ACS Publications最新文献

{"title":"CRISPRi-Linked Multimodule Negative Feedback Loops to Address Winner-Take-All Resource Competition.","authors":"Sadikshya Rijal, Kylie Standage-Beier, Rong Zhang, Austin Stone, Abdelrahman Youssef, Xiao Wang, Xiao-Jun Tian","doi":"10.1021/acssynbio.5c00394","DOIUrl":"https://doi.org/10.1021/acssynbio.5c00394","url":null,"abstract":"<p><p>Cellular resource limitations create unintended interactions among synthetic gene circuit modules, compromising circuit modularity. This challenge is particularly pronounced in circuits with positive feedback, where uneven resource allocation can lead to Winner-Takes-All (WTA) behavior, favoring one module at the expense of others. In this study, we experimentally implemented a Negatively Competitive Regulatory (NCR) controller using CRISPR interference (CRISPRi) and evaluated its effectiveness in mitigating WTA behavior in two gene circuits: dual self-activation and cascading bistable switch. We chromosomally integrated a tunable dCas9 gene and designed module-specific gRNAs, with each module encoding its own gRNA to self-repress via competition for limited dCas9. This configuration introduces strong negative feedback to the more active module while reallocating resources to the less active one, promoting balanced module activation. Compared to the control group lacking dCas9-mediated repression, the NCR controller significantly increased module coactivation and suppressed WTA behavior. Our quantitative results demonstrate that NCR provides an effective strategy for regulating resource competition and improving the modularity of synthetic gene circuits.</p>","PeriodicalId":26,"journal":{"name":"ACS Synthetic Biology","volume":" ","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028567","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reactive Molecular Dynamics Modeling of Collision-Induced Dissociation of 1-Ethyl-3-methylimidazolium Tetrafluoroborate Ionic Liquid Ions.","authors":"Abu Taqui Md Tahsin, Stefan J Bell, Elaine M Petro","doi":"10.1021/acs.jpca.5c05157","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c05157","url":null,"abstract":"<p><p>Ionic liquids (ILs) have been gaining increasing focus in a variety of applications including emerging electric-propulsion concepts. A quantitative understanding of how IL ions fragment during high-energy collisions with background gases is therefore essential for interpreting mass spectra, predicting ion lifetimes in plasma and vacuum environments, and designing IL-based technologies. This work uses molecular dynamics (MD) simulations with a reactive force field to numerically model the collision-induced dissociation (CID) of isolated ions (both positive and negative) and ion clusters (2:1 and 1:2 clusters) of the prototypical ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF₄), colliding with a nitrogen (N₂) molecule, exploring all possible fragmentation channels arising from the breaking of both ionic and covalent bonds at collision energies ranging from 10 electron volts (eV) to 100 electron volts (eV) in the laboratory frame. The molecular dynamics results are compared with the observations from tandem mass spectrometry (MS2) experiments to assess the reliability of the MD results. The MD modeling predicts the dissociation onset collision energy of the [EMIM]⁺ ion to be 20 eV (lab frame), while the [BF₄]^- ion requires a collision energy of at least 40 eV (lab frame) to undergo dissociation. The primary fragmentation product of the [EMIM]⁺ ion is found to be the 3-methylimidazolium cation, [C₄H₇N₂]⁺, with the cyanide anion, [CN]^-, being the major fragment ion at higher collision energies (≥60 eV, lab frame). The [BF₄]^- ion, on the other hand, dissociates to form the fluoride ion, [F]^-, and the neutral BF₃ molecule, with the [BF₂]⁺ ion being formed at higher collision energies (≥60 eV, lab frame). Both the 2:1 and 1:2 ion clusters are found to fragment at the lowest simulated collision energy of 10 eV (lab frame), with the fluoride ion, [F]^-, being formed with rising abundance as the collision energy is increased. When compared, the mass spectra from MD modeling and experiments demonstrate a reasonable agreement, which suggests that reactive MD can be a reliable surrogate for CID studies of complex IL ions.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Large-Scale Conformational Analysis Explains G-Quadruplex Topological Landscape.","authors":"Michał Jurkowski, Mateusz Kogut, Michał Olewniczak, Jan Glinko, Jacek Czub","doi":"10.1021/acs.jpcb.5c04372","DOIUrl":"https://doi.org/10.1021/acs.jpcb.5c04372","url":null,"abstract":"<p><p>G-quadruplexes (G4) are four-stranded nucleic acid structures formed within sequences containing repeated guanine tracts separated by intervening loop regions. Abundant in the human genome, they play crucial roles in transcription regulation and genome maintenance. Although theoretically capable to adopt 26 different folding topologies─primarily differing in loop arrangements─only 14 of these have been observed experimentally. This raises fundamental questions about whether the remaining topologies are energetically inaccessible and what molecular factors determine the folding patterns of G-quadruplexes. To address these questions, we systematically explored the conformational space of G-quadruplexes using a set of 128 DNA sequences capable of forming two- and three-tetrad structures with varying loop lengths. We conducted foldability evaluations of nearly 20,000 unique G4 conformations obtained through an in silico folding procedure. Our analysis revealed significant differences in foldability among the 26 theoretical topologies. Crucially, we demonstrated that the presence of long-distance propeller loops in 12 of these topologies imposes strict loop length constraints, hindering their formation, especially in sequences with shorter loops. Additionally, we found that the occurrence of long-distance propeller loops is governed by G4 helicity, resulting in opposite folding preferences in right-handed and left-handed G4s. By providing geometric explanation for G4 folding patterns, our study advances the understanding of the G-quadruplex topological landscape and offers valuable insights for the rational design of G4 structures.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032460","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DNA Binding and Electrochemical Characterization of Oxidative Products of the Cobalt(II) Complex.","authors":"Ijaz Ullah Muzaddadi, Arumugam Murugan, Bondana Kalita, Shankhadeep Saha, Natarajan Raman, Selvaraj Freeda Selva Sheela, Arumugam Manohar, Muthaiah Shellaiah, Radak Blange, Wen-Tai Li","doi":"10.1021/acs.jpcb.5c02888","DOIUrl":"https://doi.org/10.1021/acs.jpcb.5c02888","url":null,"abstract":"<p><p>The synthesis of <i>meso</i>-tetrakis(3,4,5-trimethoxyphenyl)porphyrin [H₂T(3,4,5-OCH₃)PP] and cobalt(II) <i>meso</i>-tetrakis(3,4,5-trimethoxyphenyl)porphyrin [Co(T(3,4,5-OCH₃)PP)] has been successfully accomplished. The oxidation properties of [Co(T(3,4,5-OCH₃)PP)] have been assessed through UV-vis, NMR, and EPR techniques. It can be seen in the UV-vis spectrum that adding SbCl₅ caused extra peaks to appear at 674 nm, which means that a π-cation radical was formed. The voltammogram shows how the ligand system helps the Co(II) electrochemical oxidation process to become Co(III). As shown by the EPR spectrum, the cobalt(II) changes its oxidation state to Co(III) due to the introduction of SbCl₅. NMR data can also support this conclusion. The interaction of DNA with [Co(T(3,4,5-OCH₃)PP)] has been evaluated. The decrease in current and the favorable alteration in the <i>E</i>_1/2 value highlight the substantial intercalative interaction between DNA and [Co(T(3,4,5-OCH₃)PP)]. Hirshfeld surface analysis has been performed to recognize the many intermolecular interactions. In vitro cytotoxicity activity results suggest that the incorporation of a metal center enhances cytotoxic activity, as the metalloporphyrin derivative consistently showed greater potency than that of the corresponding free-base porphyrin. This enhancement may be attributed to the intrinsic π-conjugated structure of the porphyrin framework, which facilitates cellular uptake and interactions with biological targets.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structure Engineering Enabled O-O Radical Coupling in Spinel Oxides for Enhanced Oxygen Evolution Reaction.","authors":"Long Shang, Shuo Xu, Youxuan Ni, Yong Lu, Haixia Li, Kai Zhang, Zhenhua Yan, Fangyi Cheng, Jun Chen","doi":"10.1021/jacs.5c13198","DOIUrl":"https://doi.org/10.1021/jacs.5c13198","url":null,"abstract":"<p><p>Developing cost-effective spinel oxide catalysts with both high oxygen evolution reaction (OER) activity and stability is crucial for advancing sustainable clean energy conversion. However, practical applications are often hindered by the activity limitations inherent in the adsorbate evolution mechanism (AEM) and the stability limitations associated with the lattice oxygen mechanism (LOM). Herein, we demonstrate structural changes induced by phase transformation in Co_1.5Mn_1.5 spinel oxides, which yield more active octahedral sites with shortened intersite distance. This structure optimization favors a direct O-O radical coupling mechanism, which circumvents the involvement of the *OOH intermediate and prevents overoxidation of the active sites, significantly enhancing both the OER activity and stability. Consequently, the optimized CoMn-400 catalyst exhibits an overpotential of 268 mV at 10 mA cm^-2 in 0.1 M KOH (310 mV for commercial RuO₂), and maintains negligible activity loss over 300 h' chronopotentiometry test at a current density of 100 mA cm^-2. This simple strategy provides fundamental insights into transition metal oxide catalyst design and opens new possibilities for optimizing electrochemical energy conversion.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145022424","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Misalignment between the Directions of Propagation and Decay of Nanoscale-Confined Polaritons.","authors":"Kirill V Voronin, Gonzalo Álvarez-Pérez, Aitana Tarazaga Martín-Luengo, Pablo Alonso-González, Alexey Y Nikitin","doi":"10.1021/acs.nanolett.5c03208","DOIUrl":"https://doi.org/10.1021/acs.nanolett.5c03208","url":null,"abstract":"<p><p>Anisotropic van der Waals crystals have gained significant attention in nano-optics and optoelectronics due to their unconventional optical properties, including anomalous reflection, canalization, and nanofocusing. Polaritons─light coupled to matter excitations─govern these effects, with their complex wavevector encoding key parameters such as wavelength, lifetime, field confinement, and propagation direction. However, determining the complex wavevector, particularly the misalignment between its real and imaginary parts, has remained a challenge due to the complexity of the dispersion relation. Here, using near-field nanoimaging, we introduce a self-consistent method to extract the complex wavevector from polaritonic near-field images. We experimentally reveal a strong misalignment between the real and imaginary components of the wavevector, significantly impacting the interpretation of near-field experiments. Our findings establish a new paradigm for optical nanoimaging, providing a robust framework for accurately extracting polariton parameters and advancing the broader field of nanooptics of lossy anisotropic crystals.</p>","PeriodicalId":53,"journal":{"name":"Nano Letters","volume":" ","pages":""},"PeriodicalIF":9.1,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145022512","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Surface-Driven Electron Localization and Defect Heterogeneity in Ceria.","authors":"Xingfan Zhang, Akira Yoko, Yi Zhou, Woongkyu Jee, Alvaro Mayoral, Taifeng Liu, Jingcheng Guan, You Lu, Thomas W Keal, John Buckeridge, Kakeru Ninomiya, Maiko Nishibori, Susumu Yamamoto, Iwao Matsuda, Tadafumi Adschiri, Osamu Terasaki, Scott M Woodley, C Richard A Catlow, Alexey A Sokol","doi":"10.1021/jacs.5c10679","DOIUrl":"https://doi.org/10.1021/jacs.5c10679","url":null,"abstract":"<p><p>The exceptional performance of ceria (CeO₂) in catalysis and energy conversion is fundamentally governed by its defect chemistry, particularly oxygen vacancies. The formation of each oxygen vacancy (V_O^••) is assumed to be compensated by two localized electrons on cations (Ce³⁺). Here, we show by combining theory with experiment that while this 1 V_O^••: 2Ce³⁺ ratio accounts for the global charge compensation, it does not apply at the local scale, particularly in nanoparticles. Hybrid quantum mechanical/molecular mechanical (QM/MM) defect calculations, together with synchrotron X-ray photoelectron spectroscopy (XPS) measurements, show that electrons have a strong preference to localize and segregate on surfaces, which can overcome the trapping force from the V_O^•• sites in the bulk. At a given Fermi level, the surface V_O^•• tends to trap more electrons than those in bulk, resulting in a higher Ce³⁺ to V_O^•• ratio on surfaces than that in the bulk, driven by the preferential localization of electrons and enhanced V_O^••-Ce³⁺coupling. Large-scale unbiased Monte Carlo simulations on ceria nanoparticles confirmed this trend and further show that the surface segregation of electrons is more pronounced at low reduction levels and in smaller nanoparticles. In highly reduced ceria nanoparticles, however, the enhanced repulsive interactions lead to a less significant extent of defect heterogeneity or even reverse the location preference of defects in some nanoparticles. Our findings underscore the need to consider both the overall nonstoichiometry and local defect behavior in easily reducible oxides, with direct relevance to their performance in catalytic and energy applications.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145022484","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Spatial Distortion-Engineered Cationic Ru-Covalent Organic Framework Overcoming Aggregation-Caused Quenching for Synergistic Photodynamic/Photothermal Anti-Infective Therapy.","authors":"Dongyan Wei, Weiwei Shi, Yudan Zhao, Jinhong Zhang, Huanhuan Li, Xiaohong Liu, Kai Zhang, Junling Liu","doi":"10.1021/acsami.5c13840","DOIUrl":"https://doi.org/10.1021/acsami.5c13840","url":null,"abstract":"<p><p>Decades of antibiotic misuse have spurred an antimicrobial resistance crisis, creating an urgent demand for alternative treatment options. Although phototherapy has therapeutic potential, the efficacy of the most advanced photosensitizers (PS) is essentially limited by aggregation-induced quenching, which significantly reduces their therapeutic effect. To address these challenges, we developed a cationic metallocovalent organic framework (CRuP-COF) via a solvent-mediated dual-reaction synthesis strategy. This material (ζ = +21.07 ± 1.04 mV) was fabricated through synergistic Knoevenagel polycondensation and SN₂ nucleophilic substitution, using bromoethane as a bifunctional modulator to copolymerize tris(4,4'-dicarboxaldehyde-2,2'-bipyridine)Ru(II) (Rubpy-6CHO) and <i>meso</i>-tetrakis(6-methylpyridin-3-yl)porphyrin (TMPP). The spatially distorted Ru(II) centers create staggered π-conjugation networks, effectively suppressing π-π stacking interactions, thereby preventing the photoactivity decay commonly observed in conventional porphyrin systems. Pyridinic N-ethylation generates a permanent cationic surface potential, enabling selective electrostatic adhesion to negatively charged bacterial membranes. This targeting mechanism, combined with the hierarchical porous structure and high specific surface area, optimizes mass and energy transport while minimizing thermal and reactive oxygen species (ROS) dissipation. CRuP-COF demonstrates superior photothermal conversion efficiency and sustained ROS generation (mixed Type I/II mechanisms), exhibiting 50% higher antibacterial potency than its noncationic analog RuP-COF. At 200 μg/mL, it achieves remarkable >98% eradication rates against both Gram-positive (<i>Staphylococcus aureus</i>) and Gram-negative (<i>Escherichia coli</i>) pathogens. The system further demonstrates self-amplifying therapeutic effects, where localized photothermal heating accelerates ROS production, which, in turn, enhances bacterial membrane permeability to facilitate cationic targeting. Biosafety assessments confirm excellent biocompatibility with minimal hemolytic activity and high cellular viability at therapeutic concentrations. This integrated approach establishes a paradigm in antimicrobial development, offering a potent, targeted, and resistance-proof therapeutic solution that meets the urgent demands of modern infection control.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028528","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"H₂O and CO₂ Sorption in Ion-Exchange Sorbents: Distinct Interactions in Amine Versus Quaternary Ammonium Materials.","authors":"Golnaz Najaf Tomaraei, Sierra Binney, Ryan Stratton, Houlong Zhuang, Jennifer L Wade","doi":"10.1021/acsami.5c12939","DOIUrl":"https://doi.org/10.1021/acsami.5c12939","url":null,"abstract":"<p><p>This study investigates the H₂O and CO₂ sorption behavior of two chemically distinct polystyrene-divinylbenzene-based ion exchange sorbents: a primary amine and a permanently charged strong base quaternary ammonium (QA⁺) group with (bi)carbonate counter anions. We compare their distinct interactions with H₂O and CO₂ through simultaneous thermal gravimetric, calorimetric, gas analysis, and molecular modeling approaches to evaluate their performance for dilute CO₂ separations like direct air capture. Thermal and hybrid (heat + low-temperature hydration) desorption experiments demonstrate that the QA⁺-based sorbent binds both water and CO₂ more strongly than the amine counterparts but undergoes degradation at moderate temperatures, limiting its compatibility with thermal swing regeneration. However, a low-temperature moisture-driven regeneration pathway is uniquely effective for the QA⁺-based sorbent. To inform the energetics of a moisture-based CO₂ separation (i.e., a moisture swing), we compare calorimetric water sorption enthalpies to Clausius-Clapeyron-derived total isosteric enthalpies. To our knowledge, this includes the first direct calorimetric measurement of water sorption enthalpy in a QA⁺-based sorbent. Both methods reveal monolayer-multilayer sorption behavior for both sorbents, with the QA⁺-based material having slightly higher water sorption enthalpies at the initially occupied strongest sorption sites. Molecular modeling supports this observation, showing higher water sorption energies and denser charge distributions in the QA⁺-based sorbent at λ_H₂O = 1 mmol/mmol_site. Mixed gas experiments in the QA⁺-based sorbent show that not only does water influence CO₂ binding, but CO₂ influences water uptake through counterion-dependent hydration states, and that moisture swing responsiveness in this material causes hydration-induced CO₂ release and drying-induced CO₂ uptake, an important feature for low-energy CO₂ separation under ambient conditions. Overall, the two classes of sorbents offer distinct pathways for the CO₂ separation.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028512","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fluorinated Imidazolidinium Cations as a Fluorine-Lean Interface Repairing Agent for Li-Metal Batteries.","authors":"Yuchen Yang, Tevin Li, Hou Runqiao, Kaixin Ren, Shouyi Yuan, Junwei Lucas Bao, Yonggang Wang","doi":"10.1021/acsami.5c12646","DOIUrl":"https://doi.org/10.1021/acsami.5c12646","url":null,"abstract":"<p><p>Li-metal batteries promise ultrahigh energy density, but their application is limited by Li-dendrite growth. Theoretically, fluorine-containing anions such as bis(fluorosulfonyl)imide (FSI^-) in electrolytes can be reduced to form LiF-rich solid-electrolyte interphases (SEIs) with high Young's modulus and ionic conductivity that can suppress dendrites. However, the anions migrate toward the cathode during the charging process, accompanied by a decrease in the concentration of interfacial anions near the anode surface. This will create a fluorine-lean (F-lean) interface and an uneven SEI. Herein, we propose an F-lean interface repairing agent utilizing the fluorinated ionic liquid 2-fluoro-1,3-dimethylimidazolidinium hexafluorophosphate ([f-Im⁺][PF₆^-]). The [f-Im⁺] cations could migrate to the Li-metal anode along with Li⁺ during the Li-deposition process and be decomposed prior to Li deposition, thus repairing the F-lean interface and forming a dense and F-enriched SEI layer on the Li-metal anode. Further theoretical calculations suggest that after fluorine substitution, the fluorinated imidazolidinium cations are more thermally vulnerable to be decomposed to form a LiF-rich SEI. Consequently, an ultrahigh Coulombic efficiency (CE) of Li deposition over 99.5% and stable cycling of Li||NCM811 full cells over 100 times have been achieved even with an N/P ratio of 1.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028551","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}