Hyeongwoo Lee, Huitae Joo, Taeyoung Moon, Yeonjeong Koo, Sujeong Kim, Soo Ho Choi, Uk Jung Kang, Kyung-Hwan Jin, Ki Kang Kim, Deep Jariwala, Kyoung-Duck Park
The exponential growth of digital information presents a critical challenge for the sustainable data preservation. While optical data storage (ODS) systems have emerged as a promising solution for economical and long-term data archiving, conventional ODS technologies face limitations due to the optical diffraction limit and inability to harness emerging excitonic properties, restricting further improvements in storage density. Here, we demonstrate a multibit excitonic data storage (EDS) system by generating nanoscale metal–insulator–semiconductor tunnel junctions. By precisely modulating the extent of Ohmic contact within these junctions, we control the doping-related exciton recombination dynamics of atomically thin semiconductors. The modulated EDS system exhibits three discrete photoluminescence intensity levels within a unit data-space of ∼60 nm, demonstrating nanoscale multilevel data encoding. Our work provides a strategy for ultrathin nano-EDS technologies for future advancements in archival storage systems.
{"title":"Nanoscale Metal–Insulator–Semiconductor Tunnel Junction for Multibit Excitonic Data Storage","authors":"Hyeongwoo Lee, Huitae Joo, Taeyoung Moon, Yeonjeong Koo, Sujeong Kim, Soo Ho Choi, Uk Jung Kang, Kyung-Hwan Jin, Ki Kang Kim, Deep Jariwala, Kyoung-Duck Park","doi":"10.1021/acsnano.5c15152","DOIUrl":"https://doi.org/10.1021/acsnano.5c15152","url":null,"abstract":"The exponential growth of digital information presents a critical challenge for the sustainable data preservation. While optical data storage (ODS) systems have emerged as a promising solution for economical and long-term data archiving, conventional ODS technologies face limitations due to the optical diffraction limit and inability to harness emerging excitonic properties, restricting further improvements in storage density. Here, we demonstrate a multibit excitonic data storage (EDS) system by generating nanoscale metal–insulator–semiconductor tunnel junctions. By precisely modulating the extent of Ohmic contact within these junctions, we control the doping-related exciton recombination dynamics of atomically thin semiconductors. The modulated EDS system exhibits three discrete photoluminescence intensity levels within a unit data-space of ∼60 nm, demonstrating nanoscale multilevel data encoding. Our work provides a strategy for ultrathin nano-EDS technologies for future advancements in archival storage systems.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"35 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145674010","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}
Nanomedicine offers promising strategies for targeted drug delivery, imaging, and molecular-level therapies. However, the clinical translation of nanomedicine has often been hindered by the complex interactions of nanoparticles (NPs) with biological systems. This study investigates a cell-based delivery platform designed to overcome some of these limitations, using clinical-grade tumor-infiltrating lymphocytes (TILs) as biological carriers of boron carbide (B4C) NPs in boron neutron capture therapy (BNCT). Biological vectors, such as TILs, could enable selective tumor targeting, leading to highly localized 10B levels and minimizing off-target accumulation. We evaluated the uptake and retention of composite Fe2O3-B4C NPs (FeBNPs) using both immortalized Jurkat T cells and primary human TILs. Both cell types efficiently internalized FeBNPs without cytotoxic effects, maintained their functionalities, and retained the boron-rich NPs for up to 72 h. Imaging confirmed intracellular localization, and neutron autoradiography demonstrated that TILs accumulated sufficient 10B for therapeutic efficacy, eliminating the need for isotopically enriched compounds like L-4-boronophenylalanine (BPA) or sodium borocaptate (BSH). Coculture experiments with Jurkat and HeLa cells confirmed that lymphocyte-delivered boron could mediate localized radiation damage via neutron capture. These findings support the concept of TILs as "Trojan Horses" for boron delivery, allowing for overcoming traditional barriers in NP-based therapies and taking advantage of their innate tumor-homing ability. This approach not only enhances BNCT selectivity and efficacy but also supports the integration of nanomedicine with adoptive cell therapy in a combined cancer treatment framework.
{"title":"Coupling Adoptive Cell Therapy with Boron Neutron Capture Therapy: Using Functional Tumor-Infiltrating Lymphocytes for Tumor Delivery of Boron Carbide Nanoparticles.","authors":"Maria Paola Demichelis,Patrizia Sommi,Nicola Romanini,Agustina Portu,Mario Gadan,Silva Bortolussi,Ian Postuma,Alberto Casu,Andrea Falqui,Maria Elisabetta Federica Palamà,Silvia Scaglione,Francesca Tauceri,Giovanni Paganelli,Marcella Tazzari,Umberto Anselmi-Tamburini","doi":"10.1021/acsnano.5c12640","DOIUrl":"https://doi.org/10.1021/acsnano.5c12640","url":null,"abstract":"Nanomedicine offers promising strategies for targeted drug delivery, imaging, and molecular-level therapies. However, the clinical translation of nanomedicine has often been hindered by the complex interactions of nanoparticles (NPs) with biological systems. This study investigates a cell-based delivery platform designed to overcome some of these limitations, using clinical-grade tumor-infiltrating lymphocytes (TILs) as biological carriers of boron carbide (B4C) NPs in boron neutron capture therapy (BNCT). Biological vectors, such as TILs, could enable selective tumor targeting, leading to highly localized 10B levels and minimizing off-target accumulation. We evaluated the uptake and retention of composite Fe2O3-B4C NPs (FeBNPs) using both immortalized Jurkat T cells and primary human TILs. Both cell types efficiently internalized FeBNPs without cytotoxic effects, maintained their functionalities, and retained the boron-rich NPs for up to 72 h. Imaging confirmed intracellular localization, and neutron autoradiography demonstrated that TILs accumulated sufficient 10B for therapeutic efficacy, eliminating the need for isotopically enriched compounds like L-4-boronophenylalanine (BPA) or sodium borocaptate (BSH). Coculture experiments with Jurkat and HeLa cells confirmed that lymphocyte-delivered boron could mediate localized radiation damage via neutron capture. These findings support the concept of TILs as \"Trojan Horses\" for boron delivery, allowing for overcoming traditional barriers in NP-based therapies and taking advantage of their innate tumor-homing ability. This approach not only enhances BNCT selectivity and efficacy but also supports the integration of nanomedicine with adoptive cell therapy in a combined cancer treatment framework.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"28 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145680758","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}
Fusarium poses a significant threat to the global crop productivity and food security. This study evaluated the mechanisms of nanoscale boron nitride (nano-BN, 0-500 mg/kg) against Fusarium oxysporum in cucumber. Fusarium infection severely impaired plant growth with biomass declining by 60%. However, 50 mg/kg nano-BN treatment significantly increased shoot biomass by 64.9% compared to disease controls, restoring photosynthetic parameters to near-healthy levels. Nano-BN inhibited Fusarium proliferation by disrupting hyphal and spore structures and reduced mycotoxin production (beauvericin and enniatin) by over 63%. Metabolomic analysis demonstrates that nano-BN mitigated oxidative stress by enhancing glutathione metabolism, with significant increases in glutathione and ascorbic acid content by 166.67% and 478.78%, respectively. Importantly, the protein-protein interaction network shows that nano-BN counteracted Fusarium-induced suppression of ribosomal proteins and endoplasmic reticulum stress-related proteins, promoting protein synthesis and folding. The coexpression network identified sucrose and geshoidin as key metabolites linked to ribosomal and mitochondrial proteins, bridging metabolic resilience with enhanced disease resistance. Multiomics analysis suggests that nano-BN alleviated the Fusarium stress by regulating the phenylpropanoid biosynthesis and restoring the expression levels of key enzymes in carbohydrate metabolism. Overall, nano-BN effectively mitigates Fusarium stress by enhancing plant growth and modulating metabolic processes, offering a promising strategy for plant protection.
{"title":"Multiomics Insights into Nanoscale Boron Nitride Mediated Antioxidant Defense and Metabolic Reprogramming in Cucumber in Response to Fusarium Infection.","authors":"Xinxin Xu,Zeyu Cai,Weili Jia,Yini Cao,Yi Hao,Xiupei Zhou,Anqi Liang,Ziqin Lin,Sixiang Zhuang,Zewei Zhang,Lanfang Han,Jian Zhao,Jason C White,Chuanxin Ma,Baoshan Xing","doi":"10.1021/acsnano.5c14128","DOIUrl":"https://doi.org/10.1021/acsnano.5c14128","url":null,"abstract":"Fusarium poses a significant threat to the global crop productivity and food security. This study evaluated the mechanisms of nanoscale boron nitride (nano-BN, 0-500 mg/kg) against Fusarium oxysporum in cucumber. Fusarium infection severely impaired plant growth with biomass declining by 60%. However, 50 mg/kg nano-BN treatment significantly increased shoot biomass by 64.9% compared to disease controls, restoring photosynthetic parameters to near-healthy levels. Nano-BN inhibited Fusarium proliferation by disrupting hyphal and spore structures and reduced mycotoxin production (beauvericin and enniatin) by over 63%. Metabolomic analysis demonstrates that nano-BN mitigated oxidative stress by enhancing glutathione metabolism, with significant increases in glutathione and ascorbic acid content by 166.67% and 478.78%, respectively. Importantly, the protein-protein interaction network shows that nano-BN counteracted Fusarium-induced suppression of ribosomal proteins and endoplasmic reticulum stress-related proteins, promoting protein synthesis and folding. The coexpression network identified sucrose and geshoidin as key metabolites linked to ribosomal and mitochondrial proteins, bridging metabolic resilience with enhanced disease resistance. Multiomics analysis suggests that nano-BN alleviated the Fusarium stress by regulating the phenylpropanoid biosynthesis and restoring the expression levels of key enzymes in carbohydrate metabolism. Overall, nano-BN effectively mitigates Fusarium stress by enhancing plant growth and modulating metabolic processes, offering a promising strategy for plant protection.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"141 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145680763","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}
Hao Wang, Zhizhen Zhang, Youqi Chu, Anjie Lai, Shaowei Kang, Guoli Xu, Fan Peng, Wenwu Li, Meilin Liu, Chenghao Yang
Na4Fe3(PO4)2P2O7 (NFPP) possesses a stable NASICON-type framework and a suitable redox potential, making it attractive as a sodium-ion battery cathode. Yet, its utility is limited by poor electronic conductivity and sluggish Na+ diffusion. Here, we design a high-entropy Na4Fe2.75Mn0.05Mg0.05Cr0.05Cu0.05Al0.05(PO4)2P2O7 (HE-NFPP) synthesized through spray drying and sintering. HE-NFPP achieves a compaction density of 2.34 g/cm3 under 300 MPa, rivaling that of LiFePO4. The high-entropy incorporation of Mn, Mg, Cr, Cu, and Al enables enhanced electron transitions and improved intrinsic conductivity. Simultaneously, the creation of wide, interconnected 3D Na+ channels significantly reduces migration barriers, accelerating transport and electrode kinetics. In situ optical fiber thermometry reveals suppressed heat evolution, leading to enhanced thermal stability, uniform reaction processes, and safer operation. Additionally, the redistribution of the local electrostatic field minimizes cation repulsion and mechanical strain during Na+ (de)intercalation, ensuring structural robustness. These synergistic effects yield excellent rate capability and cycling durability, underscoring the potential of entropy engineering as a versatile strategy to optimize polyanionic cathodes for next-generation sodium-ion batteries.
{"title":"Boosting Na+ Storage and Thermal Stability of Na4Fe3(PO4)2P2O7 via High-Entropy Engineering","authors":"Hao Wang, Zhizhen Zhang, Youqi Chu, Anjie Lai, Shaowei Kang, Guoli Xu, Fan Peng, Wenwu Li, Meilin Liu, Chenghao Yang","doi":"10.1021/acsnano.5c15785","DOIUrl":"https://doi.org/10.1021/acsnano.5c15785","url":null,"abstract":"Na<sub>4</sub>Fe<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>P<sub>2</sub>O<sub>7</sub> (NFPP) possesses a stable NASICON-type framework and a suitable redox potential, making it attractive as a sodium-ion battery cathode. Yet, its utility is limited by poor electronic conductivity and sluggish Na<sup>+</sup> diffusion. Here, we design a high-entropy Na<sub>4</sub>Fe<sub>2.75</sub>Mn<sub>0.05</sub>Mg<sub>0.05</sub>Cr<sub>0.05</sub>Cu<sub>0.05</sub>Al<sub>0.05</sub>(PO<sub>4</sub>)<sub>2</sub>P<sub>2</sub>O<sub>7</sub> (HE-NFPP) synthesized through spray drying and sintering. HE-NFPP achieves a compaction density of 2.34 g/cm<sup>3</sup> under 300 MPa, rivaling that of LiFePO<sub>4</sub>. The high-entropy incorporation of Mn, Mg, Cr, Cu, and Al enables enhanced electron transitions and improved intrinsic conductivity. Simultaneously, the creation of wide, interconnected 3D Na<sup>+</sup> channels significantly reduces migration barriers, accelerating transport and electrode kinetics. In situ optical fiber thermometry reveals suppressed heat evolution, leading to enhanced thermal stability, uniform reaction processes, and safer operation. Additionally, the redistribution of the local electrostatic field minimizes cation repulsion and mechanical strain during Na<sup>+</sup> (de)intercalation, ensuring structural robustness. These synergistic effects yield excellent rate capability and cycling durability, underscoring the potential of entropy engineering as a versatile strategy to optimize polyanionic cathodes for next-generation sodium-ion batteries.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"19 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145674011","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}
Epidemiological studies have reported that cigarette smoking promotes bladder cancer progression, but the corresponding biological mechanisms must be elucidated. Cigarette smoking-related extracellular vesicle (EV)-packaged long noncoding RNAs (lncRNAs) derived from bladder tumors were identified via RNA sequencing, tissue microarrays, and single-cell RNA sequencing. The clinical value of candidate EV-packaged lncRNAs was evaluated in the urine and plasma of bladder cancer patients with smoking history. The underlying mechanism of EV-packaged lncRNAs was explored using CRISPR/Cas9, Seahorse, and N4-acetylcytidine (ac4C) acetylation experiments in vivo and in vitro. The EV-packaged lncRNA MIR4435-2HG, which was originally secreted by M2 macrophages in response to exposure to the cigarette smoking-related carcinogen 4-aminobiphenyl (4-ABP), exhibited an abundant expression pattern. Mechanistically, 4-ABP promoted M2 macrophage polarization and increased fused in sarcoma (FUS) expression by inducing signal transducer and activator of transcription 6 (STAT6) phosphorylation, contributing to the direct packaging of MIR4435-2HG into M2 macrophage-derived EVs and subsequent delivery to recipient tumor cells. The nuclear EV-packaged MIR4435-2HG subsequently bound N-acetyltransferase 10 (NAT10) and increased the stability of the glycolysis regulator Enolase 1 (ENO1) through the ac4C modification; cytoplasmic EV-packaged MIR4435-2HG sponged miR-143-3p, increased ENO1 expression, and ultimately activated PI3K-Akt signaling for glycolytic reprogramming to promote tumor development. In addition, recipient tumor cells internalized EV-packaged MIR4435-2HG and simultaneously secreted chemokines to recruit monocytes, establishing a potential feed-forward loop between M2 macrophages and tumor cells. This study identified EV-packaged MIR4435-2HG as a crucial bladder cancer marker that mediates intercellular communication during cigarette smoke exposure, suggesting a promising approach for bladder cancer prevention and treatment.
{"title":"Extracellular Vesicle-Packaged MIR4435-2HG Facilitates Cigarette Smoke-Induced Bladder Cancer Progression through Enolase 1-Dependent Glycolytic Reprogramming.","authors":"Rui Zheng,Yanping Xiao,Jialei Yang,Zhenguang Mao,Zhiwei Tan,Chengcheng Wei,Fang Gao,Jiajin Wu,Yang Shen,Zhengkai Huang,Meilin Wang,Mulong Du,Zhengdong Zhang","doi":"10.1021/acsnano.4c15108","DOIUrl":"https://doi.org/10.1021/acsnano.4c15108","url":null,"abstract":"Epidemiological studies have reported that cigarette smoking promotes bladder cancer progression, but the corresponding biological mechanisms must be elucidated. Cigarette smoking-related extracellular vesicle (EV)-packaged long noncoding RNAs (lncRNAs) derived from bladder tumors were identified via RNA sequencing, tissue microarrays, and single-cell RNA sequencing. The clinical value of candidate EV-packaged lncRNAs was evaluated in the urine and plasma of bladder cancer patients with smoking history. The underlying mechanism of EV-packaged lncRNAs was explored using CRISPR/Cas9, Seahorse, and N4-acetylcytidine (ac4C) acetylation experiments in vivo and in vitro. The EV-packaged lncRNA MIR4435-2HG, which was originally secreted by M2 macrophages in response to exposure to the cigarette smoking-related carcinogen 4-aminobiphenyl (4-ABP), exhibited an abundant expression pattern. Mechanistically, 4-ABP promoted M2 macrophage polarization and increased fused in sarcoma (FUS) expression by inducing signal transducer and activator of transcription 6 (STAT6) phosphorylation, contributing to the direct packaging of MIR4435-2HG into M2 macrophage-derived EVs and subsequent delivery to recipient tumor cells. The nuclear EV-packaged MIR4435-2HG subsequently bound N-acetyltransferase 10 (NAT10) and increased the stability of the glycolysis regulator Enolase 1 (ENO1) through the ac4C modification; cytoplasmic EV-packaged MIR4435-2HG sponged miR-143-3p, increased ENO1 expression, and ultimately activated PI3K-Akt signaling for glycolytic reprogramming to promote tumor development. In addition, recipient tumor cells internalized EV-packaged MIR4435-2HG and simultaneously secreted chemokines to recruit monocytes, establishing a potential feed-forward loop between M2 macrophages and tumor cells. This study identified EV-packaged MIR4435-2HG as a crucial bladder cancer marker that mediates intercellular communication during cigarette smoke exposure, suggesting a promising approach for bladder cancer prevention and treatment.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"372 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145680761","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}
Christopher G. Bailey, Nicholas P. Sloane, Tik Lun Leung, Chwenhaw Liao, Adrian Mena, Damon M. de Clercq, Jianpeng Yi, Stefano Palomba, Michael P. Nielsen, David R. McKenzie, Timothy W. Schmidt, Dane R. McCamey, Anita W. Y. Ho-Baillie
Nanomaterials with a strong room-temperature optical response to magnetic fields are highly desirable for applications in sensing and photonics. Therefore, the ability to tune this response presents an opportunity to develop nanoscale magneto-optical devices. 2D metal halide perovskites are promising materials for optoelectronics, but typically exhibit very weak magneto-optical effects at room temperature. In this article, a 15× enhancement of the magnetic field effect on photoluminescence (magneto-photoluminescence) is demonstrated in colloidal (PEA)2PbI4 2D perovskite nanosheets at room temperature. The results show that an external species can influence the exchange interaction energy and consequently the splitting between bright and dark exciton states in 2D perovskite nanosheets, which ultimately governs the magneto-photoluminescence. Additionally, the average photoluminescence quantum yield (PLQY) is increased from 15.2% in bulk single crystals to 23.1% in nanosheets (with a maximum recorded PLQY of 39.61%) produced using liquid-phase exfoliation, which also exhibited reduced trap emission compared with bulk or tape-exfoliated crystals in this study. This work demonstrates a simple method of engineering exciton states in 2D perovskites, assisting the development of optoelectronic technology and representing a crucial step toward producing nanoscale room-temperature magneto-optical devices.
{"title":"Between the Nanosheets: Enhancing Electron–Hole Exchange Interaction for Room-Temperature Magneto-Photoluminescence in Liquid-phase-exfoliated 2D Perovskite","authors":"Christopher G. Bailey, Nicholas P. Sloane, Tik Lun Leung, Chwenhaw Liao, Adrian Mena, Damon M. de Clercq, Jianpeng Yi, Stefano Palomba, Michael P. Nielsen, David R. McKenzie, Timothy W. Schmidt, Dane R. McCamey, Anita W. Y. Ho-Baillie","doi":"10.1021/acsnano.5c16321","DOIUrl":"https://doi.org/10.1021/acsnano.5c16321","url":null,"abstract":"Nanomaterials with a strong room-temperature optical response to magnetic fields are highly desirable for applications in sensing and photonics. Therefore, the ability to tune this response presents an opportunity to develop nanoscale magneto-optical devices. 2D metal halide perovskites are promising materials for optoelectronics, but typically exhibit very weak magneto-optical effects at room temperature. In this article, a 15× enhancement of the magnetic field effect on photoluminescence (magneto-photoluminescence) is demonstrated in colloidal (PEA)<sub>2</sub>PbI<sub>4</sub> 2D perovskite nanosheets at room temperature. The results show that an external species can influence the exchange interaction energy and consequently the splitting between bright and dark exciton states in 2D perovskite nanosheets, which ultimately governs the magneto-photoluminescence. Additionally, the average photoluminescence quantum yield (PLQY) is increased from 15.2% in bulk single crystals to 23.1% in nanosheets (with a maximum recorded PLQY of 39.61%) produced using liquid-phase exfoliation, which also exhibited reduced trap emission compared with bulk or tape-exfoliated crystals in this study. This work demonstrates a simple method of engineering exciton states in 2D perovskites, assisting the development of optoelectronic technology and representing a crucial step toward producing nanoscale room-temperature magneto-optical devices.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"34 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145674277","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}
Na Chen, Xuantao Deng, Zuo-Chang Chen, Peng Du, Xu-Feng Liu, Jia Liu, Bilyu Hong, Ruixuan Qin, Jian-Wei Zheng, Jun Li, Su-Yuan Xie, Youzhu Yuan
Copper oxides such as Cu2O are promising catalysts for the electrochemical CO2 reduction reaction (CO2RR) to C2+ products, yet their intrinsic susceptibility to Cu+ reduction and morphology degradation severely limits their long-term performance. Herein, we report a facile two-step wet-chemical route to interface [C60]fullerene with cubic Cu2O (c-Cu2O), octahedral (o-Cu2O), and dodecahedral (d-Cu2O) crystals. The resulting composite optimal c-Cu2O–C60 achieves substantial Faradaic efficiencies of 60.4% in an H-cell and 65.6% in a flow-cell for C2+ products, which is 3-fold higher than pristine c-Cu2O, while maintaining stable operation for 100 h at –1.2 V versus RHE without detectable activity loss. Our experimental results and theoretical study demonstrate that the strategic incorporation of C60 during the synthesis of Cu2O directly endows the surfaces of the resultant Cu2O crystals with abundant Cu+/Cu0 grain boundaries. Additionally, the presence of C60 induces the formation of more Cu+/Cu0 boundaries during the CO2RR process, which synergistically facilitate the generation of C2+ products. Moreover, C60 acts as an electron buffer, preventing Cu+ from being over-reduced during the reduction process, thereby sustaining active Cu+/Cu0 interfaces and maintaining the catalytic activity for C2+ products. Extension to hydroxylated and fluorinated fullerene derivatives delivers comparable C2+ selectivity, underscoring the generality of this fullerene-mediated stabilization strategy for designing robust Cu-based CO2RR catalysts.
{"title":"Interplay of [C60]Fullerene and Cu2O Nanocrystals for Stable CO2 Electroreduction to C2+ Products","authors":"Na Chen, Xuantao Deng, Zuo-Chang Chen, Peng Du, Xu-Feng Liu, Jia Liu, Bilyu Hong, Ruixuan Qin, Jian-Wei Zheng, Jun Li, Su-Yuan Xie, Youzhu Yuan","doi":"10.1021/acsnano.5c13950","DOIUrl":"https://doi.org/10.1021/acsnano.5c13950","url":null,"abstract":"Copper oxides such as Cu<sub>2</sub>O are promising catalysts for the electrochemical CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) to C<sub>2+</sub> products, yet their intrinsic susceptibility to Cu<sup>+</sup> reduction and morphology degradation severely limits their long-term performance. Herein, we report a facile two-step wet-chemical route to interface [C<sub>60</sub>]fullerene with cubic Cu<sub>2</sub>O (<i>c</i>-Cu<sub>2</sub>O), octahedral (<i>o</i>-Cu<sub>2</sub>O), and dodecahedral (<i>d</i>-Cu<sub>2</sub>O) crystals. The resulting composite optimal <i>c</i>-Cu<sub>2</sub>O–C<sub>60</sub> achieves substantial Faradaic efficiencies of 60.4% in an H-cell and 65.6% in a flow-cell for C<sub>2+</sub> products, which is 3-fold higher than pristine <i>c</i>-Cu<sub>2</sub>O, while maintaining stable operation for 100 h at –1.2 V versus RHE without detectable activity loss. Our experimental results and theoretical study demonstrate that the strategic incorporation of C<sub>60</sub> during the synthesis of Cu<sub>2</sub>O directly endows the surfaces of the resultant Cu<sub>2</sub>O crystals with abundant Cu<sup>+</sup>/Cu<sup>0</sup> grain boundaries. Additionally, the presence of C<sub>60</sub> induces the formation of more Cu<sup>+</sup>/Cu<sup>0</sup> boundaries during the CO<sub>2</sub>RR process, which synergistically facilitate the generation of C<sub>2+</sub> products. Moreover, C<sub>60</sub> acts as an electron buffer, preventing Cu<sup>+</sup> from being over-reduced during the reduction process, thereby sustaining active Cu<sup>+</sup>/Cu<sup>0</sup> interfaces and maintaining the catalytic activity for C<sub>2+</sub> products. Extension to hydroxylated and fluorinated fullerene derivatives delivers comparable C<sub>2+</sub> selectivity, underscoring the generality of this fullerene-mediated stabilization strategy for designing robust Cu-based CO<sub>2</sub>RR catalysts.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"21 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145674014","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}
Hepatocellular carcinoma (HCC) is a leading cause of global cancer-related mortality, with delayed diagnosis adversely affecting patient outcomes. Liquid biopsy techniques using small extracellular vesicles (EVs) offer potential for cancer detection, though current methods are often time-consuming and require complex equipment, limiting clinical utility. Here, we report a metasurface-enhanced EV detection chip (metaEVchip) platform for the dynamic monitoring of HCC-specific EVs, enabling rapid detection and purification. This system provides results within 5 min. The platform integrates a plasmonic metasurface with a Kolmogorov-Arnold network (KAN) to facilitate real-time EV capture, enhancing detection speed while achieving an area under the curve (AUC) of 0.914 for HCC screening. By optimizing the purification process and incorporating complementary detection of alpha-fetoprotein (AFP) and protein induced by vitamin K absence or antagonist II (PIVKAII), the AUC for HCC screening reaches 0.961 in an external validation set. These results effectively differentiate HCC from benign liver diseases (BLD) and early-stage HCC from cirrhosis, addressing limitations of conventional EV detection and demonstrating the potential for rapid cancer screening.
{"title":"Rapid Detection and Purification of Extracellular Vesicles for Hepatocellular Carcinoma Screening Using a Plasmonic Metasurface Integrated with the Kolmogorov-Arnold Network.","authors":"Jiaheng Zhu,Chenhongmei Wang,Tianhao Huang,Lihuang Zeng,Qiang Niu,Xinyue Huang,Hanyang Chen,Mengqi Jiang,Baichang Deng,Yiming Yan,Xiaohui Liu,Junjie Chen,Yinong Xie,Jiaqing Shen,Wei Chen,Yuan Gao,Kaibin Chen,Xiangyujie Lin,Lijun Zeng,Bo Li,Yanling Song,Jinfeng Zhu,Boan Li","doi":"10.1021/acsnano.5c11740","DOIUrl":"https://doi.org/10.1021/acsnano.5c11740","url":null,"abstract":"Hepatocellular carcinoma (HCC) is a leading cause of global cancer-related mortality, with delayed diagnosis adversely affecting patient outcomes. Liquid biopsy techniques using small extracellular vesicles (EVs) offer potential for cancer detection, though current methods are often time-consuming and require complex equipment, limiting clinical utility. Here, we report a metasurface-enhanced EV detection chip (metaEVchip) platform for the dynamic monitoring of HCC-specific EVs, enabling rapid detection and purification. This system provides results within 5 min. The platform integrates a plasmonic metasurface with a Kolmogorov-Arnold network (KAN) to facilitate real-time EV capture, enhancing detection speed while achieving an area under the curve (AUC) of 0.914 for HCC screening. By optimizing the purification process and incorporating complementary detection of alpha-fetoprotein (AFP) and protein induced by vitamin K absence or antagonist II (PIVKAII), the AUC for HCC screening reaches 0.961 in an external validation set. These results effectively differentiate HCC from benign liver diseases (BLD) and early-stage HCC from cirrhosis, addressing limitations of conventional EV detection and demonstrating the potential for rapid cancer screening.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"443 Pt B 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145664199","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}
The treatment of osteoporotic bone fractures remains a critical challenge due to the dysregulated bone remodeling microenvironment characterized by excessive osteoclastic resorption, impaired osteogenic differentiation, angiogenic dysfunction, and chronic inflammation. In this work, we engineered a metal–organic network as a bone repair “band-aid” by integrating poly(ethylene glycol)-alendronate (PEG-ALN) conjugates with bioactive epigallocatechin gallate (EGCG), zinc, and calcium ions into a multifunctional scaffold. This design leverages the synergistic effects of anti-inflammatory and antioxidant properties of EGCG with the balancing osteogenic and osteoclastic functions of ALN, zinc, and calcium ions. In vitro studies demonstrated that the band-aid significantly enhanced the proliferation and differentiation of osteoblasts while promoting endothelial cell migration and tubule formation, indicating the robust osteogenic and angiogenic potential. In vivo evaluations in an osteoporotic bone fracture model revealed accelerated bone regeneration and improved microvascularization while maintaining a balanced immune response to prevent chronic inflammation. Mechanistically, the band-aid modulated macrophage polarization toward a pro-regenerative M2 phenotype and suppressed excessive osteoclast activity, thereby restoring the osteogenic-osteoclastic equilibrium. This study not only provides a therapeutic implant for osteoporotic bone repair but also proposes a strategy for designing immunomodulatory scaffolds that target the pathological bone microenvironment.
{"title":"Engineering of Metal–Organic Networks as Band-Aid for the Repair of Osteoporotic Bone Fractures","authors":"Shaoyin Wei, Yunhao You, Zhiliang Gao, Liangyu Wang, Qian Cheng, Mingzheng Chang, Qingliang Ma, Xinyu Liu, Lianlei Wang, Jiwei Cui","doi":"10.1021/acsnano.5c15619","DOIUrl":"https://doi.org/10.1021/acsnano.5c15619","url":null,"abstract":"The treatment of osteoporotic bone fractures remains a critical challenge due to the dysregulated bone remodeling microenvironment characterized by excessive osteoclastic resorption, impaired osteogenic differentiation, angiogenic dysfunction, and chronic inflammation. In this work, we engineered a metal–organic network as a bone repair “band-aid” by integrating poly(ethylene glycol)-alendronate (PEG-ALN) conjugates with bioactive epigallocatechin gallate (EGCG), zinc, and calcium ions into a multifunctional scaffold. This design leverages the synergistic effects of anti-inflammatory and antioxidant properties of EGCG with the balancing osteogenic and osteoclastic functions of ALN, zinc, and calcium ions. <i>In vitro</i> studies demonstrated that the band-aid significantly enhanced the proliferation and differentiation of osteoblasts while promoting endothelial cell migration and tubule formation, indicating the robust osteogenic and angiogenic potential. <i>In vivo</i> evaluations in an osteoporotic bone fracture model revealed accelerated bone regeneration and improved microvascularization while maintaining a balanced immune response to prevent chronic inflammation. Mechanistically, the band-aid modulated macrophage polarization toward a pro-regenerative M2 phenotype and suppressed excessive osteoclast activity, thereby restoring the osteogenic-osteoclastic equilibrium. This study not only provides a therapeutic implant for osteoporotic bone repair but also proposes a strategy for designing immunomodulatory scaffolds that target the pathological bone microenvironment.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"129 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145674022","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}
Yixuan Wang, Jingyao Li, Prashant Gupta, Zixiao Wang, Qisheng Jiang, Avishek Debnath, Ruixue Zhang, Hengbo Huang, Minkyu Kim, Fuzhong Zhang, Vladimir V. Tsukruk, Srikanth Singamaneni
A biotemplated in situ growth method was employed to fabricate self-supporting metal–organic framework (MOF) aerogels using bacterial nanocellulose (BNC) and collagen foam as templates. The one-step synthesis method enables uniform and dense coating of MOF crystals (ZIF-8 and ZIF-L) on nanocellulose and collagen nanofibers, resulting in an interconnected 3D open porous network. Integrating plasmonic nanostructures with metal–organic frameworks (MOFs) in three-dimensional (3D) aerogels enables the realization of multifunctional materials that combine high porosity, thermal stability, electromagnetic field enhancement, and photothermal properties, therefore simultaneously supporting surface-enhanced Raman scattering (SERS)-based sensing and antimicrobial functions. The plasmonic/MOF hybrid aerogels allow highly sensitive vapor-phase detection of toxic volatile organics (TVOs) including p-aminothiophenol (p-ATP), formalin, and aniline, harnessing the synergistic effects of MOF-assisted analyte trapping and electromagnetic field enhancement from the plasmonic nanostructures. The photothermal properties of the plasmonic/MOF aerogels together with Zn2+/Ag+ ion release resulted in high antibacterial efficacy (>99%) against Escherichia coli and Staphylococcus aureus under low-power laser irradiation. The simple, scalable, and versatile method demonstrated here can be extended to other functional nanomaterials and MOFs for realizing multifunctional materials with a 3D open porous architecture.
{"title":"Multifunctional Plasmonic/Metal–Organic Framework Biohybrid Aerogels","authors":"Yixuan Wang, Jingyao Li, Prashant Gupta, Zixiao Wang, Qisheng Jiang, Avishek Debnath, Ruixue Zhang, Hengbo Huang, Minkyu Kim, Fuzhong Zhang, Vladimir V. Tsukruk, Srikanth Singamaneni","doi":"10.1021/acsnano.5c12221","DOIUrl":"https://doi.org/10.1021/acsnano.5c12221","url":null,"abstract":"A biotemplated <i>in situ</i> growth method was employed to fabricate self-supporting metal–organic framework (MOF) aerogels using bacterial nanocellulose (BNC) and collagen foam as templates. The one-step synthesis method enables uniform and dense coating of MOF crystals (ZIF-8 and ZIF-L) on nanocellulose and collagen nanofibers, resulting in an interconnected 3D open porous network. Integrating plasmonic nanostructures with metal–organic frameworks (MOFs) in three-dimensional (3D) aerogels enables the realization of multifunctional materials that combine high porosity, thermal stability, electromagnetic field enhancement, and photothermal properties, therefore simultaneously supporting surface-enhanced Raman scattering (SERS)-based sensing and antimicrobial functions. The plasmonic/MOF hybrid aerogels allow highly sensitive vapor-phase detection of toxic volatile organics (TVOs) including <i>p</i>-aminothiophenol (p-ATP), formalin, and aniline, harnessing the synergistic effects of MOF-assisted analyte trapping and electromagnetic field enhancement from the plasmonic nanostructures. The photothermal properties of the plasmonic/MOF aerogels together with Zn<sup>2+</sup>/Ag<sup>+</sup> ion release resulted in high antibacterial efficacy (>99%) against <i>Escherichia coli</i> and <i>Staphylococcus aureus</i> under low-power laser irradiation. The simple, scalable, and versatile method demonstrated here can be extended to other functional nanomaterials and MOFs for realizing multifunctional materials with a 3D open porous architecture.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"15 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145674013","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}