Emmanuel U Osuagwu,Dalton Compton,Erin E Taylor,Hirotomo Nishihara,Nicholas A Strange,Nicholas P Stadie
Materials that exhibit negative thermal expansion (NTE) are of fundamental interest due to their rarity and counterintuitive behavior. While research in this area has been directed toward the discovery of materials that display NTE and explaining its origin, there has been less attention to describing the complexities of a secondary phase or other guests that could influence the magnitude and mechanism of NTE. We report herein that zeolite-templated carbon (ZTC), a soft carbonaceous framework solid with ordered microporosity, exhibits a large and widely tunable thermal expansion in the presence of adsorbed guests. For ZTC in the presence of CO2 at 1 bar, the largest coefficient of isotropic NTE ever observed (-8.4 × 10-4 K-1) is measured between 200 and 220 K. These results comprise a tunable mechanism of thermal expansion based on the interaction between two independent, positively expanding phases that together give rise to an anomalous guest-induced NTE under certain conditions.
{"title":"Guest-Induced Large and Tunable Negative Thermal Expansion in Soft Microporous Carbon.","authors":"Emmanuel U Osuagwu,Dalton Compton,Erin E Taylor,Hirotomo Nishihara,Nicholas A Strange,Nicholas P Stadie","doi":"10.1021/acsnano.5c17601","DOIUrl":"https://doi.org/10.1021/acsnano.5c17601","url":null,"abstract":"Materials that exhibit negative thermal expansion (NTE) are of fundamental interest due to their rarity and counterintuitive behavior. While research in this area has been directed toward the discovery of materials that display NTE and explaining its origin, there has been less attention to describing the complexities of a secondary phase or other guests that could influence the magnitude and mechanism of NTE. We report herein that zeolite-templated carbon (ZTC), a soft carbonaceous framework solid with ordered microporosity, exhibits a large and widely tunable thermal expansion in the presence of adsorbed guests. For ZTC in the presence of CO2 at 1 bar, the largest coefficient of isotropic NTE ever observed (-8.4 × 10-4 K-1) is measured between 200 and 220 K. These results comprise a tunable mechanism of thermal expansion based on the interaction between two independent, positively expanding phases that together give rise to an anomalous guest-induced NTE under certain conditions.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"50 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146042494","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}
Clinical management of trigeminal neuralgia (TN) is hindered by poor neural bioavailability and systemic toxicity of oral drugs. While the nasal route offers a direct pathway to target the trigeminal nerve, rapid mucociliary clearance and competition from systemic absorption limit its effectiveness. To address these limitations, this study aimed to develop a biomimetic nasal gel system for targeted drug delivery to the trigeminal nerve. Inspired by the neurotropism of rabies virus, we engineered a thermoresponsive nasal spray gel (OMRLP@NSG). The system utilizes rabies virus glycoprotein (RVG)-modified liposomes coloaded with oxcarbazepine and mecobalamin. The liposomal formulation was specifically chosen to enhance drug stability, facilitate mucosal penetration, and provide a platform for neuron-specific targeting via RVG modification. Upon nasal administration, the OMRLP@NSG transitions from spray to gel, enhancing nasal distribution, mucosal adhesion, and neuron-specific targeting. Pharmacokinetics demonstrated a 3 h earlier Tmax and 537.25% higher relative bioavailability in trigeminal nerves versus oral Trileptal. OMRLP@NSG at 1/10th the Trileptal dose achieved comparable trigeminal nerve exposure while reducing off-target site concentrations by 74.18∼92.00% (plasma, brain, liver). Pharmacodynamics showed that the OMRLP@NSG significantly alleviated TN pain in rats, increasing the pain threshold by 3.92-fold over Trileptal. It also normalized the expression of pain-related neuropeptides (substance P and β-endorphin) to 112.05 and 98.81% of normal levels, respectively. Mechanistically, it suppressed P2 × 7R/NLRP3 inflammasome activation, downregulating IL-1β and TNF-α, thereby reducing neuronal damage and promoting remyelination. Additionally, long-term toxicity studies confirmed the favorable in vivo biosafety. This strategy transcends conventional systemic administration paradigms by resolving the tripartite challenge of spatial control, temporal retention, and cellular precision, thereby addressing the critical clinical demand for effective nose-to-brain delivery in trigeminal neuralgia.
{"title":"Rabies Virus Glycoprotein-Decorated Liposomes in Thermosensitive Nasal Spray Gels: Facilitating Retrograde Neural Transport for Targeted Trigeminal Neuralgia Therapy.","authors":"Guanlin Wang,Xi Kong,Xiaofan Li,Chuangxin Chen,Kaiqing Zhang,Yue Zhou,Xiao Yue,Siyuan Peng,Wentao Wu,Wenhao Wang,Ziyu Zhao,Ying Huang,Xin Pan,Chuanbin Wu,Xuejuan Zhang","doi":"10.1021/acsnano.5c12628","DOIUrl":"https://doi.org/10.1021/acsnano.5c12628","url":null,"abstract":"Clinical management of trigeminal neuralgia (TN) is hindered by poor neural bioavailability and systemic toxicity of oral drugs. While the nasal route offers a direct pathway to target the trigeminal nerve, rapid mucociliary clearance and competition from systemic absorption limit its effectiveness. To address these limitations, this study aimed to develop a biomimetic nasal gel system for targeted drug delivery to the trigeminal nerve. Inspired by the neurotropism of rabies virus, we engineered a thermoresponsive nasal spray gel (OMRLP@NSG). The system utilizes rabies virus glycoprotein (RVG)-modified liposomes coloaded with oxcarbazepine and mecobalamin. The liposomal formulation was specifically chosen to enhance drug stability, facilitate mucosal penetration, and provide a platform for neuron-specific targeting via RVG modification. Upon nasal administration, the OMRLP@NSG transitions from spray to gel, enhancing nasal distribution, mucosal adhesion, and neuron-specific targeting. Pharmacokinetics demonstrated a 3 h earlier Tmax and 537.25% higher relative bioavailability in trigeminal nerves versus oral Trileptal. OMRLP@NSG at 1/10th the Trileptal dose achieved comparable trigeminal nerve exposure while reducing off-target site concentrations by 74.18∼92.00% (plasma, brain, liver). Pharmacodynamics showed that the OMRLP@NSG significantly alleviated TN pain in rats, increasing the pain threshold by 3.92-fold over Trileptal. It also normalized the expression of pain-related neuropeptides (substance P and β-endorphin) to 112.05 and 98.81% of normal levels, respectively. Mechanistically, it suppressed P2 × 7R/NLRP3 inflammasome activation, downregulating IL-1β and TNF-α, thereby reducing neuronal damage and promoting remyelination. Additionally, long-term toxicity studies confirmed the favorable in vivo biosafety. This strategy transcends conventional systemic administration paradigms by resolving the tripartite challenge of spatial control, temporal retention, and cellular precision, thereby addressing the critical clinical demand for effective nose-to-brain delivery in trigeminal neuralgia.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"56 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034030","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}
Xinya Zhao,Kai Guo,Xueli Xu,Li Xian Yip,Ao Liu,Gongzheng Wang,Jin Cui,Yufang Gong,Qiang Zhu,David Tai Leong,Ximing Wang,Xiao Sun
Liver fibrosis is a chronic, progressive liver disease that can lead to irreversible cirrhosis and hepatocellular carcinoma. However, the early and accurate diagnosis of liver fibrosis remains a dilemma in clinical research. In this study, a gadolinium-palladium nanocluster with decapeptide (L10) and glucose oxidase (GOx) grafting (GPPGL) was developed for accurate liver fibrosis staging and synergistic antifibrotic therapy. L10, with a strong affinity for Collagen I, can mediate this nanoplatform to target the liver fibrosis region, enabling it to achieve enhanced accumulation in the liver. Therefore, GPPGL, with magnetic resonance imaging (MRI) contrast enhancement capacity, can accurately grade liver fibrosis to different degrees. Then, three-dimensional reconstruction and histogram-based features of MRI images are further conducted to quantitatively and qualitatively analyze the degree of liver fibrosis. GOx, with strong glucose consumption, can enhance the catalase- and peroxidase-like activities of the nanoplatform in a cascade. Systemic delivery of GPPGL can synergistically inhibit the activation of hepatic stellate cells and reduce their collagen production by alleviating liver fibrosis hypoxia, inducing ferroptosis, and achieving starvation therapy. No significant side effects during both histological and hematological examinations were observed. Therefore, GPPGL has promising prospects for achieving accurate liver fibrosis staging and synergistic antifibrotic therapy.
{"title":"Heterogeneous Magnetic Resonance Nanoprobe for Assisting Liver Fibrosis Three-Dimensional Reconstruction and Cascaded Therapy.","authors":"Xinya Zhao,Kai Guo,Xueli Xu,Li Xian Yip,Ao Liu,Gongzheng Wang,Jin Cui,Yufang Gong,Qiang Zhu,David Tai Leong,Ximing Wang,Xiao Sun","doi":"10.1021/acsnano.5c17091","DOIUrl":"https://doi.org/10.1021/acsnano.5c17091","url":null,"abstract":"Liver fibrosis is a chronic, progressive liver disease that can lead to irreversible cirrhosis and hepatocellular carcinoma. However, the early and accurate diagnosis of liver fibrosis remains a dilemma in clinical research. In this study, a gadolinium-palladium nanocluster with decapeptide (L10) and glucose oxidase (GOx) grafting (GPPGL) was developed for accurate liver fibrosis staging and synergistic antifibrotic therapy. L10, with a strong affinity for Collagen I, can mediate this nanoplatform to target the liver fibrosis region, enabling it to achieve enhanced accumulation in the liver. Therefore, GPPGL, with magnetic resonance imaging (MRI) contrast enhancement capacity, can accurately grade liver fibrosis to different degrees. Then, three-dimensional reconstruction and histogram-based features of MRI images are further conducted to quantitatively and qualitatively analyze the degree of liver fibrosis. GOx, with strong glucose consumption, can enhance the catalase- and peroxidase-like activities of the nanoplatform in a cascade. Systemic delivery of GPPGL can synergistically inhibit the activation of hepatic stellate cells and reduce their collagen production by alleviating liver fibrosis hypoxia, inducing ferroptosis, and achieving starvation therapy. No significant side effects during both histological and hematological examinations were observed. Therefore, GPPGL has promising prospects for achieving accurate liver fibrosis staging and synergistic antifibrotic therapy.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"19 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034029","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}
Philipp Wutz,Yinong Zhang,Felix Hofmann,Paulo E Faria Junior,Yao Lu,Philip Soul,Yu-Han Bao,Kenji Watanabe,Takashi Taniguchi,Jaroslav Fabian,Sebastian Bange,John M Lupton,Kai-Qiang Lin
Semiconducting quantum wells have enabled revolutionary applications in diode lasers, IR photodetectors, and optical modulators. Recently, van der Waals (vdW) quantum wells have emerged as a promising frontier, offering inherently atomically sharp interfaces and facile integration into device structures without the constraints of lattice matching. Tunability of intersubband transitions is essential for applications of quantum wells but remains unexplored in vdW structures. Here, we report valley-selective, electric-field-activated electronic Raman scattering from intersubband transitions in natural WSe2 multilayers and demonstrate electrical tunability by over 100 meV. We validate the generality of such tunability in 3 to 7 layers of WSe2 and quantify the effective dipole moments and polarizabilities that determine the quantum-confined Stark effect. These intersubband transitions are also found in artificially stacked multilayers, where they can be manipulated by twist angle. Our work lays foundations for exploiting vdW quantum wells in next-generation optoelectronic applications, including tunable photodiodes and atomically compact IR spectrometers.
{"title":"Electrical Control of Intersubband Transitions in Few-Layer WSe2 Multivalley Quantum Wells Probed by Electronic Raman Scattering.","authors":"Philipp Wutz,Yinong Zhang,Felix Hofmann,Paulo E Faria Junior,Yao Lu,Philip Soul,Yu-Han Bao,Kenji Watanabe,Takashi Taniguchi,Jaroslav Fabian,Sebastian Bange,John M Lupton,Kai-Qiang Lin","doi":"10.1021/acsnano.5c08378","DOIUrl":"https://doi.org/10.1021/acsnano.5c08378","url":null,"abstract":"Semiconducting quantum wells have enabled revolutionary applications in diode lasers, IR photodetectors, and optical modulators. Recently, van der Waals (vdW) quantum wells have emerged as a promising frontier, offering inherently atomically sharp interfaces and facile integration into device structures without the constraints of lattice matching. Tunability of intersubband transitions is essential for applications of quantum wells but remains unexplored in vdW structures. Here, we report valley-selective, electric-field-activated electronic Raman scattering from intersubband transitions in natural WSe2 multilayers and demonstrate electrical tunability by over 100 meV. We validate the generality of such tunability in 3 to 7 layers of WSe2 and quantify the effective dipole moments and polarizabilities that determine the quantum-confined Stark effect. These intersubband transitions are also found in artificially stacked multilayers, where they can be manipulated by twist angle. Our work lays foundations for exploiting vdW quantum wells in next-generation optoelectronic applications, including tunable photodiodes and atomically compact IR spectrometers.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"186 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034056","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}
Shahab Amirabadi,Zitang Wei,Michelle Quien,Michael S Strano
Two-dimensional (2D) polyaramids (2DPAs) have recently emerged as a class of organic 2D nanomaterials exhibiting high mechanical strength and gas barrier properties. However, their characterization remains challenging due to their hybrid molecular structure, combining features of conventional 2D inorganic materials with those of organic polymers, which results in limited solvent dispersibility. Herein, we elucidate how thermal degradation, monitored by thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), can provide chemical insights into the end group and discoidal molecular structure of 2DPAs. We find that distinct thermogravimetric loss regimes correlate with the ratio of aromatic-to-end group proton peak integrations from 1H NMR, referred to as the r value. This informs the end group chemical composition, which can be linked to a consistent set of mechanistic steps for thermal degradation. For instance, isopropyl-ester-terminated 2DPA-1 decomposes first through a six-centered intermediate formed from the intramolecular methyl hydrogen interaction with the carbonyl, yielding 1-propene after cleavage of the C-O bond, consistent with mass spectrometry. Kinetic parameters, including activation energies, are determined using the Coats-Redfern method from TGA data, with values spanning 11.8 to 63.6 kJ/mol. The analysis is extended to ethyl-ester- and carboxyl-terminated 2DPA-1 for comparison. This study establishes the utility of TGA and TGA-MS as versatile characterization tools for 2D polyaramids with distinct terminal groups, allowing measurement and therefore control of nanoplatelet functionalization and molecular weight.
{"title":"Thermogravimetric Analysis and Mass Spectrometry of 2D Polyaramid Nanoplatelets.","authors":"Shahab Amirabadi,Zitang Wei,Michelle Quien,Michael S Strano","doi":"10.1021/acsnano.5c19391","DOIUrl":"https://doi.org/10.1021/acsnano.5c19391","url":null,"abstract":"Two-dimensional (2D) polyaramids (2DPAs) have recently emerged as a class of organic 2D nanomaterials exhibiting high mechanical strength and gas barrier properties. However, their characterization remains challenging due to their hybrid molecular structure, combining features of conventional 2D inorganic materials with those of organic polymers, which results in limited solvent dispersibility. Herein, we elucidate how thermal degradation, monitored by thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), can provide chemical insights into the end group and discoidal molecular structure of 2DPAs. We find that distinct thermogravimetric loss regimes correlate with the ratio of aromatic-to-end group proton peak integrations from 1H NMR, referred to as the r value. This informs the end group chemical composition, which can be linked to a consistent set of mechanistic steps for thermal degradation. For instance, isopropyl-ester-terminated 2DPA-1 decomposes first through a six-centered intermediate formed from the intramolecular methyl hydrogen interaction with the carbonyl, yielding 1-propene after cleavage of the C-O bond, consistent with mass spectrometry. Kinetic parameters, including activation energies, are determined using the Coats-Redfern method from TGA data, with values spanning 11.8 to 63.6 kJ/mol. The analysis is extended to ethyl-ester- and carboxyl-terminated 2DPA-1 for comparison. This study establishes the utility of TGA and TGA-MS as versatile characterization tools for 2D polyaramids with distinct terminal groups, allowing measurement and therefore control of nanoplatelet functionalization and molecular weight.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"7 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034032","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}
Km Mamata Patel, , , Saurabh Chaubey, , , Yogita Rani, , and , Prabhat Tripathi*,
Electric fields often lead to the opening of pores by activating statistical defects in lipid bilayer membranes. These electropores are ubiquitous in biology and are widely used in biotechnology and medicine. Our understanding of electropores has been limited by the poor time resolution of experiments, causing a discrepancy in the observed time scale of electropores. Here, using high-resolution ionic current measurements, we have characterized the μs–ms duration Å-nm scale single pores in the vertical bilayer membranes. Our experiments on over 2500 membranes revealed highly nonexponential kinetics of pores due to the dynamic heterogeneity of defects, and we were able to resolve the population of hydrophobic and hydrophilic pores, which were postulated before in theory but rarely resolved in experiments. Such dynamic heterogeneity of defects is likely a general feature of lipid membranes for selectively translocating diverse sets of molecules across cellular compartments on different time scales without requiring a receptor channel.
{"title":"High-Resolution Characterization of Single Å-nm Scale Pores Revealed Dynamical Heterogeneity of Statistical Defects in Lipid Bilayer Membranes","authors":"Km Mamata Patel, , , Saurabh Chaubey, , , Yogita Rani, , and , Prabhat Tripathi*, ","doi":"10.1021/acsnano.5c16552","DOIUrl":"10.1021/acsnano.5c16552","url":null,"abstract":"<p >Electric fields often lead to the opening of pores by activating statistical defects in lipid bilayer membranes. These electropores are ubiquitous in biology and are widely used in biotechnology and medicine. Our understanding of electropores has been limited by the poor time resolution of experiments, causing a discrepancy in the observed time scale of electropores. Here, using high-resolution ionic current measurements, we have characterized the μs–ms duration Å-nm scale single pores in the vertical bilayer membranes. Our experiments on over 2500 membranes revealed highly nonexponential kinetics of pores due to the dynamic heterogeneity of defects, and we were able to resolve the population of hydrophobic and hydrophilic pores, which were postulated before in theory but rarely resolved in experiments. Such dynamic heterogeneity of defects is likely a general feature of lipid membranes for selectively translocating diverse sets of molecules across cellular compartments on different time scales without requiring a receptor channel.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"20 4","pages":"3582–3592"},"PeriodicalIF":16.0,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021705","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}
DNA molecular circuits offer significant promise for biomedical applications by combining computational functionality with inherent biocompatibility. However, their operational logic fundamentally differs from electronic systems as they utilize the physical presence or absence of DNA strands rather than voltage levels to encode information. This distinction creates a critical barrier for implementing single-rail NOT gates. Consequently, existing systems typically employ dual-rail architectures that increase the complexity and elevate leakage risks. To address this limitation, we developed optically and thermally controlled NOT gates that perform rapid logical inversion while maintaining compatibility with both polymerase-driven and toehold-mediated circuit systems. We validated these gates in multilayer computational networks and demonstrated their practical utility across diverse biosensing applications, including molecular diagnostics and live-cell imaging. This work establishes a robust platform for scalable DNA computing with direct translational potential in biological environments.
{"title":"Stimulus-Responsive NOT Gate for Single-Rail DNA Logic Circuits and Biosensing","authors":"Xingyu Zhong, , , Tianci Xie, , , Xi Gong, , , Qidong Xia*, , , Shaogang Wang*, , and , Tongbo Wu*, ","doi":"10.1021/acsnano.5c17487","DOIUrl":"10.1021/acsnano.5c17487","url":null,"abstract":"<p >DNA molecular circuits offer significant promise for biomedical applications by combining computational functionality with inherent biocompatibility. However, their operational logic fundamentally differs from electronic systems as they utilize the physical presence or absence of DNA strands rather than voltage levels to encode information. This distinction creates a critical barrier for implementing single-rail NOT gates. Consequently, existing systems typically employ dual-rail architectures that increase the complexity and elevate leakage risks. To address this limitation, we developed optically and thermally controlled NOT gates that perform rapid logical inversion while maintaining compatibility with both polymerase-driven and toehold-mediated circuit systems. We validated these gates in multilayer computational networks and demonstrated their practical utility across diverse biosensing applications, including molecular diagnostics and live-cell imaging. This work establishes a robust platform for scalable DNA computing with direct translational potential in biological environments.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"20 4","pages":"3653–3666"},"PeriodicalIF":16.0,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021648","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}
Kang Wu, , , Xiaozhi Zhan, , , Peilin Ran, , , Fangwei Wang, , , Tao Zhu*, , , Jinkui Zhao*, , and , Enyue Zhao*,
The solid electrolyte interphase (SEI) governs key electrochemical properties in batteries. While additive-driven SEI engineering constitutes the most promising strategy for tailoring interfacial composition, the impact of specific additives on SEI’s dynamic evolution remains unresolved. Herein, we performed operando neutron reflectometry (NR) to quantitatively resolve the SEI’s structural dynamics under cycling conditions. Employing model additives with well-defined decomposition mechanisms, fluoroethylene carbonate (FEC) and vinylene carbonate (VC), we establish a robust operando NR framework that enables transferable mechanistic insights for emerging additive systems. Our data reveal contrasting SEI architectures: FEC produces a thin, inorganic-rich SEI (LiF-dominant) that enhances mechanical integrity and cycling stability, while VC yields a flexible organic-dominated SEI which mitigates stress-induced microcracking. These findings provide atomically resolved design principles for advanced electrolyte additives via operando interfacial analysis, advancing high-energy-density Li-ion batteries and beyond.
{"title":"Quantifying the Dynamic and Additives-Dependent Interface Evolution by Operando Neutron Reflectometry","authors":"Kang Wu, , , Xiaozhi Zhan, , , Peilin Ran, , , Fangwei Wang, , , Tao Zhu*, , , Jinkui Zhao*, , and , Enyue Zhao*, ","doi":"10.1021/acsnano.5c20565","DOIUrl":"10.1021/acsnano.5c20565","url":null,"abstract":"<p >The solid electrolyte interphase (SEI) governs key electrochemical properties in batteries. While additive-driven SEI engineering constitutes the most promising strategy for tailoring interfacial composition, the impact of specific additives on SEI’s dynamic evolution remains unresolved. Herein, we performed <i>operando</i> neutron reflectometry (NR) to quantitatively resolve the SEI’s structural dynamics under cycling conditions. Employing model additives with well-defined decomposition mechanisms, fluoroethylene carbonate (FEC) and vinylene carbonate (VC), we establish a robust <i>operando</i> NR framework that enables transferable mechanistic insights for emerging additive systems. Our data reveal contrasting SEI architectures: FEC produces a thin, inorganic-rich SEI (LiF-dominant) that enhances mechanical integrity and cycling stability, while VC yields a flexible organic-dominated SEI which mitigates stress-induced microcracking. These findings provide atomically resolved design principles for advanced electrolyte additives via <i>operando</i> interfacial analysis, advancing high-energy-density Li-ion batteries and beyond.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"20 4","pages":"3855–3866"},"PeriodicalIF":16.0,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021769","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}
Sodium-ion batteries hold promise for grid-scale energy storage thanks to abundant resources and superior safety, but their wide-temperature operation is hindered by sluggish electronic–ionic transport and structural instability of cathode materials. Herein, a cation-intermixing strategy driven by stoichiometric regulation is proposed for Na2+2xFe2–x(SO4)3 cathodes, which can simultaneously enhance structural stability, improve charge transfer, and facilitate Na+ transport kinetics. Specifically, derived Fe vacancies and concomitant Na+ insertion reconstruct the electronic environment, strengthening Fe–O bonds to stabilize the crystal framework while optimizing Fe 3d electron energy level distribution to facilitate charge transfer. This alteration concurrently widens Na+ migration channels and reduces diffusion barriers, enabling rapid ion transport. Consequently, the Na2.48Fe1.76(SO4)3 cathode (x = 0.24 in Na2+2xFe2–x(SO4)3, with a Na/Fe molar ratio of 1.4) with optimal cation intermixing exhibits exceptional wide-temperature performance. It delivers 85.9% capacity retention following 3000 cycles at 30 C (25 °C) and 88.3% following 4000 cycles at 1 C (−20 °C). Even at an ultrahigh 100 C (60 °C), it still retains 83.2% relative to its capacity measured at 25 °C and 0.1 C. This work provides a stoichiometry-driven approach to designing superior-performance sulfate-based cathodes for wide-temperature sodium-ion batteries.
{"title":"Modulating Cation Intermixing Behavior Enables Wide-Temperature-Stable Na2+2xFe2–x(SO4)3 Cathode for Sodium-Ion Batteries","authors":"Jingjing Hou, , , Shizhong Lv, , , Jian Liu, , , Jiaji Tang, , , Yuwei Wang, , , Lirui Liu, , , Zaohui He, , , Gang Sun, , , Ai-Min Lv, , , Liang Deng*, , , Yunlong Zhang*, , , Lei Zhao*, , and , Zhenbo Wang*, ","doi":"10.1021/acsnano.5c18360","DOIUrl":"10.1021/acsnano.5c18360","url":null,"abstract":"<p >Sodium-ion batteries hold promise for grid-scale energy storage thanks to abundant resources and superior safety, but their wide-temperature operation is hindered by sluggish electronic–ionic transport and structural instability of cathode materials. Herein, a cation-intermixing strategy driven by stoichiometric regulation is proposed for Na<sub>2+2<i>x</i></sub>Fe<sub>2–<i>x</i></sub>(SO<sub>4</sub>)<sub>3</sub> cathodes, which can simultaneously enhance structural stability, improve charge transfer, and facilitate Na<sup>+</sup> transport kinetics. Specifically, derived Fe vacancies and concomitant Na<sup>+</sup> insertion reconstruct the electronic environment, strengthening Fe–O bonds to stabilize the crystal framework while optimizing Fe 3d electron energy level distribution to facilitate charge transfer. This alteration concurrently widens Na<sup>+</sup> migration channels and reduces diffusion barriers, enabling rapid ion transport. Consequently, the Na<sub>2.48</sub>Fe<sub>1.76</sub>(SO<sub>4</sub>)<sub>3</sub> cathode (<i>x</i> = 0.24 in Na<sub>2+2<i>x</i></sub>Fe<sub>2–<i>x</i></sub>(SO<sub>4</sub>)<sub>3</sub>, with a Na/Fe molar ratio of 1.4) with optimal cation intermixing exhibits exceptional wide-temperature performance. It delivers 85.9% capacity retention following 3000 cycles at 30 C (25 °C) and 88.3% following 4000 cycles at 1 C (−20 °C). Even at an ultrahigh 100 C (60 °C), it still retains 83.2% relative to its capacity measured at 25 °C and 0.1 C. This work provides a stoichiometry-driven approach to designing superior-performance sulfate-based cathodes for wide-temperature sodium-ion batteries.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"20 4","pages":"3748–3761"},"PeriodicalIF":16.0,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146015171","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}
Jillian M. Buriak, , , Deji Akinwande, , , Natalie Artzi, , , Sara Bals, , , Erick. M. Carreira, , , Yang Chai, , , Warren C. W. Chan, , , Christopher J. Chang, , , Chunying Chen, , , Xiaodong Chen, , , Cathleen Crudden, , , Vincent Dusastre, , , Mark. C. Hersam, , , Anita Ho-Baillie, , , Tony Hu, , , Prashant V. Kamat, , , Kazunori Kataoka, , , Il-Doo Kim, , , Yan Li, , , Xing Yi Ling, , , Luis M. Liz-Marzán, , , Maria R. Lukatskaya, , , Jill Millstone, , , Teri W. Odom, , , Rahmi Oklu, , , Wolfgang J. Parak, , , Mathieu Salanne, , , Paolo Samorì, , , Raymond E. Schaak, , , Kirk S. Schanze, , , Tsuyoshi Sekitani, , , Sara. E. Skrabalak, , , Berend Smit, , , Ajay Sood, , , Ilja K. Voets, , , Katherine A. Willets, , , Huolin Xin, , and , Jinhua Ye,
{"title":"Peer Review and AI: Your (Human) Opinion Is What Matters","authors":"Jillian M. Buriak, , , Deji Akinwande, , , Natalie Artzi, , , Sara Bals, , , Erick. M. Carreira, , , Yang Chai, , , Warren C. W. Chan, , , Christopher J. Chang, , , Chunying Chen, , , Xiaodong Chen, , , Cathleen Crudden, , , Vincent Dusastre, , , Mark. C. Hersam, , , Anita Ho-Baillie, , , Tony Hu, , , Prashant V. Kamat, , , Kazunori Kataoka, , , Il-Doo Kim, , , Yan Li, , , Xing Yi Ling, , , Luis M. Liz-Marzán, , , Maria R. Lukatskaya, , , Jill Millstone, , , Teri W. Odom, , , Rahmi Oklu, , , Wolfgang J. Parak, , , Mathieu Salanne, , , Paolo Samorì, , , Raymond E. Schaak, , , Kirk S. Schanze, , , Tsuyoshi Sekitani, , , Sara. E. Skrabalak, , , Berend Smit, , , Ajay Sood, , , Ilja K. Voets, , , Katherine A. Willets, , , Huolin Xin, , and , Jinhua Ye, ","doi":"10.1021/acsnano.6c00490","DOIUrl":"10.1021/acsnano.6c00490","url":null,"abstract":"","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"20 4","pages":"3171–3174"},"PeriodicalIF":16.0,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021762","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}