ACS NanoPub Date : 2025-04-03DOI: 10.1021/acsnano.5c00025
Han Li, Ming Zheng, Jeffrey A. Fagan
{"title":"Precise Partitioning of Metallic Single-Wall Carbon Nanotubes and Enantiomers through Aqueous Two-Phase Extraction","authors":"Han Li, Ming Zheng, Jeffrey A. Fagan","doi":"10.1021/acsnano.5c00025","DOIUrl":"https://doi.org/10.1021/acsnano.5c00025","url":null,"abstract":"Separation of single-chirality single-wall carbon nanotubes (SWCNTs) and their enantiomers holds significant potential for materials science and various applications but challenges in scalability and precision persist. In this study, we introduce a systematic approach to identify separation conditions for metallic SWCNTs in aqueous two-phase extraction (ATPE), precisely identifying improved conditions for isolating multiple armchair and chiral (<i>n</i>,<i>m</i>) species. We quantify these conditions by determining partition coefficient change condition (PCCC) values for both binary and ternary surfactant combinations. This information enables optimization for efficient separation of high-purity armchair nanotubes such as (6,6), (7,7), (8,8) and (9,9), and for isolation of enantiomeric nonarmchair nanotubes, including challenging metallic species such as the (8,5), (7,4), (9,3), (10,4) and (10,7). Lastly, separated single (<i>n</i>,<i>m</i>) populations are reseparated in ATPE at precise steps in both binary and ternary surfactant mixtures to resolve their enantiomers, extracting information on the underlying mechanism of metallic SWCNT ATPE and highlighting the utility of sodium cholate for achieving single enantiomer level separations.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"23 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775895","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}
ACS NanoPub Date : 2025-04-03DOI: 10.1021/acsnano.5c01732
Yuming Wang, Ni Fan, Rui Wang, Xue Li, Feng Zhao, Lin Miao, Xi Wang, Xiaohui Yan, Zhang Zhang, Xuanjun Wu, Zhonggao Gao, Yunfei Li, Yubo Li
{"title":"Discovery of Airway-Administered Ionophores for Mn<sup>2+</sup> to Mitigate Lung Metastasis by Targeting Disseminated Tumor Cell.","authors":"Yuming Wang, Ni Fan, Rui Wang, Xue Li, Feng Zhao, Lin Miao, Xi Wang, Xiaohui Yan, Zhang Zhang, Xuanjun Wu, Zhonggao Gao, Yunfei Li, Yubo Li","doi":"10.1021/acsnano.5c01732","DOIUrl":"https://doi.org/10.1021/acsnano.5c01732","url":null,"abstract":"<p><p>Activation of the STING pathway is essential for restoring immune surveillance against dormant disseminated tumor cells (DTCs) in the lungs. Inhaled Mn<sup>2+</sup> has potential as a STING agonist; however, its clinical application is limited by the risk of chronic inflammation and metastasis, primarily due to reactive oxygen species (ROS) generation during inhalation. To address these risks, salvianolic acid B (salB) was identified as an effective ionophore for Mn<sup>2+</sup>, enhancing STING activation while mitigating ROS-induced inflammation. In this study, salB mitigated Mn<sup>2+</sup>-induced ROS levels and enhanced STING signaling, providing a safer, noninflammatory approach to activating immune surveillance in lung DTCs. The salB-Mn<sup>2+</sup> complexes were encapsulated in human serum albumin nanoparticles (HSA NPs) for inhalation. PET and MRI analyses revealed that intratracheal administration of HSA NP@salB-Mn<sup>2+</sup> restricted Mn<sup>2+</sup>'s systemic distribution, retaining it primarily in the lungs and minimizing central nervous system accumulation. Subsequent lung immunofluorescence further confirmed that HSA NP@salB-Mn<sup>2+</sup> effectively targeted lung metastatic lesions. Despite this extended retention in lung tissue, histological analysis showed minimal inflammation in mice treated with HSA NP@salB-Mn<sup>2+</sup>, in contrast to those receiving MnCl<sub>2</sub> or MnO. Consequently, HSA NP@salB-Mn<sup>2+</sup> demonstrated superior suppression of 4T1 cell lung metastasis in postsurgical mice relative to MnCl<sub>2</sub> or MnO. Mechanistically, salB functions as an agonist, independently activating p-STING, which synergizes with Mn<sup>2+</sup>-induced STING activation to significantly amplify signaling and downstream target engagement. In a postsurgical mouse model, the combination of HSA NP@salB-Mn<sup>2+</sup> and αPD-1 antibody significantly reduced DTC dormancy and enhanced immune detection, confirming its immunotherapeutic potential. These findings establish salB as a promising inhalable ionophore for Mn<sup>2+</sup> in DTC treatment, providing three key advantages: prolonged lung retention, reduced inflammation risk, and enhanced STING-activating efficacy.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":" ","pages":""},"PeriodicalIF":15.8,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143770700","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":"Synchronously Evoking Disulfidptosis and Ferroptosis via Systematical Glucose Deprivation Targeting SLC7A11/GSH/GPX4 Antioxidant Axis","authors":"Mengsi Zhang, Hao Zheng, Xuanqi Zhu, Shuwei Liu, Hao Jin, Yang Chen, Lanlan Wan, Songling Zhang, Hao Zhang","doi":"10.1021/acsnano.5c00730","DOIUrl":"https://doi.org/10.1021/acsnano.5c00730","url":null,"abstract":"Disulfidptosis and ferroptosis are recently identified programmed cell deaths for tumor therapy, both of which highly depend on the intracellular cystine/cysteine transformation on the cystine transporter solute carrier family 7 member 11/glutathione/glutathione peroxidase 4 (SLC7A11/GSH/GPX4) antioxidant axis. However, disulfidptosis and ferroptosis are usually asynchronous due to the opposite effect of cystine transport on them. Herein, systematic glucose deprivation, by both inhibiting upstream glucose uptake and promoting downstream glucose consumption, is proposed to synchronously evoke disulfidptosis and ferroptosis. As an example, Au nanodots and Fe-apigenin (Ap) complexes coloaded FeOOH nanoshuttles (FeOOH@Fe-Ap@Au NSs) are employed to regulate the SLC7A11/GSH/GPX4 axis for performing disulfidptosis- and ferroptosis-mediated tumor therapy synchronously. In this scenario, Au nanodots exhibit glucose oxidase-like activity when consuming massive glucose. Meanwhile, Ap can inhibit glucose uptake by downregulating glucose transporter 1, depriving glucose fundamentally. The systematical glucose deprivation limits the supplement of NADPH and suppresses cystine/cysteine transformation on the SLC7A11/GSH/GPX4 axis, thus solving the contradiction of cystine transport on disulfidptosis and ferroptosis. In addition, the efficient delivery of exogenous iron ions by FeOOH@Fe-Ap@Au NSs and self-supplied H<sub>2</sub>O<sub>2</sub> through Au nanodots-catalytic glucose oxidation facilitate intracellular Fenton reaction and therewith help to amplify ferroptosis. As a result of synchronous occurrence of disulfidptosis and ferroptosis, FeOOH@Fe-Ap@Au NSs exhibit good efficacy in an ovarian cancer therapeutic model.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"38 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766576","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":"High-Performance Bipolar Small-Molecule Organic Cathode for Wide-Temperature-Range Aqueous Zinc-Ion Batteries","authors":"Kang Hua, Quanwei Ma, Yangyang Liu, Peng Xiong, Rui Wang, Libei Yuan, Junnan Hao, Longhai Zhang, Chaofeng Zhang","doi":"10.1021/acsnano.5c00833","DOIUrl":"https://doi.org/10.1021/acsnano.5c00833","url":null,"abstract":"Organic small-molecules with redox activity are promising cathode candidates for aqueous zinc-ion batteries (AZIBs) due to their low cost, high safety and high theoretical capacity. However, their severe dissolution leads to unsatisfactory electrochemical performance. Here, a dihydro-octaaza-pentacene (DOP) compound is synthesized as a cathode for AZIBs by extending its N heterocyclic molecular structure. The extended N heterocyclic structure provides dual active sites of n-type (C═N) and p-type (−NH−) redox reactions while reducing dissolution through enhanced π-conjugation. Hence, the Zn//DOP battery demonstrates improved performance, e.g., an enhanced capacity of 360 mAh g<sup>–1</sup> at 0.05 A g<sup>–1</sup>. Even under extended temperature conditions of – 50 and 50 °C, the batteries still maintain the capacities of 172 and 312 mAh g<sup>–1</sup>, respectively. In/<i>ex-situ</i> spectroscopy provide a thorough understanding of the storage mechanisms of cations and anions (Zn<sup>2+</sup>/H<sup>+</sup> and ClO<sub>4</sub><sup>–</sup>) through multielectron transfer process occurring at dual electroactive sites. This strategy offers a promising approach to designing high-performance zinc-organic batteries for sustainable energy storage.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"29 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775896","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}
ACS NanoPub Date : 2025-04-03DOI: 10.1021/acsnano.5c03944
Arnab Ghosh, Carlos Mora Perez, Patrick Brosseau, Dmitry N. Dirin, Oleg V. Prezhdo, Maksym V. Kovalenko, Patanjali Kambhampati
{"title":"Coherent Multidimensional Spectroscopy Reveals Hot Exciton Cooling Landscapes in CsPbBr3 Quantum Dots","authors":"Arnab Ghosh, Carlos Mora Perez, Patrick Brosseau, Dmitry N. Dirin, Oleg V. Prezhdo, Maksym V. Kovalenko, Patanjali Kambhampati","doi":"10.1021/acsnano.5c03944","DOIUrl":"https://doi.org/10.1021/acsnano.5c03944","url":null,"abstract":"Hot exciton relaxation dynamics is one of the main processes in quantum dots (QD), conferring their functions in optoelectronic devices spanning photovoltaics and solar fuel generation to light emitting diodes, lasers, and quantum light sources. The challenge has been to monitor energy relaxation dynamics in parallel with resolution of excitation or excess energy. Here, we exploit the unique capacity of Coherent Multi-Dimensional Spectroscopy (CMDS) to provide the first observation of the hot exciton cooling landscape of a large size range of CsPbBr<sub>3</sub> lead halide perovskite QD, notable for their impact on optoelectronic devices, as well as their strong and unique exciton-lattice coupling. The CMDS data reveal that the hot exciton relaxation landscape is a complex function of the energy. Ab initio quantum dynamics simulations rationalize the observed behavior through energy dependent nonadiabatic exciton–phonon coupling. This first observation of cooling landscapes in QD suggests that materials science that either accelerates or slows hot exciton cooling can better be understood as a landscape to optimize for applications.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"4 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766577","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}
ACS NanoPub Date : 2025-04-03DOI: 10.1021/acsnano.4c18280
Xiumin Zhang, Ronggang Liu, Yannan Chen, Huihui Wang, Wentao Su, Yukun Song, Mingqian Tan
{"title":"Dual-Targeted Nanoparticles Hitchhiking on Lactobacillus rhamnosus Bacterial Ghosts to Alleviate Nonalcoholic Steatohepatitis","authors":"Xiumin Zhang, Ronggang Liu, Yannan Chen, Huihui Wang, Wentao Su, Yukun Song, Mingqian Tan","doi":"10.1021/acsnano.4c18280","DOIUrl":"https://doi.org/10.1021/acsnano.4c18280","url":null,"abstract":"Oral nutritional interventions for nonalcoholic steatohepatitis (NASH) have garnered significant interest due to their potential benefits. Astaxanthin (AXT) has the potential to enhance liver function and act as an effective antioxidant for NASH intervention, but its application is limited by its stability and bioavailability. This study aims to develop dual-targeted AXT nanoparticles (AXT@TWG) for precise liver-targeted delivery by ″hitchhiking″ on <i>Lactobacillus rhamnosus</i> bacterial ghosts (LBGs) to effectively intervene in NASH. <i>In vitro</i> experiments demonstrated that AXT@TWG nanoparticles significantly reduced LPS-induced reactive oxygen species production and apoptosis while effectively alleviating lipid accumulation. <i>In vivo</i> experiments demonstrated that LBGs significantly enhanced the intestinal accumulation efficiency of AXT@TWG. Pharmacokinetic evaluations revealed that the efficiency of AXT@TWG@LBGs entering the bloodstream was approximately 2.7 times higher than that of AXT@TWG nanoparticles and their accumulation in the liver was about 1.3 times greater. AXT@TWG@LBGs effectively alleviated NASH by reducing triglycerides, free fatty acids, and malondialdehyde levels by 23.07, 65.32, and 21.42%, respectively, compared to the model group, thereby mitigating lipid accumulation and enhancing antioxidant capacity. Additionally, AXT@TWG@LBGs effectively reduced insulin resistance, lowered inflammatory cytokine levels, and corrected disturbances in lipid metabolism. Therefore, this study provides a potentially effective strategy for the treatment of NASH.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"62 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775894","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}
ACS NanoPub Date : 2025-04-03DOI: 10.1021/acsnano.5c00222
Zubin Wang, Lei Jiang, Liping Heng
{"title":"Liquid Adhesion Regulation on Bioinspired Slippery Surfaces: From Theory to Application","authors":"Zubin Wang, Lei Jiang, Liping Heng","doi":"10.1021/acsnano.5c00222","DOIUrl":"https://doi.org/10.1021/acsnano.5c00222","url":null,"abstract":"Regulation of liquid adhesion on functional surfaces has attracted increasing attention due to its significant implications for fundamental research in liquid manipulation and a wide array of applications. Inspired by the slippery peristomes of <i>Nepenthes</i> pitcher plants, the concept of slippery surfaces with regulatable liquid adhesion under external stimuli was proposed and demonstrated. This review concentrates on the advancements in liquid adhesion regulation on these bioinspired slippery surfaces. Initially, we provide a concise introduction to the basic theory and design criteria of stable slippery surfaces. Following this, we summarize the characterization methods and influence factors of liquid adhesion on these surfaces. We then categorize the smart regulation modes of liquid adhesion into four key aspects: modulating the lubricant’s phase, thickness, structure, and the interactions between the lubricant and the repellent liquid. Additionally, we systematically emphasize multibehavioral liquid manipulation strategies, such as movement, merging, splitting, bouncing, and rotating, along with the emerging applications of slippery surfaces, including pipetting devices, fog collection, microreactors, biochips, and nanogenerators. Finally, we discuss the remaining challenges and future perspectives for regulating liquid adhesion and the potential applications of smart slippery surfaces.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"73 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766612","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}
ACS NanoPub Date : 2025-04-03DOI: 10.1021/acsnano.4c17011
Igor Khalin, Nagappanpillai Adarsh, Martina Schifferer, Antonia Wehn, Valeria J. Boide-Trujillo, Uta Mamrak, Joshua Shrouder, Thomas Misgeld, Severin Filser, Andrey S. Klymchenko, Nikolaus Plesnila
{"title":"Nanocarrier Drug Release and Blood-Brain Barrier Penetration at Post-Stroke Microthrombi Monitored by Real-Time Förster Resonance Energy Transfer","authors":"Igor Khalin, Nagappanpillai Adarsh, Martina Schifferer, Antonia Wehn, Valeria J. Boide-Trujillo, Uta Mamrak, Joshua Shrouder, Thomas Misgeld, Severin Filser, Andrey S. Klymchenko, Nikolaus Plesnila","doi":"10.1021/acsnano.4c17011","DOIUrl":"https://doi.org/10.1021/acsnano.4c17011","url":null,"abstract":"Nanotechnology holds great promise for improving the delivery of therapeutics to the brain. However, current approaches often operate at the organ or tissue level and are limited by the lack of tools to dynamically monitor cargo delivery in vivo. We have developed highly fluorescent lipid nanodroplets (LNDs) that enable tracking of nanocarrier behavior at the subcellular level while also carrying a Förster resonance energy transfer (FRET)-based drug delivery detection system (FedEcs) capable of monitoring cargo release in vivo. Using two-photon microscopy, we demonstrate that circulating LNDs in naïve mouse brain vasculature exhibit 3D real-time FRET changes, showing size-dependent stability over 2 h in blood circulation. Further, in the Nanostroke model, dynamic intravital two-photon imaging revealed that LNDs accumulated within cerebral postischemic microthrombi, where they released their cargo significantly faster than in normal blood circulation. Furthermore, the blood-brain barrier (BBB) became permeable at the microclot sites thereby allowing accumulated FedEcs-LNDs to cross the BBB and deliver their cargo to the brain parenchyma. This microthrombi-associated translocation was confirmed at the ultrastructural level via volume-correlative light-electron microscopy. Consequently, FedEcs represents an advanced tool to quantitatively study the biodistribution and cargo release of nanocarriers at high resolution in real-time. By enabling us to resolve passive targeting mechanisms poststroke, specifically, accumulation, degradation, and extravasation via poststroke microthrombi, this system could significantly enhance the translational validation of nanocarriers for future treatments of brain diseases.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"23 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775893","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}
ACS NanoPub Date : 2025-04-02DOI: 10.1021/acsnano.5c00816
Yun An, Taiping Hu, Quanquan Pang, Shenzhen Xu
{"title":"Observing Li Nucleation at the Li Metal–Solid Electrolyte Interface in All-Solid-State Batteries","authors":"Yun An, Taiping Hu, Quanquan Pang, Shenzhen Xu","doi":"10.1021/acsnano.5c00816","DOIUrl":"https://doi.org/10.1021/acsnano.5c00816","url":null,"abstract":"Benefiting from the significantly improved energy density and safety, all-solid-state lithium batteries (ASSLBs) are considered to be one of the most promising next-generation energy technologies. Their practical applications, however, are strongly impeded by Li dendrite formation. Despite this recognized challenge, a comprehensive understanding of the Li dendrite nucleation and formation mechanism remains elusive. In particular, the initial locations of Li dendrite formation are still ambiguous: do Li clusters form directly at the Li anode surface, inside the bulk solid electrolyte (SE), or within the solid-electrolyte interphase (SEI)? Here, based on the deep-potential molecular dynamics simulations combined with enhanced sampling techniques, we investigate the atomic-level mechanism of Li cluster nucleation and formation at the Li anode/SE interface. We observe that an isolated Li cluster initially forms inside the SEI between the Li<sub>6</sub>PS<sub>5</sub>Cl SE and the Li metal anode, located ∼1 nm away from the Li anode/SEI boundary. The local electronic structure of the spontaneously formed SEI is found to be a key factor enabling the Li cluster formation within the SEI, in which a significantly decreased band gap could facilitate electronic conduction through the SEI and reduce Li<sup>+</sup> ions to metallic Li atoms therein. Our work provides atomic-level insights into Li-dendrite nucleation at anode/SE interfaces in ASSLBs and could guide future design for developing Li-dendrite-inhibiting strategies.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"71 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766611","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}
ACS NanoPub Date : 2025-04-02DOI: 10.1021/acsnano.4c14805
Huijie He, Xueyang Zhen, Ran Chen, Xing Chen
{"title":"Mechanisms of Electron Transfer between Metal Clusters and Molecules in Plasmonic Junctions","authors":"Huijie He, Xueyang Zhen, Ran Chen, Xing Chen","doi":"10.1021/acsnano.4c14805","DOIUrl":"https://doi.org/10.1021/acsnano.4c14805","url":null,"abstract":"Surface plasmons can localize the optical field and energy at the nanoscale, significantly enhancing various light–matter interactions, such as in photocatalysis. The hot electrons generated by plasmon decay play a crucial role in driving chemical reactions. To better understand the mechanisms behind electron transfer, we have developed a polarizability bond model to visualize how the electron transfer influences bond polarization. In this study, we examine molecule-metal coupled systems, where the molecules of varying dimensions are embedded between metal clusters. Our findings show that electron transfer is significantly enhanced when the molecular component is directly excited. The efficiency of electron transfer decreases as the cavity gap widens. Distinct electron transfer behaviors are observed across different molecule-metal coupled systems with the most pronounced enhancement occurring between one-dimensional molecules and metal clusters. Further analysis reveals that the atoms in the first and second layers of the metal clusters are critical in facilitating interfacial polarization. Intramolecular bond polarization is particularly strong when electron excitation originates from the molecular component, and bonds near the cavity center or those aligned with near-field polarization are more easily polarized by plasmon excitation. This study reveals the atomic-level electron transfer mechanisms and provides a theoretical basis for optimizing plasmon-mediated catalytic reactions.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"183 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758619","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}