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At least 703 records · Page 39

Understanding why poly(acrylic acid) works: decarbonylation and cross-linking provide an ionically conductive passivation layer in silicon anodes

Poly(acrylic acid) (PAA) is commonly used as a binder for fabricating silicon (Si) anode active materials in lithium-ion batteries due to its useful properties including high polar solvent solubility, good rheology, and strong adhesive properties. However, the role and evolution of PAA during electrode fabrication, cycling, and calendar aging are not well understood. In this work, we reveal the evolution of PAA during electrode curing and relate its chemical change to the final electrode properties and performance. These studies are made possible using two types of in situ attenuated total reflectance-infrared Fourier transform (ATR-FTIR) spectroscopy: thermal ATR-FTIR to probe the cross-linking reaction, and ATR-FTIR spectroelectrochemistry of three-dimensional composite electrodes, a unique technique developed herein that probes the solvation dynamics of lithium ions at the silicon anode interface under electrochemical polarization. Specifically, we show that PAA undergoes a thermally-mediated, cross-linking decarbonylation reaction to form an ether-based network polymer. To show the importance of the polyether moieties, we synthesize partially esterified PAA analogues that do not undergo this cross-linking decarbonylation reaction and correlate the degree of cross-linking to half-cell performance metrics. Finally, we unveil the mechanism of the polyether binder performance through in situ ATR-FTIR spectroelectrochemistry and show that PAA acts as an interfacial material that conducts lithium-ions, limits solvent molecule access to the Si surface, and stabilizes the electrode against parasitic lithium inventory loss at high state of charge for an extended period of time.

25 ENERGY STORAGE↗

From the laboratory to space: unveiling isomeric diversity of C 5 H 2 in the reaction of tricarbon (C 3 , X 1 Σ g + ) with the vinyl radical (C 2 H 3 , X 2 A′)

By connecting laboratory dynamics with cosmic observables, this work highlights the critical role of reactions between highly reactive species in shaping the molecular inventory of the interstellar medium and opens new windows into the spectroscopically elusive corners of astrochemical complexity. The gas phase formation of distinct C 5 H 2 isomers is explored through the bimolecular reaction of tricarbon (C 3 , X 1 Σ + g ) with the vinyl radical (C 2 H 3 , X 2 A′) at a collision energy of 44 ± 1 kJ mol −1 employing the crossed molecular beam technique augmented by electronic structure and Rice–Ramsperger–Kassel–Marcus (RRKM) calculations. This barrierless and exoergic reaction follows indirect dynamics and is initiated by the addition of tricarbon to the radical center of the vinyl radical forming a Cs symmetric doublet collisional complex (CCCCHCH 2 ). Subsequent low-barrier isomerization steps culminate in the resonantly stabilized 2,4-pentadiynyl-1 radical (CHCCCCH 2 ), which decomposes via atomic hydrogen loss. Statistical calculations identify linear, triplet pentadiynylidene (p2, X 3 Σ − g ) as the dominant product, while singlet carbenes ethynylcyclopropenylidene (p1, X 1 A′), pentatetraenylidene (p3, X 1 A 1 ), and ethynylpropadienylidene (p4, X 1 A′) are formed with lower branching ratios. The least stable isomer, 2-cyclopropen-1-ylidenethenylidene (‘eiffelene’; p5, X 1 A 1 ), remains thermodynamically feasible, but exhibits negligible branching ratios. Two isomers detected in TMC-1 to date (p1 and p3) possess significant dipole moments making them amenable to radio telescopic observations, whereas linear pentadiynylidene (p2; D ∞h ) is only traceable via infrared spectroscopy or through its cyanopentadiynylidene derivative (HCCCCCCN). This study highlights the isomer diversity accessed in the low temperature hydrocarbon chemistry of barrierless and exoergic bimolecular reactions involving two unstable, reactants in cold molecular clouds.

Medvedkov, Iakov A. [University of Hawai'i at Mano↗

Deciphering the local structure of Prussian blue analogue cathodes with Raman spectroscopy for sodium-ion batteries

Iron-based Prussian blue analogues (PBAs) have gained attention as low-cost, relatively higher-potential cathodes for sodium-ion batteries, due to their open 3D-framework structures. However, understanding the local structural changes is critical to unveiling the intercalation pathways and degradation mechanisms. We employ here operando Raman spectroscopy to probe the changes in the cyanide vibrational modes during cycling and degradation after cycling, which are not adequately resolved by X-ray diffraction due to the low structure factor and limited X-ray sensitivity of the cyanide groups. Vibrational spectroscopy has thus proven essential for deciphering these complex materials. Additionally, we implement pre-sodiation strategies to assess the impact of sodium inventory loss by pairing PBAs with a hard carbon anode in a full-cell configuration. Operando galvanostatic electrochemical impedance spectroscopy (EIS) and ex situ X-ray photoelectron spectroscopy (XPS) further elucidate the interface evolution and the role of water molecules in forming the cathode-electrolyte interphase (CEI) and solid-electrolyte interphase (SEI). The insights gained advance the understanding of PBAs and enhance their practical viability.

25 ENERGY STORAGE↗

Controlled lithium stripping enables a stable interface for long-cycling anode-free solid-state batteries

Anode-free solid-state batteries (AFSSBs) are a promising route toward achieving high energy density. In these cells, the anode contains no pre-stored lithium (Li). Instead, the entire Li inventory originates from the cathode and is freshly deposited onto a bare current collector during charging. However, achieving uniform and defect-free Li plating on this bare current collector remains a major challenge, often resulting in low Li plating/stripping efficiency and rapid capacity decay. Here, for the first time, operando neutron imaging is employed to visualize Li plating/stripping behavior in an anode-free full cell with LiNi0.82Mn0.07Co0.11O2 (NMC) as the cathode. Operando measurements reveal that complete stripping of Li leaves isolated Li residues on the current collector, which degrades the interfacial contact between the current collector and the solid-state electrolyte. To mitigate this interfacial issue and promote more uniform Li deposition, we implement a discharge-cutoff-voltage strategy that intentionally retains a thin residual Li layer after stripping. This preserved Li-containing interfacial reservoir not only improves interfacial contact but also serves as an in situ formed seed layer that enables more homogeneous subsequent Li plating. As a result, the optimized anode-free cell with limited stripping depth exhibits excellent long-term cycling stability, maintaining a discharge capacity of 112.1 mAh g−1 with a capacity retention of 80.6% and an average coulombic efficiency of approximately 99.9% after 500 cycles at 0.25 C. In contrast, the cell with a conventional discharge cutoff voltage of 2.8 V exhibits rapid capacity decay, retaining only 59.7 mAh g−1 after 50 cycles with a capacity retention of 40.7%. This work demonstrates that limiting deep stripping to preserve a thin Li-containing interfacial layer can effectively improve the cycling stability of sulfide-based AFSSBs.

Wang, Jiwei [Northeastern University, Boston]↗

Surfactants and cloud droplet activation: A systematic extension of Köhler theory based on analysis of droplet stability

The activation of aerosol particles to form cloud droplets, a necessary first step in cloud formation, controls much of the impact that aerosols have on clouds and climate. Recently, there has been a surge of interest in extending the Köhler theory of cloud droplet activation to include surface active (typically organic) as well as water-soluble (typically inorganic) aerosol components, but a systematic framework for doing this has yet to be developed. Here, we apply a droplet stability analysis to this end. Ideal and Szyszkowski–Langmuir surfactant models are analyzed to demonstrate the new approach, but the underlying theoretical framework is fundamental and model free. A key finding is that superficial densities at the cloud activation threshold (Köhler maximum) are significantly sub-monolayer, with fractional coverage ranging from 69% to 85% for the organic compounds and mixtures studied. The result, significant for model inventories of cloud condensation nuclei, is a weakening of the surfactant effect relative to expectations based on bulk sample measurements. Analytical results are obtained for the loci of Köhler maxima and applied to aerosol mixtures containing an arbitrary number of water-soluble and surfactant components.

54 ENVIRONMENTAL SCIENCES↗

Development of five-moment two-fluid modeling for Z-pinch physics

The Z-pinch m = 0 instability as well as its stabilization by radially sheared axial flow is studied using the nonlinear ideal five-moment twofluid (5M2F) model with an extension of that model to include Braginskii heat and momentum transport. Using the ideal 5M2F model, linear growth rate results are compared with prior work using MHD and Hall MHD. At small normalized wavenumber, 1 < k a < 4 , where a is the effective pinch radius, 5M2F results agree with Hall MHD within 20% in scenarios without radially sheared axial flow. With the sheared flow and focusing on ka = 10/3, agreement with Hall MHD is excellent. In the limit of small ion inertial length, results also match with MHD. A comparison with PIC modeling of shear-free m = 0 stability focuses on a plasma scenario based on recent experimental results. In a scan of mode wavenumber, ideal 5M2F results are qualitatively similar to PIC: the growth rate rises to a peak at a moderate wavenumber and declines at a large wavenumber in contrast to MHD results, which show the saturation of the growth rate with the increasing wavenumber rather than a decline. The peak normalized 5M2F growth rate is &#x3B3; &#x3C4; A = 1.5 , where sA is the Alfven transit time across the pinch. The peak occurs at normalized wavenumber ka = 10. For comparison, PIC results have a peak growth of &#x3B3; &#x3C4; A = 0.77 at ka = 5. Including Braginskiibased closure of the 5M2F model does not qualitatively change the ideal results in this particular case. Nonlinear saturation is studied using the 5M2F model with the dissipative Braginskii-based closure in cases with pinch-edge sheared-flow speed equal to half the Alfven speed. Nonlinear mixing due to the sheared flow yields a quasi-steady state after modest losses of pinch ion inventory and pinch thermal energy, approximately 30% and 10%, respectively. 5M2F modeling captures the essential physics of m = 0 instability and offers a computationally tractable route to high-fidelity modeling of 3D Z-pinch behavior, including m = 1 instability.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Laboratory study of the failed torus mechanism in arched, line-tied, magnetic flux ropes

Coronal mass ejections (CMEs) are some of the most energetic and violent events in our solar system. The prediction and understanding of CMEs are of particular importance due to the impact that they can have on Earth-based satellite systems and, in extreme cases, ground-based electronics. CMEs often occur when long-lived magnetic flux ropes (MFRs) anchored to the solar surface destabilize and erupt away from the Sun. One potential cause for these eruptions is an ideal magnetohydrodynamic (MHD) instability, such as the kink or torus instability. Previous experiments on the magnetic reconnection experiment revealed a class of MFRs that were torus-unstable but kink-stable, which failed to erupt. These “failed-tori” went through a process similar to Taylor relaxation, where the toroidal current was redistributed before the eruption ultimately failed. Herein we have investigated this behavior through additional diagnostics that measure the current distribution at the foot points and the energy distribution before and after an event. These measurements indicate that ideal MHD effects are sufficient to explain the energy distribution changes during failed torus events. This excludes Taylor relaxation as a possible mechanism of current redistribution during an event. A new model that only requires non-ideal effects in a thin layer above the electrodes is presented to explain the observed phenomena. This work broadens our understanding of the stability of MFRs and the mechanism behind the failed torus through the improved prediction of the torus instability and through new diagnostics to measure the energy inventory and current profile at the foot points.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Particle balance of deuterium during deuterium shattered pellet injection shutdown in DIII-D

A particle balance analysis was conducted during a deuterium (D 2 ) shattered pellet injection-induced plasma shutdown on the DIII-D tokamak to determine why less than 20% of the pellet material is assimilated into the core plasma by the mid-current quench (CQ). Initially, most of the D 2 is injected as frozen shards and ionized upon entering the vessel. During the thermal quench, ionized particles move to the divertors and subsequently to the center post (CP) walls, where they rapidly recycle and partially accumulate as neutrals without assimilating into the core plasma. In contrast, the particle flux to the outer midplane walls is negligible, despite being accompanied by hot plasma with electron temperatures exceeding 100 eV. During mid-CQ, volume recombination effects, although not large enough to impact overall particle balance, were significant enough to require accounting for accurate interpretation of fast-framing camera D-alpha signals and the estimation of the CP wall particle flux. In addition, toroidal asymmetries, observed in measurements of toroidal electron density perturbations and the phase of magnetohydrodynamic modes, are present throughout the shutdown and can account for a discrepancy in the assimilation rate for up to 50% of the observed D 2 particle inventory. These sources and sinks of particles and fluxes were identified using absolutely calibrated D-alpha brightness and Langmuir probes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The MuFusE large-volume diamond anvil cell for exploring muon-catalyzed fusion at higher pressures and temperatures

A new large-volume diamond anvil cell (DAC) has been developed for the Muon-catalyzed Fusion (μCF) Experiment (MuFusE), enabling the compression and heating of deuterium–tritium (d–t) mixtures to pressures and temperatures needed to advance μCF research. The MuFusE DAC achieves the large sample volumes necessary for high-precision fusion measurements while integrating cryogenic loading, all-metal sealing, and flexible bellows to maintain a secure environment during cell compression. Combined with remote pneumatic actuation and secondary containment, the DAC safely managed a 25 Ci tritium inventory while providing a clear optical path for in situ measurements of sample pressure and composition via laser spectroscopy. Utilizing 5 mm diameter diamond anvils oriented in the path of a high-intensity muon beam, the apparatus achieved a stable sample volume of 19.2 mm 3 at liquid density, pressures up to 933 MPa and temperatures up to 400 K—benchmarks that significantly exceed previously reported limits for static d–t targets.

Kalow, J. D. [Acceleron Fusion, Inc., Cambridge, M↗

The carbon content of Earth and its core

Earth’s core is likely the largest reservoir of carbon (C) in the planet, but its C abundance has been poorly constrained because measurements of carbon’s preference for core versus mantle materials at the pressures and temperatures of core formation are lacking. Using metal–silicate partitioning experiments in a laser-heated diamond anvil cell, we show that carbon becomes significantly less siderophile as pressures and temperatures increase to those expected in a deep magma ocean during formation of Earth’s core. Based on a multistage model of core formation, the core likely contains a maximum of 0.09(4) to 0.20(10) wt% C, making carbon a negligible contributor to the core’s composition and density. However, this accounts for ~80 to 90% of Earth’s overall carbon inventory, which totals 370(150) to 740(370) ppm. The bulk Earth’s carbon/sulfur ratio is best explained by the delivery of most of Earth’s volatiles from carbonaceous chondrite-like precursors.

Geosciences↗

Niche expansion for phototrophic sulfur bacteria at the Proterozoic–Phanerozoic transition

Significance Carotenoid pigments afford valuable clues about the chemistry and biology of both modern and ancient aquatic environments. This study reveals that fossil aromatic carotenoids—long considered biomarkers for anoxygenic, phototrophic sulfur bacteria and their physiological requirement for hydrogen sulfide and illumination—can also be biosynthesized by oxygen-producing cyanobacteria. Cyanobacterial aromatic carotenoids, which are distinct in their chemical structures and occurrence patterns, are the most commonly encountered compounds in Proterozoic marine settings as well as in lakes from more recent eras. In contrast, carotenoids diagnostic for green sulfur bacteria of the family Chlorobiaceae became both prevalent and abundant in marine paleoenvironments beginning in the Phanerozoic Eon. This expansion occurs as marine sulfate inventories increased toward the end of the Proterozoic Eon.

59 BASIC BIOLOGICAL SCIENCES↗

Acclimation to high and low diurnal light is flexible in Chlamydomonas reinhardtii

Chlamydomonas acclimates to repeated low (LL) or high light (HL) days by changing the abundance of photosynthetic complexes and the ultrastructure of its thylakoid membranes. These phenotypes persist through the night phases, suggesting a readiness for the daylight environment that is routinely experienced despite the intervening dark periods [S. Dupuis et al., Plant Cell 37, koaf086 (2025), 10.1093/plcell/koaf086]. Here, we investigate how prior acclimation impacts algal fitness upon a change in daylight intensity and how quickly Chlamydomonas can reprogram its photoprotective strategy in a diurnal context. We performed a systems analysis of synchronized populations acclimated to diurnal LL when subjected to HL days and of populations acclimated to diurnal HL when subjected to LL days. In the latter case, diurnal photoacclimation decreased fitness during the first day at a new light intensity: HL-acclimated cells barely increased in size over the first LL period, and they failed to complete a cell cycle. However, although LL-acclimated cells showed severe photodamage after 6 h of HL, they recovered chloroplast form and function later that afternoon and successfully divided at nightfall. These cells rapidly altered their thylakoid membrane ultrastructure, increased their photoprotective quenching capacity, and decreased their inventory of photosystem and antenna proteins by the end of the first HL day. Transcriptomic and proteomic analyses revealed rapid induction of thousands of genes, including those encoding proteases, chaperones, and other proteins involved in the chloroplast unfolded protein response. These results show that the alga is highly flexible and competent to rapidly acclimate to changes in diurnal light intensity.

Diel↗

Coupled machine learning–ecosystem ensemble models substantially improve predictions of nitrous oxide (N 2 O) fluxes from US croplands

Nitrous oxide (N 2 O) is a potent and persistent greenhouse gas, with rising atmospheric concentrations driven in part by inefficient use of synthetic nitrogen (N) fertilizers in agriculture. Predicting soil N 2 O emissions is challenging due to high spatial and temporal variability arising from complex soil biogeochemical processes. Process-based ecosystem models and standalone machine learning (ML) approaches without extensive site-specific calibration often miss high-emission episodes. Here, we show how an Ensemble Modeling System (EMS) based on outputs from an ensemble of ecosystem models coupled to an ensemble of ML models can improve predictions and understanding of N 2 O fluxes from US cropland. Trained and validated on ~12,000 N 2 O chamber measurements at 17 US Midwest sites (six crops, 35 management practices), the EMS accurately predicted daily fluxes of N 2 O at both training (R 2 = 0.84, RMSE = 16.4 g N ha −1 d −1 ) and held-out testing sites (R 2 = 0.84, RMSE = 6.2 g N ha −1 d −1 ). Analyses identified six dominant N 2 O drivers: soil organic carbon (SOC), NH 4 + , NO 3 - , water-filled pore space, temperature, and aboveground biomass production. Wet, warm soils produced large N 2 O peaks only with sufficient SOC and mineral N; in low-SOC soils, fluxes remained low. Incorporating these drivers into process-based models might significantly improve their predictive capacity. The EMS demonstrates a strong potential to predict N 2 O fluxes at unseen sites, enabling more reliable regional inventories, improved gap-filling where measurements are sparse, and enhanced understanding of mechanisms to advance targeted mitigation strategies in food, feed, and bioenergy crops.

AI↗

An Analysis of Potentially Implementing Standardized Canisters in the U.S. Commercial Waste Management System

This analytical study focuses on loading standardized transportation, aging, and disposal canisters (STADs) at commercial reactor sites and subsequent transportation, e.g., to a consolidated interim storage facility (CISF). Specifically, the amount of spent nuclear fuel (SNF) available to load into STADs with varying deployment dates is explored, and the scenarios are compared with a scenario in which STADs are never loaded at reactor sites. Two key findings are that about half of the U.S. inventory of commercial SNF could be captured in STADs if they were fully deployed by 2035 and that the percentage of SNF available to load into STADs decreases as STAD deployment is delayed.In additional scenarios, the effects of shipping STADs directly from at-reactor spent fuel pools (SFPs) to a CISF are analyzed for a STAD full deployment year of 2035. A key finding from the analysis is that the dry storage of SNF in STADs at reactor sites can be minimized by direct shipment to a CISF from reactor site SFPs. Furthermore, minimizing dry storage at reactor sites means maximizing the receipt rate for STADs at a CISF, and there is likely a more optimal point between the two scenarios for an overall cost-effective operation of waste management systems.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A MOOSE-Based Model for Fission Product Transport and Source Term Estimation for High-Temperature Gas-Cooled Reactors

Thanks to fuel elements containing tristructural isotropic (TRISO) particles combined with a low core power density and passive feedback mechanisms leading to modest temperature rises in the event of accidental events, high-temperature gas-cooled reactors (HTGRs) offer a high degree of reliability in terms of fission product retention. While the anticipated source term for HTGRs is expected to be very low, it is important to provide a quantitative estimate of radiological releases during nominal and accidental conditions. Here, we propose a computationally efficient mechanistic source term methodology relying on the Multiphysics Object Oriented Simulation Environment (MOOSE) for tracking fission product transport from TRISO particles up to the coolant pressure boundary, as well as modeling the transport and potential deposition of these nuclides inside the reactor coolant loop. The proposed computational scheme is applied to estimate source term inventories for a representative 10-MW(thermal) prismatic high-temperature microreactor and is qualitatively compared against known release fractions. In addition to providing an alternate analysis tool, this MOOSE model can help reactor designers quantify the influence of key design parameters relevant for studies of radiological dose consequences.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Depletion Benchmark Analysis on a Lead Fast Reactor Using PyARC/OpenMC

PyARC is a user-friendly fast reactor analysis tool that automates multiphysics workflows using the “extended suite” of Argonne Reactor Computation (ARC) codes by providing a single common input for model definition, code execution, and output post-processing. A lead fast reactor (LFR) benchmark model is used to perform depletion calculations using the newly integrated OpenMC depletion capability in PyARC, building on previous analysis using the ARC codes through PyARC and Serpent. Results for core lifetime k-effective, shutdown decay heat, and end-of-life heavy-metal inventory are compared to verify the PyARC/OpenMC integration against the PyARC/ARC workflow and Serpent for depletion analysis of LFR designs. The results show satisfactory agreement among all three methods, with remaining discrepancies largely attributable to differences in nuclear data libraries and decay-chain modeling detail rather than to fundamental modeling limitations.

Kiesling, Kalin R.↗

Used Nuclear Fuel Management Using the Next Generation System Analysis Model

The U.S. Department of Energy (DOE) is leading the National effort to manage the back end of the nuclear fuel cycle, encompassing the safe transportation, storage/staging, and/or eventual disposal of used nuclear fuel (UNF) and high-level radioactive waste. The Next Generation System Analysis Model (NGSAM) is DOE’s discrete-event, agent-based simulation tool designed to model the full life cycle of UNF from reactor discharge to final disposal. NGSAM supports the DOE Office of Spent Fuel and High-Level Waste Disposition by enabling a detailed, scenario-based analysis of logistics, infrastructure, and shipping strategies. NGSAM replaces legacy models with a modern, flexible platform built on Repast Simphony and enhanced by the Process Analysis Tool. NGSAM simulates the movement and interaction of individual fuel assemblies with system components such as canisters, casks, railcars, and facilities. The model integrates with the Java Transportation Operations Model to plan and execute transportation scenarios, supporting both constrained and unconstrained resource allocation. Key features include customizable allocation and acceptance algorithms, detailed facility-level operations, and a Quick Edit tool for rapid scenario adjustments. NGSAM supports multimodal transportation modeling (e.g. rail, road, barge) and provides comprehensive cost, schedule, and infrastructure data. NGSAM utilizes data from sources such as DOE’s STANDARDS UNF database and DOE’s Stakeholder Tool for Assessing Radioactive Transportation, while also allowing user-defined inputs for scenario customization. NGSAM enables stakeholders to evaluate complex UNF management strategies, assess system performance under varying assumptions, and inform decision making for future infrastructure investments. Its modular architecture and integration with other Integrated Waste Management System tools make it a critical asset for planning the safe and efficient disposition of the Nation’s growing UNF inventory.

Craig, Brian [Argonne National Laboratory (ANL)]↗

A New Era of Nuclear Criticality Experiments: The First 10 Years of Planet Operations at NCERC

Planet is a vertical-lift assembly machine currently located at the National Criticality Experiments Research Center (NCERC) at the Nevada National Security Site. In the past, Planet resided at Technical Area-18 in Los Alamos, New Mexico, as part of the Los Alamos Critical Experiments Facility (LACEF). Following the de-inventorying of LACEF, the Planet assembly was relocated to NCERC in 2008 and became fully operational in June of 2011. The Class Foils experiment, which involves stacking highly enriched uranium foils to obtain a critical configuration, was the first critical experiment performed on Planet. As a major component of the Nuclear Criticality Safety Class taught for the U.S. Department of Energy (DOE) Nuclear Criticality Safety Program, the Class Foils experiment allows personnel from all over the DOE complex to handle nuclear material and to complete the approach to critical safely and successfully. This paper describes the Planet vertical assembly and recent engineering upgrade and a selection of the experiments that have been performed on Planet since its transition to NCERC 10 years ago.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗