Employing the Richards-Wolf formalism that adequately describes an electromagnetic field near the sharp focus of an ideal spherical lens, we demonstrate that certain light fields (linearly polarized optical vortex, cylindrical vector fields of an arbitrary order) have a reverse canonical energy flow in the focus plane. When the numerical aperture is 0.95, maximal magnitude of the reverse energy flow amounts to nearly 0.7% of the maximal magnitude of the direct energy flow. The distribution of the reverse canonical flow in the focus plane can have the shape of concentric rings or only arcs of the concentric rings. For certain light fields, for instance, for an azimuthally polarized light field, the longitudinal component of the canonical energy flow vector coincides with the longitudinal component of the Poynting vector. It is shown that a circularly polarized optical vortex does not have the reverse flow at the focus.
Extreme heat is a significant and growing health hazard in urban locations around the world, particularly in the Southeastern United States (U.S.). While most extreme heat research and interventions are focused on ambient outdoor conditions and the neighborhood environment, the indoor residential environment is where the most severe heat-health consequences occur. The aim of this study was to characterize the indoor thermal environments and identify predictors of high indoor temperatures for residents of heat-vulnerable neighborhoods within New Orleans, Louisiana, within the context of current heat adaptation measures and issues of energy insecurity. We conducted surveys with both open- and closed-ended questions and measured indoor temperature over 2-week sampling periods in 114 households across two heat vulnerable New Orleans wards during the warm seasons of 2023 and 2024. Our study found that a combination of AC type and use, along with outdoor daily maximum temperature, were significant predictors of indoor maximum overnight temperature. Our results indicate that households without AC, using window AC units, or those not running central AC all or most of the time struggled to maintain 80 degrees Fahrenheit overnight (a threshold deemed appropriate by a recent healthy homes ordinance) once outdoor daily maximum temperatures exceeded 90 degrees Fahrenheit. Homeownership, compared to renting, was associated with higher overnight indoor temperatures, greater variability in typical AC use patterns, and greater sensitivity of summer monthly energy expenditures to differences in AC use patterns, potentially indicating that this group is practicing energy limiting behavior. This paper contributes to limited literature on indoor thermal environments, particularly in the Southeastern U.S., and underscores the importance of housing and energy burden in heat adaptation.
We developed a high-energy pulsed laser at 1572 nm based on an all-fiber master oscillator power amplifier (MOPA) for coherent lidar detection of carbon dioxide profiles. By applying two acoustic-optic modulators (AOMs), the signal-to-noise ratio of the output signal is greater than 50 dB. Near-Gaussian pulses are realized by modulating the first AOM with a specifically designed asymmetric triangular wave. The optical-to-optical conversion efficiency of the main amplifier is improved to 7.2% with water cooling and is nearly doubled compared to that under air cooling conditions. The efficiency reaches a high level in 1572 nm amplification with erbium-ytterbium co-doped fibers pumped by 976 nm laser diodes. The system delivers 140 µJ pulses at a 10 kHz repetition rate with a 400 ns pulse width and a peak power of 350 W. The output pulse exhibits a 2 MHz linewidth and stable energy with a root-mean-square (RMS) energy deviation of only 2.2% in 90 min. The laser generates pulses with beam quality factors (M2) of 1.63 in the x direction and 1.68 in the y direction. The overall performance of the laser system meets the requirements for high-precision carbon dioxide coherent lidar detection.
Taurine (TAU) is a conditionally essential amino acid whose consumption has recently increased, particularly among young people, through supplements and energy drinks. It has potential beneficial effects on physical performance; however, scientific evidence remains limited. To evaluate the effects of acute ingestion of 1 g of TAU on metabolic and aerobic capacity in physically active young adults. This experimental, randomized, triple-blind, cross-over study included 16 volunteers (11 women and 5 men). Data were collected during a progressive cardiopulmonary exercise test (CPET) at the Ergoespirometry Laboratory of the Department of Physical Education, Federal University of Pernambuco (DEF-UFPE). After familiarization with the test, participants completed two CPETs, 1 hour after ingesting either TAU or placebo (PLA) capsules, with a 7-day washout period between sessions. A significance level of 5% (p < .05) was adopted for all analyses. No significant differences were observed between the TAU and PLA conditions in the main aerobic capacity variables, including peak oxygen consumption (p = .160), time to exhaustion (p = .361), and respiratory compensation point (p = .166), and in lipid metabolism variables (duration-p = .559 and peak-p = 1.000) and glycolytic metabolism (duration-p = .904 and peak-p = .383). Acute intake of 1 g of TAU did not significantly alter aerobic capacity and energy metabolism in physically active young adults. Future research should consider other dosages and types of activities, different levels of physical fitness, and exercise durations.
Computational ghost imaging (CGI) for edge detection, particularly speckle-shifting ghost imaging (SSGI), faces a severe trade-off between sampling cost and edge quality. We propose energy-descending ordered compressed ghost edge imaging (EDO-CGEI), an adaptive edge detection method that reorders binary illumination patterns in descending order of energy. Simulations and experiments show that EDO-CGEI outperforms existing schemes at low sampling rates, achieving a satisfactory 256×256 edge image with a sampling rate of only 15%. This approach effectively pushes forward the trade-off between efficiency and clarity in ghost imaging edge detection under resource constraints.
Accurately predicting micropollutant degradation kinetics during water purification via heterogeneous photocatalysis remains a major challenge. Here, the highest occupied molecular orbital energy (EHOMO) of typical micropollutant is established as the dominant descriptor in the TpBpy-COF system governing photocatalytic oxidation rates, using a versatile and robust TpBpy-COF (β-ketoenamine covalent organic frameworks) platform that achieves efficient phenol removal (100% within 15 min, 85.4% mineralization) with excellent environmental adaptability. Employing this model system and 15 structurally diverse pollutants (10 phenolic and 5 nonphenolic compounds), it is demonstrated that while the catalyst generates identical reactive species (•O2- and h+), their utilization efficiency is dictated exclusively by EHOMO via a dual-pathway mechanism: surface-confined hole oxidation governed by micropollutant adsorption affinity, and electron donation to superoxide radical that triggers cascade hydroxyl radical generation. Integration of 12 descriptors and machine learning-derived quantitative structure-activity relationships (QSAR) model, reveals that EHOMO and ionization potential (IP) are highly correlated with the degradation rate constant (R2 > 0.86). Further, the Extremely Randomized Trees (ET) algorithm performs best and SHapley Additive exPlanations (SHAP) analysis identify EHOMO as the overwhelmingly dominant predictive feature. This work establishes a predictive framework linking micropollutant electronic structure to degradation kinetics, shifting the paradigm from a catalyst-centric to a catalyst-pollutant electronic coupling view.
The breathing vibrational modes of WSe2 nanoflakes deposited onto a glass surface have been studied by transient absorption microscopy. A wide range of both vibrational frequencies and quality factors are observed in the measurements. The differences in the frequencies simply arise from differences in the thickness of the WSe2 nanoflakes. However, the variation in quality factor has a more complicated origin. The measured quality factors range from less than 10 to over 200, with the lower value being close to that expected for WSe2 nanoflakes deposited directly on glass. The higher values are attributed to the presence of an organic spacer layer between the WSe2 nanoflakes and the glass that reduces mechanical contact and, thus, decreases the transfer efficiency of acoustic energy from the nanoflakes to the substrate. A simple one-dimensional continuum mechanics calculation is used to model the results. These calculations show that the data can be explained by the presence of a spacer layer with thicknesses between a few and tens of nanometers.
Nanoparticles (NPs) are alternative chemiluminescence (CL) luminophores to molecular luminophores and are strongly anticipated to extend molecular luminophore-tagged commercial CL immunoassays (CLIA) with wavebands beyond the eye-visible region and sensitivity beyond the pg/mL level. Herein, a surficial bond-involved repetitive excitation strategy for near-infrared CL with enhanced photons per luminophore is proposed by exploiting l-methionine (l-Met)-capped gold NPs (AuNPs) as luminophores. The surficial Au-S bonds of l-Met@AuNPs can be involved in the procedure of NP core excitation via oxidation, and bring out defect-involved CL around 830 nm. Because there are plenty of Au-S bonds on every AuNP core, l-Met@AuNPs can be repetitively excited over a hundred times and give off greatly enhanced CL photons per luminophore than all molecular CL luminophores. CL of l-Met@AuNPs/(NH4)2S2O8 can directly enable automatic near-infrared CLIA for myoglobin (MYO) determination on in vitro diagnostic instruments, with a limit of detection of 10 fg/mL (S/N = 3), which significantly surpasses the threshold of molecular luminophores. This Au-S bond-triggered AuNP CL strategy not only offers an alternative to molecular CL strategies with improved sensitivity and to II-VI NP CL strategies with fewer toxic concerns, but also indicates that exploiting the surficial bond energy of NPs could be an alternative to designing NPs with unique morphology, structure, and composition in the CL domain.
A synergistic strategy by merging N,S-difunctionalization of alkenes with CN migration was successfully accomplished by virtue of the newly designed bifunctional reagent bearing the SCN functionality. This protocol exhibits a broad substrate scope for alkenes with tunable alkyl chains, and the corresponding cyanoalkyl β-aminosulfide derivatives were successfully obtained in moderate to high yields. The facile 1,4- and 1,5-CN relocations via intramolecular radical rearrangement allow simultaneous access to remote functionalization and difunctionalization of alkenes with controllable reactivities. Under simple, mild, and easily achievable conditions, this protocol unlocks new synthetic routes to densely functionalized molecules with a high degree of structural diversity.
Model-based analysis of fuel pathways is essential for informing energy and environmental policies. Two major model types are typically used: multisector dynamics models, which capture the broader energy economy, such as GCAM (Global Change Analysis Model), and life-cycle assessment models, such as GREET (Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation). Each has distinct strengths and limitations, and recent studies have increasingly adopted hybrid approaches to harness the advantages of both. However, such integration is often time-consuming and complicated by inconsistencies in the system boundaries and technology definitions. We present LC-GCAM, a new tool that enables estimation of life-cycle greenhouse gas emissions and primary energy use for any fuel pathway represented in GCAM. We apply LC-GCAM to 300 scenarios designed to explore key uncertainties affecting the life-cycle performance of future fuel options in the U.S. freight sector. To evaluate LC-GCAM, we compared its results with those from GREET for nine fuel types in a 2030 reference scenario. When input assumptions are modestly aligned, LC-GCAM and GREET estimates typically agree within 13% (aggregate absolute-sum error), although discrepancies can be larger for pathways involving large amounts of land use change emissions. LC-GCAM offers a flexible and efficient approach to generating life-cycle metrics within an integrated modeling framework, supporting robust policy analysis across a wide range of interacting energy system uncertainties.
We present a new instrument for soft x-ray absorption and emission spectroscopy based on the latest generation of transition edge sensor array optimized for soft x-ray detection, built on microwave superconducting quantum interference device multiplexing readout, and cooled with a dilution refrigerator. Its extreme collecting efficiency enables spectroscopy measurements on dilute systems. It also enables shorter acquisition time and large energy-range spectra. We describe the design and operation of the spectrometer and characterize its performance in terms of energy resolution, photon collecting efficiency, and stability. A resolution of 0.7-1.8 eV in the energy range 260-900 eV with a high detection rate of up to 10 000 photons per second across the array is achieved with minimal performance degradation. In addition, the use of the dilution refrigerator to cool the detector results in a robust and stable energy calibration over time. The spectrometer is attached to a dedicated ultra-high vacuum sample chamber equipped with a fully motorized sample cryostat for experiments at temperatures between 10 and 300 K, multi-sample mounting, and electric field-gated devices. The spectrometer-sample chamber is installed at a beamline providing full polarization control. We demonstrate the capabilities of the setup using two representative examples of XES on extremely low-concentration systems, namely monolayer hexagonal boron nitride and the K3[Fe(CN)6] molecular system at sub-millimolar concentration.
Colistin remains a last-line antibiotic against multidrug-resistant Gram-negative pathogens, but its clinical utility is limited by nephrotoxicity and emerging resistance. This study identifies macelignan, a natural lignan from nutmeg, as a potent synergist that enhances colistin activity against Escherichia coli (E. coli) through a novel metabolic disruption mechanism. In vitro, macelignan reduced the colistin minimum inhibitory concentration (MIC) by approximately 100-fold, with the combination (8 µg/mL macelignan + 0.008 µg/mL colistin) achieving complete bacterial eradication within 4 h. In vivo, combination therapy significantly reduced bacterial burden in a mouse thigh infection model (P < 0.05). Mechanistic studies revealed that macelignan disrupts bacterial energy metabolism by inhibiting the citric acid cycle, leading to ATP depletion. This energy compromise impairs the bacterial capacity to repair colistin-induced membrane damage, exacerbating membrane disruption and accelerating bacterial death. These findings establish macelignan as a promising adjuvant for colistin-based therapy and elucidate a dual "internal and external pincer" mechanism that could inform future antibiotic combination strategies. The continued efficacy of colistin, a last-line antibiotic against multidrug-resistant Gram-negative pathogens, is increasingly threatened by dose-limiting nephrotoxicity and the global spread of resistance determinants. This study introduces macelignan-a naturally occurring lignan from nutmeg-as a highly effective colistin adjuvant that operates through a previously unrecognized mechanism centered on metabolic disruption. By targeting the bacterial citric acid cycle, macelignan depletes intracellular ATP, thereby crippling the energy-dependent machinery required for membrane repair following colistin-induced damage. This dual "internal and external pincer" strategy not only dramatically reduces the colistin concentration needed for bactericidal activity but also significantly lowers bacterial burden in vivo. These findings provide a mechanistic framework for developing metabolism-targeting adjuvants to revitalize last-resort antibiotics and expand the therapeutic arsenal against recalcitrant Gram-negative infections.
Focusing high-energy photons above 80 keV remains a significant challenge due to the absorption edges of conventional high-Z thin film materials such as W, Ir, Pt, and Au, which lead to substantial reflectance losses above this energy. In this work, we introduce a novel approach, to our knowledge, for fabrication of Ni-based thin film multilayers, deposited by DC magnetron sputtering, offering efficient reflection of photon energies beyond 80 keV. These coatings were characterized using XRR at 8.048 keV with a laboratory X-ray source and at synchrotron beamlines. Structural and morphological characterization of the layers was carried out by STEM and XPS. Furthermore, we produced depth-graded multilayers of Ni and W and successfully integrated them into hybrid structures, advancing a concept originally proposed for focusing light up to the sub-MeV range. These promising results have applications not only in astronomical telescope optics but also in synchrotron beamline instrumentation.
The pursuit of high-energy-density and intrinsically safe lithium-ion batteries (LIBs) has intensified interest in quasi-solid-state electrolytes (QSSEs) coupled with silicon (Si) anodes. However, most in situ-formed polymer electrolytes suffer from low ionic conductivity and limited Li+ transference numbers, primarily arising from high polymer crystallinity and sluggish segmental dynamics. Herein, a 1,3,5-trioxane (TXE)-derived QSSE is engineered by incorporating fluoroethylene carbonate (FEC) and methyl propionate (MP) as plasticizers, together with a lithiated covalent organic framework (COFLi) as a functional filler to suppress crystallization, enhance Li+ transport, and improve interfacial stability. Consequently, the optimized COFLi-modified TXE-based electrolyte enables the Si anode to deliver a high reversible capacity of 1814.6 mAh g-1 at 2 A g-1 after 200 cycles and to retain 1530 mAh g-1 at 0.5 A g-1 even at -20°C. Moreover, a molecular-level interfacial model is proposed to elucidate the role of COFLi in regulating the Li+ solvation structure, reducing desolvation energy, and promoting the formation of a LiF-rich inorganic solid-electrolyte interphase), thereby suppressing electrolyte decomposition and mitigating Si pulverization. This work provides fundamental insights into solvation chemistry and interfacial evolution in TXE-based QSSEs and offers a rational design strategy for high-performance, Si-compatible quasi-solid-state LIBs.
Ultramarathon performance reflects a complex interplay of physiological, biomechanical, and psychosocial factors, yet data from multi-day events remain limited, particularly in females. The demands and key determinants of performance in these events, including the longest ratified world-record event, the 6-day ultramarathon, are not well-characterized. This study aimed to provide a comprehensive, multi-disciplinary profile of the demands and performance determinants in an all-female 6-day ultramarathon. 10 heterogenous female athletes (27-48y, Tier 2-5, V̇O2 peak: 21.0-62.9 ml∙min-1·kg-1) ran a self-paced, certified 6-day ultramarathon. Data were collected over the preceding year, 2-4d pre-race, during the race, and post-race. We assessed V̇O2 peak with ventilatory thresholds and running economy; haemoglobin mass; body composition; total daily energy expenditure (TDEE, via doubly-labelled water) and dietary energy intake (EI); continuous heart rate, glucose, and core temperature; neuromuscular and cognitive fatigue; biomechanical parameters; in-race blood sampling to assess inflammatory markers; and psychosocial outcomes. All athletes achieved personal distance records over 6 days (463.6±199.6 km), with the top athlete covering 901.8 km, breaking the female world record. Exercise intensity was low (~46±6%V̇O2 peak), but demands were extreme: up to 20 h·day-1 racing with 82,699±17,192 steps·day-1, total sleep 5.2±1.9 h·day-1, 4188±1109 kcal·day-1 EI, and 6698±2071 kcal·day-1 TDEE; including three of the highest female TDEEs reported. Average active race pace was 8:41±2:27 min:sec·km-1 and the average decline in running velocity from the first 2 days to the last 2 days was 9±13.1%. There was no evidence of neuromuscular or cognitive fatigue 24 h post-race. The top athlete, who ran 258.2 km farther than the next finisher, had similar lab-tested physiology compared to the next four top finishers, but spent the most time on course with the highest TDEE, EI, running and total step count, and exhibited significantly greater neuromuscular fatigue, inflammatory markers, sleep deprivation, and pacing decline. The only clear difference between the top athlete and the next 4 athletes was years of running experience (29 vs. 9.7±7.4 years). The 6-day ultramarathon imposes an extreme physical and psychological challenge. Success may depend less on physical capacity and biomechanical efficiency than on the ability to persevere through fatigue.
Pulmonary arterial hypertension (PAH) is a complex disease characterized by chronically elevated pulmonary arterial pressure, with early onset and progression linked to structural, metabolic, and morphological changes in the pulmonary vasculature. Understanding the interplay between hemodynamics and arterial wall mechanics is essential to capture the pathology of the distal vasculature in PAH. This study aims to develop a data-driven framework that establishes a baseline state of PAH vasculature, incorporating key features of arterial wall constituents, geometry, and their interaction with PAH-specific hemodynamics. Illustrative examples of symmetrically bifurcating arterial trees are used to define representative baseline characteristics of PAH-affected pulmonary arteries. Compared with healthy homeostatic vasculature, the computational results demonstrate pronounced geometric and mechanical alterations: Arterial stiffness increases from approximately 7-10 kPa in healthy arteries to 300-800 kPa in PAH, representing a ~ 40-85 times increase across generations. Because wall thickening is imposed from histological measurements while outer diameter is preserved, the diameter-to-thickness ratio (D/h) decreases from ~ 14 in healthy arteries to ~ 3.8 in PAH, reflecting severe lumen narrowing and medial hypertrophy. In addition, the metabolic energy cost per unit length in PAH is more than double that of healthy arteries when assuming unchanged metabolic consumption per unit volume, whereas enforcing equal total energy cost yields a reduced per-volume metabolic consumption of ~ 450-500 W/m3. These findings suggest that maintaining constant metabolic consumption per unit volume would impose excessive energetic demand on the pulmonary vasculature in PAH, whereas redistribution of metabolic expenditure through altered wall composition may represent a more physiologically plausible adaptation. Furthermore, this framework provides a quantitative baseline state for PAH vasculature and lays the groundwork for future integration of growth-and-remodeling analyses and pharmacological pathway modeling to evaluate treatment response.
While pursuing high energy density in sodium-ion battery cathodes, ensuring intrinsic safety remains challenging. This study establishes a complete evidence chain linking "intrinsic chemical stability-metal dissolution-electrolyte catalytic decomposition-thermal safety" using NaNi1/3Fe1/3Mn1/3O2 (NFM), Na4Fe3(PO4)2(P2O7) (NFPP), and NaCrO2 (NCO) as models. We reveal that multivalent ions (Mn3+/Fe2+) in both NFM and NFPP trigger severe thermal runaway via a "dissolution-catalysis-runaway" cascade, despite their distinct structures. In contrast, NCO leverages the extreme chemical inertness of Cr3+ (unique d3 configuration and high Cr-O bond energy) to effectively sever this catalytic pathway, achieving counterintuitive high safety with minimal capacity sacrifice. This work elucidates that chemical inertness, rather than mere structural robustness, governs thermal safety, providing a new paradigm for designing intrinsically safe cathode materials.
Developing efficient electrocatalysts for nitrate reduction to ammonia is critical for both environmental remediation and energy conservation, yet it demands highly active and selective catalysts to overcome competing pathways and sluggish kinetics. Herein, we report a Fe single-atom-cluster coupled catalyst synthesized via a controlled pyrolysis strategy, which features atomically dispersed Fe-N4 sites coexisting with subnanometer Fe clusters embedded in a nitrogen-doped carbon matrix. This unique architecture significantly enhances the electrocatalytic NO3RR performance, achieving a high NH3 yield rate of 12.5 mg h-1 cm cat . - 2 $cm_{cat .}^{- 2}$ and a Faradaic efficiency of ≈92% at -0.5 V versus reversible hydrogen electrode, substantially outperforming Fe3O4 nanoparticle and bare carbon paper benchmarks. Combined experimental characterizations and density functional theory calculations reveal that the adjacent Fe nanoclusters electronically modulate the Fe-N4 sites, strengthening nitrate adsorption and facilitating the critical *NO to *NOH step by shifting the rate-determining step and lowering the overall energy barrier. Moreover, the catalyst exhibits exceptional long-term stability over 24 h and remarkable cyclability, attributed to the robust Fe-N coordination within the graphitic carbon framework. This work highlights the immense potential of synergistically coupling single atoms with clusters as a powerful design principle for advanced electrocatalysts in sustainable ammonia synthesis and beyond.
The U.S. Army Ranger Training Course (RTC) is a multi-stressor environment including cognitive and physical stress coupled with repeated sleep and energy deficits over 61+ days. Previous investigations of physiological responses to RTC operational stressors were conducted exclusively in males, leaving female responses uncharacterized. Therefore, this study aimed to identify changes in metabolic, growth, and sex hormones, inflammatory and iron markers in males and females undergoing RTC. Blood samples and body composition assessments (DXA) were collected at the start of RTC (Baseline (BL)) and at the end of each phase (Phase (P)1 - general field, P2 - mountains, P3 - swamp). During each phase, daily urine sampling and measures of energy balance (doubly labeled water method) occurred. Females experienced physiological changes primarily in P2, with reductions in estradiol (mean difference [95% Confidence Interval]: -79.29 [-115.32, -43.26]), progesterone (-1.48 [-2.70, -0.26]), testosterone (-0.74 [-1.43, -0.04]), free testosterone: -12.70 [-23.23, -2.17]), thyroid stimulating hormone (TSH; -0.54 [-1.03, -0.05]), and insulin-like growth factor 1 (IGF-1; -92.58 [-121.28, -63.88]) compared to BL. Males demonstrated significant decreases in free testosterone, TSH, triiodothyronine (T3), IGF-1, hemoglobin, and hematocrit across all three phases compared to BL (all, p < 0.05), with the largest changes in P3 for TSH (-0.66, [-1.21, -0.11]), T3 (-0.30 [-0.41, -0.20]), IGF-1 (-104.70 [-116.52, -92.88]), hemoglobin (-1.32 [-1.71, -0.94]), and hematocrit (-3.89 [-5.02, -2.75]). Ferritin increased across all phases compared to BL regardless of sex (p < 0.05). These findings indicate that multi-stressor environments may disproportionately affect male physiological markers, whereas females exhibited fewer, phase-specific changes.
The energy-free activation of ambient molecular oxygen (O2) to singlet oxygen (1O2) under neutral conditions is highly desirable for green oxidation chemistry, yet remains fundamentally limited by sluggish proton-coupled *OOH formation and desorption. Here, we engineer an interfacial proton-relay microenvironment between MoS2 and CuCl that enables self-driven O2-to-1O2 conversion without external energy inputs. Electron-deficient sulfur sites act as a proton reservoir by forming S-Hads species, facilitating directional proton migration through Cu-S-Mo channels to activate adsorbed O2 on electron-rich Cu sites. This coupled electron-proton relay accelerates *OOH hydrogenation while maintaining moderate *O2/*OOH binding, effectively suppressing O─O bond cleavage and favoring a 1O2-dominated pathway. As a result, the system achieves quantitative pollutant removal and sustained operation for over 16 h in pilot-scale membrane filtration. This interfacial design is broadly applicable to transition metal sulfides, offering a general strategy to overcome proton-transfer limitations and advance autonomous catalytic platforms for sustainable oxidation and environmental remediation.