the Microwave Synthesis of <i>d</i> <sup>0</sup> ‐Free Disordered Rocksalt Cathodes Using In Situ Infrared Pyrometry
ABSTRACT A detailed understanding of solid‐state reaction pathways is essential for connecting predictive frameworks, such as density functional theory and machine learning, with experimental synthesis. Microwave synthesis has emerged as a powerful route for preparing inorganic materials, yet the mechanisms governing microwave‐driven processes remain poorly understood, particularly for metastable compounds whose formation is highly sensitive to synthesis conditions. Disordered rocksalt oxides (DRX) are high‐temperature metastable phases of interest as next‐generation Li‐ion cathodes. Here, we investigate the microwave reaction pathway of . Combining ex situ phase identification using x‐ray diffraction and solid‐state NMR with in situ infrared thermography, we show that the reaction proceeds through a reentrant order–disorder–order transformation. Layered Li‐Mn‐O intermediates disorder above 945 to form the DRX phase, while continued heating drives reordering back to layered structures. Infrared profiles reveal a distinct feature marking completion of the disordering transition, enabling precise reaction termination to maximize DRX phase purity. We further examine the impact of phase purity on the “‐phase” transition during electrochemical cycling and find that residual layered phases minimally affect performance. These findings indicate that is only stable near 945, yet its electrochemical performance tolerates synthesis‐induced impurities.
Development and evaluation of a hybrid clinical and deep-learning ECG model for predicting in-hospital cardiac arrest
Light‐Defined Reaction Fields via Topochemical Control for Single‐Shot Projection Photoprinting
ABSTRACT A central challenge in three‐dimensional (3D) photoprinting lies in the absence of a deterministic translation from optical fields into volumetric chemical reaction fields. Here, we establish a photoprinting strategy in which light acts not merely as a trigger, but as a programmable input that defines a spatial chemical reaction field enabled by molecular spatial homogeneity and topochemical control. Within this light‐defined reaction field, topochemical reactions are spatially confined and propagated along the depth direction, generating continuous reaction gradients that deterministically translate optical projections into 3D chemical transformations. We realize this concept using a large‐area ADCA‐based single‐cocrystalline photoresist film, in which well‐defined molecular packing supports efficient cascade reactions. The resulting light‐defined spatial reaction field enables low‐power (µW), millimeter‐scale projection photoprinting, producing 3D nanostructures with a sub‐diffraction‐limited lateral resolution of 153 nm and an axial resolution of 3.5 nm. By integrating a home‐built projection system with computational modeling, arbitrary graphic inputs can be directly compiled into programmable 3D chemical reaction fields and rapidly translated into nanoarchitectures within seconds. These results establish topochemical reaction‐field‐guided projection photoprinting as a powerful strategy for rapid, high‐resolution three‐dimensional fabrication in ADCA‐based single‐cocrystalline photoresists and suggest a broader molecular‐design principle for future co‐crystalline photoprinting materials.
A resource efficient IoT intrusion detection model using hybrid feature selection for edge computing
Synthesis of Chiral Bowl‐Shaped <i>N</i> ‐Heterocycles via Pd‐Catalyzed Enantioselective Intramolecular C–H Arylation
ABSTRACT Chirality arising from curved molecular frameworks represents a unique stereochemical motif with growing importance in materials science and supramolecular chemistry, yet its catalytic asymmetric construction remains highly challenging. Herein, we report a palladium‐catalyzed enantioselective intramolecular C–H arylation strategy for the synthesis of bowl‐shaped tribenzo[ b , d , f ]azepines possessing framework‐defined chirality. Enabled by a P‐chiral monophosphine ligand, this transformation proceeds with high efficiency, delivering a diverse array of bowl‐shaped N ‐heterocycles in excellent yields and enantioselectivities (up to 95% yield, 97% ee). The method accommodates a broad range of substrates and provides direct access to previously inaccessible bowl‐shaped chiral frameworks. Mechanistic studies suggest that C–H activation is turnover‐limiting and that stereocontrol originates from a monoligated palladium species. DFT studies were performed to elucidate the detailed reaction mechanism and the origins of enantioselectivity. This work establishes a general catalytic platform for constructing bowl‐shaped chiral medium‐sized rings and expands the synthetic toolbox for chiral π‐functional molecules.
Thickness-driven optimization of tungsten first walls for tritium breeding with 14.1 MeV fusion neutron irradiation
Room‐Temperature Depolymerization of Waste Polycarbonate and Polyester Enabled by an Electrochemically Generated Local Alkaline Microenvironment
ABSTRACT Driven by massive production and inadequate end‐of‐life management, polycarbonate and polyester plastic pollution has become one of the most critical environmental crises. To address this mounting challenge, decades of research have yielded a variety of polycarbonate and polyester recycling technologies. Nevertheless, the majority of existing methods either afford low‐quality, low‐value products or depend on harsh conditions such as high temperature, high pressure, and corrosive bases or acids, severely restricting their scalability and economic feasibility for industrial‐scale implementation. Herein, we present an efficient electrochemical approach for the room‐temperature depolymerization of polycarbonate and polyester into value‐added monomers and derivatives, enabled by a cathodically in situ generated alkaline interfacial microenvironment at neutral bulk pH. This approach shows broad substrate compatibility with commercial‐grade and contaminated waste polycarbonate, polyester, and their blends, affording corresponding products in up to 99% yields, with its industrial potential demonstrated by a kilogram‐scale depolymerization reaction. Significantly, it realizes the direct recovery of high‐performance long carbon fibers from reinforced composites without fiber‐damaging pulverization, creating a viable upcycling route. Mechanistic studies confirm that water electroreduction generates surface hydroxyl species that act as proton shuttles, driving methanol deprotonation to form depolymerization‐active species and establishing the indispensable alkaline microenvironment.
Comparison of propofol/fentanyl and midazolam/fentanyl for pediatric procedural sedation in the emergency department: a randomized clinical trial
Molecular Segments Reorganization Strategy Coupled With Retrosynthetic Analysis for Designing Sustainable Alternatives to Alkylphenol Ethoxylates
ABSTRACT Alkylphenol ethoxylates is an important fine chemical that has been used in industrial cleaning, textile manufacture, and emulsion polymerization. However, their petrochemical origin and adverse health effects, particularly xeno‐oestrogenic activity, pose a challenge for sustainability and have been almost banned globally. Herein, we report a novel bio‐based cyclohexyl fatty alcohol ethoxylates (CyCC n E 9 ) by applying molecular segments reorganization strategy and retrosynthetic analysis method. By constructing acid‐base bifunctional Zn‐based single‐atom catalyst, we achieved efficient synthesis of CyCC n E 9 . These bio‐based CyCC n E 9 displayed outstanding defoaming ability, super‐wettability, and better emulsification ability. More excitingly, the primary degradation products of CyCC n E 9 demonstrated markedly reduced toxicity toward zebrafish embryos and larvae, suggesting superior biocompatibility. The CyCC n E 9 showed excellent low‐temperature cleaning performance toward stains of various metallic surfaces. This work paves new ways to create sustainable alternative of alkylphenol ethoxylates using renewable biomass resources, as well as provide inspiring insights for the transformative revolution of other petroleum‐based restricted products.
Residential-area nighttime light exposure and biological aging patterns in the UK Biobank
Ambiphilic Ligand Stabilization of Aluminum(I) Fragments: Halides, Cations, and a Hydride
ABSTRACT Z‐type ligands have been highly successful in stabilizing transition‐metal fragments in unique coordination geometries and in enabling novel reactivities. However, examples of the use of these ligands in stabilizing elusive main‐group metal fragments are scarce. In this study, we present the stabilization of aluminum (I) halides by an ambiphilic tris(phosphine)borane ligand. Unlocking unprecedented coordination chemistry at aluminum, the unique electronic structure of the novel compounds is analyzed in detail experimentally and computationally. Successful post‐functionalization via coordination of Lewis bases to the Al atom enables isolation of elusive Al cations with the metal in a low redox state. In addition, the Al(I)Br transfer onto 2,2′‐bipyridine ligands is presented.
Metabolic response to oncolytic myxoma virus construct in ovarian cancer cell lines as revealed by NMR spectroscopy studies
Abstract Oncolytic viruses have emerged as novel promising therapeutic agents for some hard-to-cure cancers. In the present study, we examined different types of ovarian cancer cell lines to determine the permissiveness of myxoma virus constructs and assessed the metabolic changes associated with viral infection. The Kuramochi, OAW42, and OVP10 cell lines were found to be permissive for the viral constructs, while the OVPA8 line was resistant to this treatment. Nuclear magnetic resonance (NMR) spectra of the cellular extracts and intact cells were acquired using a Bruker Avance III 400 MHz spectrometer. The decreased phosphocholine and succinate, as well as the increased glutamine and uridine nucleotides/uridine diphosphate nucleotide sugars are the common metabolic abnormalities detected in the NMR spectra of aqueous extracts obtained from all virus-sensitive cell lines tested 24 h after infection. The decrease in phosphocholine, increased phosphatidylcholine, and uridine nucleotides/uridine diphosphate nucleotide sugars were also evident in the NMR spectra of intact cells. There was no association between infection and increased lactate levels. Such metabolic changes were not observed for non-permissive OVPA8 cells. We conclude that changes in the metabolome could find use in attempts at ovarian cancer therapy based on these oncolytics, as well as in testing combined approaches exploring such changes.
Defect‐Rich CoNi Prussian Blue Analogues Enable Highly Selective Electrochemical Hydrogen Peroxide Production
ABSTRACT Decentralized electrosynthesis of hydrogen peroxide (H 2 O 2 ) via the two‐electron oxygen reduction reaction (2e − ORR) offers a promising alternative to the traditional anthraquinone process, though developing non‐precious metal electrocatalysts with high activity, selectivity, and industrial durability remains challenging. Herein, we report a defect‐engineering strategy to synthesize CoNi Prussian blue analogues (PBAs) with precisely tunable [Co(CN) 6 ] 3− vacancy concentrations via kinetic trapping. Advanced synchrotron X‐ray diffraction and absorption spectroscopy (EXAFS) reveal that these vacancies transform the local coordination of adjacent nickel atoms from saturated octahedral geometries to unsaturated square‐planar Ni–N 4 motifs. This structural modulation triggers a fundamental shift in the ORR pathway, delivering an H 2 O 2 selectivity exceeding 97% and a remarkable production rate of 6.2 in a flow‐cell device. Crucially, our defect‐rich catalyst demonstrates exceptional durability under a rigorous 120‐h variable‐current stability test. Density functional theory (DFT) calculations identify the coordinatively unsaturated Ni–N 4 sites as the intrinsic active centers, which optimize the binding energy of the *OOH intermediate and suppress the four‐electron ORR pathway. This work identifies a robust H 2 O 2 synthesis electrocatalyst and establishes a validated protocol for defect engineering in coordination frameworks.
Characterization of acute kidney injury induced by a cecum ligation and puncture model
Open‐Shell Guest Acceptors Manipulate Charge‐Transfer Spin Dynamics in Organic Solar Cells
ABSTRACT Non‐radiative energy loss in high‐efficiency organic solar cells (OSCs) is closely associated with triplet‐mediated recombination involving triplet charge‐transfer ( 3 CT) states. Here, rather than suppressing this pathway solely through excited‐state energetic engineering, we explore a spin‐manipulation strategy using intrinsically open‐shell non‐fullerene acceptors (NFAs) as spin‐active guest acceptors in OSC blends. Two (thio)barbituric acid‐terminated open‐shell NFAs, MAZ‐1 and MAZ‐2, were incorporated into D18:N3 solar cells. Electron spin resonance (ESR), variable‐temperature ESR, and variable‐temperature 1 H NMR measurements confirm their open‐shell character and thermally accessible triplet states. Upon MAZ incorporation, the ternary devices exhibit weakened high‐field magneto‐photocurrent responses and accelerated decay of long‐lived CT states, consistent with modulated CT‐state spin evolution and suppressed triplet‐related recombination. Consequently, the non‐radiative energy loss is reduced by up to ∼20 meV, accompanied by enhanced charge transport, improved morphology, and a power conversion efficiency increase from 18.52% to 20.23%. This work establishes open‐shell guest acceptors as an intrinsic spin‐active platform for manipulating CT‐state spin dynamics and reducing non‐radiative recombination losses in OSCs.
Experimental infection of acute bee paralysis virus induces differential responses of selected honey bee immune genes, independent of varroa resistance
Abstract Honeybees ( Apis mellifera ) have a complex immune system, with both innate and social immunity. The mite-resistant honeybee population from Gotland, Sweden, is well-known for their independent resistance to Varroa destructor mites and tolerance to virus infections, particularly deformed wing virus and acute bee paralysis virus (ABPV). However, the immune mechanisms underlying their virus tolerance remains unclear. Adult bees from this mite-resistant (MR) and a mite-susceptible (MS) control population were orally inoculated with either ABPV or a mock inoculum, in a laboratory time-course experiment. Two representative genes from five major immune signalling pathways, previously shown to respond to viral infections, were quantified using RT-qPCR. The genes exhibited distinct responses to ABPV inoculation, with some genes showing clear treatment-related differential expression between 24 and 48 h post-inoculation while other genes remained unaffected. However, there was no difference in the expression patterns between MR and MS populations. These findings suggest that the enhanced virus tolerance of the Gotland mite-resistant population is not due to differential regulation of the immune genes examined here. They also highlight the dynamic nature of immune gene expression, refine hypotheses for further studies of honeybee virus tolerance and motivate more comprehensive molecular analyses of a selection of these samples.
Deciphering Kinetic Principles of Dual‐Anion Electrolytes for Extreme Fast‐Charging Lithium‐Ion Batteries
ABSTRACT Tailoring Li + solvation coordination has been recognized as a strategy to enhance the electrochemical performance of lithium‐ion batteries (LIBs) under extreme fast‐charging (XFC) conditions. Beyond weakening Li + solvation, increased Li–anion pairing plays a crucial role in the formation of anion‐derived, inorganic‐rich electrode–electrolyte interfaces (EEIs). In this study, we propose an anion‐screening guideline leveraging transport in bulk electrolyte, desolvation energy and interfacial kinetics. We investigated mechanisms governed by dual‐anion electrolytes in both carbonate‐ and ester‐based solvents, aiming to address key challenges such as interfacial instability, lithium plating, and structural degradation. Integrated computational and experimental studies reveal that optimized dual‐anion systems create partially ion‐paired solvation structures and robust anion‐derived EEI on both electrodes, enabling principal merits of improved kinetics under XFC conditions. In LiNi 0.6 Mn 0.2 Co 0.2 || graphite pouch cells, the optimized dual‐anion formulation, PF 6 − /TFSI − , in dimethyl carbonate‐based electrolyte retains over 85% of its original capacity and 94% retention after 500 cycles at 4C, while the ester‐based variant in methyl propionate achieves 94%/83% retention after 500/1000 cycles at 4C. These improvements are attributed to reduced charge‐transfer impedance with enriched inorganic fluorides and sulfates interface. Overall, this work provides a framework for anion regulations and offers a promising pathway to realizing fast‐charging, high‐energy‐density LIBs.
First insights into the insecticidal mechanism of natural zeolite against Sitophilus granarius: effects on the antioxidant defence system and glyoxalase pathway
Asymmetric Conjugated Molecule Co‐Deposition for High‐Performance HTL‐Free Carbon‐Based Perovskite Solar Cells
ABSTRACT Planar hole‐transport‐layer (HTL)‐free carbon‐based perovskite solar cells (C‐PSCs) show great promise due to their chemical stability and cost‐effectiveness. However, the power conversion efficiency (PCE) of HTL‐free C‐PSCs remains limited by severe interfacial nonradiative recombination and inefficient charge extraction. Herein, we designed an asymmetric D−A−D'−A' conjugated molecule 2BCz‐BD and employed a co‐deposition strategy by incorporating 2BCz‐BD into the perovskite precursor solution during film fabrication. The coordination ability of 2BCz‐BD regulates perovskite crystallization and passivates surface defects, thereby suppressing interfacial non‐radiative recombination. The favored p ‐type semiconducting characters also optimize energy‐level alignment to enhance charge extraction. Additionally, the large dipole moment of 2BCz‐BD induces an ordered orientation on the perovskite surface, serving as a template for controlled carbon electrode deposition and enabling high‐quality electrode fabrication. As a result, small‐area (0.062 cm 2 ) and large‐area (1.004 cm 2 ) devices achieved remarkable PCEs of 23.24% and 22.09%, respectively. The unencapsulated devices retained over 90.4% of their initial PCE after 3100 h of operation.