Hualong Wu, Jiahao Dong, Jiantao Li, Guiyang Gao, Liang Lin, Ailin Liu, Hongfei Zheng, Guanyi Wang, Junxiang Liu, Laisen Wang, Jie Lin, Khalil Amine, Dong-Liang Peng, Qingshui Xie, Jun Lu
Low initial Coulombic efficiency and severe capacity/voltage fading during cycling caused by serious irreversible oxygen release, especially in the initial cycle, and resultantly induced unstable electrode/electrolyte interfacial chemistry, largely prohibit the commercial application of high-capacity Li-rich layered oxide cathodes (LLOs). In this work, a dual reductive gas interface cotreatment strategy is applied to regulate the lattice oxygen redox activity and reversibility with a multiple defective structure design including Li/O/TM (TM = transition metal) vacancies and the intrinsic TM doping as well as a full-surface protective layer, which can suppress the irreversible TM migration and then undesirable phase transformation, resisting the corrosion of electrolyte during cycling effectively. Importantly, the introduced reversible SO32–/SO42– redox couple that provides extra capacity compensation could alleviate the distortion of oxygen-central octahedral structure and structural collapse caused by immoderate oxygen oxidation. Thus, the lattice oxygen redox chemistry is optimized, with negligible oxygen loss during the initial cycle. And the designed AS-LLO cathode with greatly enhanced structure stability shows high-capacity retentions of 99.2% at 0.3C after 100 cycles and 82.4% even after 1000 cycles at 5C. This work provides a guideline for manipulating the oxygen redox chemistry to achieve long-lifespan Li-rich layered oxide cathodes for high-energy-density lithium batteries.
{"title":"Modulating Surface Anionic Redox Chemistry toward Highly Stable Li-Rich Cathodes with Negligible Oxygen Loss","authors":"Hualong Wu, Jiahao Dong, Jiantao Li, Guiyang Gao, Liang Lin, Ailin Liu, Hongfei Zheng, Guanyi Wang, Junxiang Liu, Laisen Wang, Jie Lin, Khalil Amine, Dong-Liang Peng, Qingshui Xie, Jun Lu","doi":"10.1021/acsnano.5c00630","DOIUrl":"https://doi.org/10.1021/acsnano.5c00630","url":null,"abstract":"Low initial Coulombic efficiency and severe capacity/voltage fading during cycling caused by serious irreversible oxygen release, especially in the initial cycle, and resultantly induced unstable electrode/electrolyte interfacial chemistry, largely prohibit the commercial application of high-capacity Li-rich layered oxide cathodes (LLOs). In this work, a dual reductive gas interface cotreatment strategy is applied to regulate the lattice oxygen redox activity and reversibility with a multiple defective structure design including Li/O/TM (TM = transition metal) vacancies and the intrinsic TM doping as well as a full-surface protective layer, which can suppress the irreversible TM migration and then undesirable phase transformation, resisting the corrosion of electrolyte during cycling effectively. Importantly, the introduced reversible SO<sub>3</sub><sup>2–</sup>/SO<sub>4</sub><sup>2–</sup> redox couple that provides extra capacity compensation could alleviate the distortion of oxygen-central octahedral structure and structural collapse caused by immoderate oxygen oxidation. Thus, the lattice oxygen redox chemistry is optimized, with negligible oxygen loss during the initial cycle. And the designed AS-LLO cathode with greatly enhanced structure stability shows high-capacity retentions of 99.2% at 0.3C after 100 cycles and 82.4% even after 1000 cycles at 5C. This work provides a guideline for manipulating the oxygen redox chemistry to achieve long-lifespan Li-rich layered oxide cathodes for high-energy-density lithium batteries.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"29 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846806","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}
Although the oxygen evolution reaction (OER) activity of BiVO4 photoanodes has been significantly enhanced, achieving long-term photostability is still challenging due to the gradual dissolution of V5+ during photoelectrochemical (PEC) water splitting. Herein, we deliberately generate ligand defects in a (Co0.91V0.09)3(BTC)2 metal–organic framework (CoV-MOF) that creates more undercoordinated sites, forming strong chemical bonds with BiVO4. Consequently, the dissolution of V5+ from BiVO4 during PEC water splitting can be effectively suppressed, leading to significantly enhanced stability. The optimized Co3O4/CoV-MOF/BiVO4 photoanode exhibits a high photocurrent density of 6.0 mA cm–2 at 1.23 V vs the reversible hydrogen electrode (RHE). Impressively, the photoanode can stably operate for 500 h at 0.6 V vs RHE under AM 1.5 G illumination. This work demonstrates the proof-of-concept of anchoring V5+ in BiVO4 photoanodes achieving ultrastable PEC water splitting.
{"title":"Strengthening Bonding Interaction of a (Co0.91V0.09)3(BTC)2 Metal–Organic Framework with BiVO4 Photoanodes Enabling Ultrastable Photoelectrochemical Water Oxidation","authors":"Liangcheng Xu, Yingjuan Zhang, Boyan Liu, Kang Wan, Xin Wang, Tingsheng Wang, Lianzhou Wang, Songcan Wang, Wei Huang","doi":"10.1021/acsnano.5c01111","DOIUrl":"https://doi.org/10.1021/acsnano.5c01111","url":null,"abstract":"Although the oxygen evolution reaction (OER) activity of BiVO<sub>4</sub> photoanodes has been significantly enhanced, achieving long-term photostability is still challenging due to the gradual dissolution of V<sup>5+</sup> during photoelectrochemical (PEC) water splitting. Herein, we deliberately generate ligand defects in a (Co<sub>0.91</sub>V<sub>0.09</sub>)<sub>3</sub>(BTC)<sub>2</sub> metal–organic framework (CoV-MOF) that creates more undercoordinated sites, forming strong chemical bonds with BiVO<sub>4</sub>. Consequently, the dissolution of V<sup>5+</sup> from BiVO<sub>4</sub> during PEC water splitting can be effectively suppressed, leading to significantly enhanced stability. The optimized Co<sub>3</sub>O<sub>4</sub>/CoV-MOF/BiVO<sub>4</sub> photoanode exhibits a high photocurrent density of 6.0 mA cm<sup>–2</sup> at 1.23 V vs the reversible hydrogen electrode (RHE). Impressively, the photoanode can stably operate for 500 h at 0.6 V vs RHE under AM 1.5 G illumination. This work demonstrates the proof-of-concept of anchoring V<sup>5+</sup> in BiVO<sub>4</sub> photoanodes achieving ultrastable PEC water splitting.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"24 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842083","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}
Charlie W. F. Freeman, Harry Youel, Adam K. Budniak, Zekun Xue, Henry De Libero, Thomas Thomson, Michel Bosman, Goki Eda, Hidekazu Kurebayashi, Murat Cubukcu
Antiferromagnetic (AFM) magnons in van der Waals (vdW) materials offer substantial potential for applications in magnonics and spintronics. In this study, we demonstrate ultrastrong magnon–magnon coupling in the GHz regime within a vdW AFM, achieving a maximum coupling rate of 0.91. Our investigation shows the tunability of coupling strength through temperature-dependent magnetic anisotropies. We compare coupling strength values derived from the gap size from the measured spectrum with those calculated directly through the coupling parameter and show that the gap size as a measure of coupling strength is limited for the ultrastrong coupling regime. Additionally, analytical calculations show the possibility to reach the deep-strong coupling regime by engineering the magnetic anisotropy. These findings highlight the potential of vdW AFMs as a model case to study magnetization dynamics in low-symmetry magnetic materials.
{"title":"Tunable Ultrastrong Magnon–Magnon Coupling Approaching the Deep-Strong Regime in a van der Waals Antiferromagnet","authors":"Charlie W. F. Freeman, Harry Youel, Adam K. Budniak, Zekun Xue, Henry De Libero, Thomas Thomson, Michel Bosman, Goki Eda, Hidekazu Kurebayashi, Murat Cubukcu","doi":"10.1021/acsnano.5c02576","DOIUrl":"https://doi.org/10.1021/acsnano.5c02576","url":null,"abstract":"Antiferromagnetic (AFM) magnons in van der Waals (vdW) materials offer substantial potential for applications in magnonics and spintronics. In this study, we demonstrate ultrastrong magnon–magnon coupling in the GHz regime within a vdW AFM, achieving a maximum coupling rate of 0.91. Our investigation shows the tunability of coupling strength through temperature-dependent magnetic anisotropies. We compare coupling strength values derived from the gap size from the measured spectrum with those calculated directly through the coupling parameter and show that the gap size as a measure of coupling strength is limited for the ultrastrong coupling regime. Additionally, analytical calculations show the possibility to reach the deep-strong coupling regime by engineering the magnetic anisotropy. These findings highlight the potential of vdW AFMs as a model case to study magnetization dynamics in low-symmetry magnetic materials.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"37 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846899","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}
Siwon Choi, Seongwook Chae, Taemin Kim, Hyeonsol Shin, Jin-Gyu Bae, Seung Geol Lee, Ji Hoon Lee, Hyeon Jeong Lee
Lithium (Li) metal has received significant attention as an anode material for next-generation batteries due to its high theoretical capacity and low redox potential. However, the high reactivity of Li metal leads to the formation of a native layer on its surface, inducing nonuniform Li+ flux at the electrolyte/Li metal interface, which promotes the growth of Li metal dendrites. In this study, perfluorooctyltriethoxysilane (PFOTES) was vaporized to chemically react with the native layer and modify the Li metal surface. This gas–solid reaction removes the native layer while simultaneously forming a homogeneous solid electrolyte interphase (SEI) layer. The Si–O–Si network formed through condensation reactions between PFOTES molecules, combined with the fluorinated carbon chain of PFOTES, facilitates rapid Li+ kinetics at the Li metal/electrolyte interface. Consequently, the exchange current density of PFOTES-modified Li (PFOTES-Li) increased to 0.2419 mA cm–2, which is 20 times higher than that of Bare-Li (0.0119 mA cm–2). The SEI layer derived from PFOTES effectively mitigates Li pulverization and the formation of dead Li during the long-term cycling. As a result, the PFOTES-Li||LiNi0.8Mn0.1Co0.1O2 full cell exhibits an excellent discharge capacity of 203.4 mAh g–1 under a high areal loading of 4.2 mAh cm–2. This study demonstrates a gas–solid reaction strategy for removing the native layer from the Li metal surface while forming a stable SEI layer, thereby ensuring high Li+ conductivity and mechanical stability, thus improving the cycling stability of Li metal batteries.
{"title":"Strategic Surface Engineering of Lithium Metal Anodes: Simultaneous Native Layer Elimination and Protective Layer Formation via Gas–Solid Reaction","authors":"Siwon Choi, Seongwook Chae, Taemin Kim, Hyeonsol Shin, Jin-Gyu Bae, Seung Geol Lee, Ji Hoon Lee, Hyeon Jeong Lee","doi":"10.1021/acsnano.5c03708","DOIUrl":"https://doi.org/10.1021/acsnano.5c03708","url":null,"abstract":"Lithium (Li) metal has received significant attention as an anode material for next-generation batteries due to its high theoretical capacity and low redox potential. However, the high reactivity of Li metal leads to the formation of a native layer on its surface, inducing nonuniform Li<sup>+</sup> flux at the electrolyte/Li metal interface, which promotes the growth of Li metal dendrites. In this study, perfluorooctyltriethoxysilane (PFOTES) was vaporized to chemically react with the native layer and modify the Li metal surface. This gas–solid reaction removes the native layer while simultaneously forming a homogeneous solid electrolyte interphase (SEI) layer. The Si–O–Si network formed through condensation reactions between PFOTES molecules, combined with the fluorinated carbon chain of PFOTES, facilitates rapid Li<sup>+</sup> kinetics at the Li metal/electrolyte interface. Consequently, the exchange current density of PFOTES-modified Li (PFOTES-Li) increased to 0.2419 mA cm<sup>–2</sup>, which is 20 times higher than that of Bare-Li (0.0119 mA cm<sup>–2</sup>). The SEI layer derived from PFOTES effectively mitigates Li pulverization and the formation of dead Li during the long-term cycling. As a result, the PFOTES-Li||LiNi<sub>0.8</sub>Mn<sub>0.1</sub>Co<sub>0.1</sub>O<sub>2</sub> full cell exhibits an excellent discharge capacity of 203.4 mAh g<sup>–1</sup> under a high areal loading of 4.2 mAh cm<sup>–2</sup>. This study demonstrates a gas–solid reaction strategy for removing the native layer from the Li metal surface while forming a stable SEI layer, thereby ensuring high Li<sup>+</sup> conductivity and mechanical stability, thus improving the cycling stability of Li metal batteries.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"30 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846900","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}
A critical barrier to commercializing aqueous Zn-metal batteries lies in the dual challenges of dendritic Zn growth and parasitic side reactions at the anode/electrolyte interface. Here, this study presents a front-end design optimization strategy for Zn metal anodes (ZMAs), combining surface laser texturing with alloying treatment to stabilize the interfacial chemistry. Specifically, laser texturing creates a geometrically ordered microstructure on the Zn surface, while subsequent chemical permeation induces the in situ transformation of this microstructured layer into a CuZn5 alloy, forming the LT-Zn@CuZn5 anode. The geometrically ordered alloy coating homogenizes the electronic filed distribution across the zinc surface and enhances corrosion resistance. Thereby, the LT-Zn@CuZn5 anode demonstrated optimized electrochemical reversibility, sustaining over 3000 cycles at 3 mA cm–2/1 mAh cm–2. This performance translates into a high improvement in the cycling behavior of the assembled Zn||I2 soft pack battery, which acquired an initial capacity of 225.8 mAh g–1 and retained 79.1% after 4000 cycles. In contrast, the counterpart employing untreated Zn foil started with a lower initial capacity of 180.7 mAh g–1 and failed after less than 478 cycles. The demonstrated effective approach improves the front-end design strategy of ZMAs and contributes to the development of dendrite-free ZMAs.
{"title":"Surface Laser Texturing and Alloying: Front-End Design Optimization of Zinc Metal Anode for Dendrite-Free Deposition","authors":"Peng Kang, Yi Yuan, Funian Mo, Haibo Hu","doi":"10.1021/acsnano.5c02450","DOIUrl":"https://doi.org/10.1021/acsnano.5c02450","url":null,"abstract":"A critical barrier to commercializing aqueous Zn-metal batteries lies in the dual challenges of dendritic Zn growth and parasitic side reactions at the anode/electrolyte interface. Here, this study presents a front-end design optimization strategy for Zn metal anodes (ZMAs), combining surface laser texturing with alloying treatment to stabilize the interfacial chemistry. Specifically, laser texturing creates a geometrically ordered microstructure on the Zn surface, while subsequent chemical permeation induces the in situ transformation of this microstructured layer into a CuZn<sub>5</sub> alloy, forming the LT-Zn@CuZn<sub>5</sub> anode. The geometrically ordered alloy coating homogenizes the electronic filed distribution across the zinc surface and enhances corrosion resistance. Thereby, the LT-Zn@CuZn<sub>5</sub> anode demonstrated optimized electrochemical reversibility, sustaining over 3000 cycles at 3 mA cm<sup>–2</sup>/1 mAh cm<sup>–2</sup>. This performance translates into a high improvement in the cycling behavior of the assembled Zn||I<sub>2</sub> soft pack battery, which acquired an initial capacity of 225.8 mAh g<sup>–1</sup> and retained 79.1% after 4000 cycles. In contrast, the counterpart employing untreated Zn foil started with a lower initial capacity of 180.7 mAh g<sup>–1</sup> and failed after less than 478 cycles. The demonstrated effective approach improves the front-end design strategy of ZMAs and contributes to the development of dendrite-free ZMAs.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"75 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842087","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}
Yao Yao, Yue Zhao, Huijuan Zhang, Wenting Pan, Wei Liang, Yijian Jiang, Xinlong Yan, Yinzhou Yan
The development of surface-enhanced Raman spectroscopy (SERS) as an ultrasensitive fingerprint analysis technique in precision medicine requires high-performance SERS substrates with controllable nanostructure (hot-spot) distribution, simple fabrication, superior stability, biocompatibility, and extraordinary optical responses. Unfortunately, fabrication of arbitrary nanostructures with high homogeneity on a large scale for SERS is still challenging. Herein, we report an ultrafast laser parallel fabrication protocol for Au/2D-transition-metal dichalcogenide hybrid SERS biosensors. The leveraged photonic nanojets (PNJs) are generated by a micron-sized microsphere monolayer to simultaneously trigger localized phase transition in 2H-MoTe2, achieving a 1T′-MoTe2 nanopattern array with a density of 1 million per mm2 by a single laser shot. The Au nanoparticle clusters (AuNCs) are subsequently grown in situ from the 1T′ regions, creating a AuNCs on 1T′/2H-MoTe2 (AuNCs@1T’/2H-MoTe2) hybrid SERS substrate. The fabricated feature diameter and overlay accuracy of the patterned AuNCs are 210.1 ± 3.4 and 9.2 ± 1.7 nm, respectively. To eliminate background noise, we designed dimer-AuNCs@1T′/2H-MoTe2 (dAuNCs@1T′/2H-MoTe2), achieving a detection limit of 10–13 M with an enhancement factor of 4.9 × 108 for the methylene blue (MB) analyte. The strong localized surface plasmon resonances in the dAuNCs as well as efficient charge transfers between Au, 2H-MoTe2, and MB contribute to the majority of Raman enhancement. The multiscale dAuNCs@1T′/2H-MoTe2 array provides a powerful SERSome (comprising multiple SERS spectra) platform for therapeutic drug monitoring, by which we successfully identified the metabolic behaviors of living gastric adenocarcinoma cells administered with two drugs, i.e., capecitabine, oxaliplatin, and their combination. The present work establishes opportunities for creating a highly ordered nanopattern array for ultrasensitive SERSome analysis of cell metabolism in cancer therapy.
{"title":"Ultrafast Laser-Induced 1T′/2H-MoTe2 Nanopattern with Au-Nanoclusters for Raman Monitoring of Cellular Drug Metabolism","authors":"Yao Yao, Yue Zhao, Huijuan Zhang, Wenting Pan, Wei Liang, Yijian Jiang, Xinlong Yan, Yinzhou Yan","doi":"10.1021/acsnano.5c01351","DOIUrl":"https://doi.org/10.1021/acsnano.5c01351","url":null,"abstract":"The development of surface-enhanced Raman spectroscopy (SERS) as an ultrasensitive fingerprint analysis technique in precision medicine requires high-performance SERS substrates with controllable nanostructure (hot-spot) distribution, simple fabrication, superior stability, biocompatibility, and extraordinary optical responses. Unfortunately, fabrication of arbitrary nanostructures with high homogeneity on a large scale for SERS is still challenging. Herein, we report an ultrafast laser parallel fabrication protocol for Au/2D-transition-metal dichalcogenide hybrid SERS biosensors. The leveraged photonic nanojets (PNJs) are generated by a micron-sized microsphere monolayer to simultaneously trigger localized phase transition in 2H-MoTe<sub>2</sub>, achieving a 1T′-MoTe<sub>2</sub> nanopattern array with a density of 1 million per mm<sup>2</sup> by a single laser shot. The Au nanoparticle clusters (AuNCs) are subsequently grown in situ from the 1T′ regions, creating a AuNCs on 1T′/2H-MoTe<sub>2</sub> (AuNCs@1T’/2H-MoTe<sub>2</sub>) hybrid SERS substrate. The fabricated feature diameter and overlay accuracy of the patterned AuNCs are 210.1 ± 3.4 and 9.2 ± 1.7 nm, respectively. To eliminate background noise, we designed dimer-AuNCs@1T′/2H-MoTe<sub>2</sub> (dAuNCs@1T′/2H-MoTe<sub>2</sub>), achieving a detection limit of 10<sup>–13</sup> M with an enhancement factor of 4.9 × 10<sup>8</sup> for the methylene blue (MB) analyte. The strong localized surface plasmon resonances in the dAuNCs as well as efficient charge transfers between Au, 2H-MoTe<sub>2</sub>, and MB contribute to the majority of Raman enhancement. The multiscale dAuNCs@1T′/2H-MoTe<sub>2</sub> array provides a powerful SERSome (comprising multiple SERS spectra) platform for therapeutic drug monitoring, by which we successfully identified the metabolic behaviors of living gastric adenocarcinoma cells administered with two drugs, i.e., capecitabine, oxaliplatin, and their combination. The present work establishes opportunities for creating a highly ordered nanopattern array for ultrasensitive SERSome analysis of cell metabolism in cancer therapy.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"24 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846898","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}
Ping Zhang, Han Yan, Zhihe Liang, Peng Zhang, Xiao-Hua Li, Xian-Zheng Yuan, Guangli Yu, Wei Wang, Chao Cai
Synthetic glycopolymers can be designed to mimic the structure and biological function of natural polysaccharides, offering a wide range of potential applications in the pharmaceutical and medicine. Nevertheless, amphiphilic synthetic glycopolymers commonly form biologically inert nanomicelle structures in aqueous solutions through spontaneous self-assembly. Envisioning that preventing self-assembly is pivotal to the full realization of the biological activities of the glycopolymers, we design and prepare a class of norbornene-derived hydrophilic glycopolymers containing sulfated fucose amenable to skeleton modification through ring-opening metathesis polymerization (ROMP). The skeleton of the fucoidan glycopolymers was chemically modified with hydrogen reduction, dihydroxylation, and oxidation following subsequent sulfation. We conducted physicochemical property characterization of the skeleton-modified glycopolymers to demonstrate that the hydrophilic glycopolymers have a more flexible structure compared to conventional polymers, and the sulfated fucoidan glycopolymers form a non-assembly morphology similar to the natural polysaccharides. Furthermore, the non-assembly glycopolymers exhibit significantly enhanced anti-HSV-1 activities. Our findings underscore the significance of the rational design of polymer skeletons in the development of structural and functional mimics of natural polysaccharides.
{"title":"Synthesis of Fucoidan-Biomimetic Glycopolymers with Flexible Skeletons for Enhanced Anti-Herpes Virus Efficacy","authors":"Ping Zhang, Han Yan, Zhihe Liang, Peng Zhang, Xiao-Hua Li, Xian-Zheng Yuan, Guangli Yu, Wei Wang, Chao Cai","doi":"10.1021/acsnano.4c15060","DOIUrl":"https://doi.org/10.1021/acsnano.4c15060","url":null,"abstract":"Synthetic glycopolymers can be designed to mimic the structure and biological function of natural polysaccharides, offering a wide range of potential applications in the pharmaceutical and medicine. Nevertheless, amphiphilic synthetic glycopolymers commonly form biologically inert nanomicelle structures in aqueous solutions through spontaneous self-assembly. Envisioning that preventing self-assembly is pivotal to the full realization of the biological activities of the glycopolymers, we design and prepare a class of norbornene-derived hydrophilic glycopolymers containing sulfated fucose amenable to skeleton modification through ring-opening metathesis polymerization (ROMP). The skeleton of the fucoidan glycopolymers was chemically modified with hydrogen reduction, dihydroxylation, and oxidation following subsequent sulfation. We conducted physicochemical property characterization of the skeleton-modified glycopolymers to demonstrate that the hydrophilic glycopolymers have a more flexible structure compared to conventional polymers, and the sulfated fucoidan glycopolymers form a non-assembly morphology similar to the natural polysaccharides. Furthermore, the non-assembly glycopolymers exhibit significantly enhanced anti-HSV-1 activities. Our findings underscore the significance of the rational design of polymer skeletons in the development of structural and functional mimics of natural polysaccharides.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"4 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842082","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 repair of articular cartilage defects remains a major regenerative and clinical challenge. Exosomes (Exos) derived from mesenchymal stem cells (MSCs) have good application potential in cartilage tissue engineering. Numerous studies have indicated that appropriate preconditioning methods can promote the therapeutic effect of Exos. Growth differentiation factor 5 (GDF-5) plays a critical role in chondrogenesis and regeneration. In this study, GDF-5 was used to precondition synovial mesenchymal stem cells (SMSCs) to increase the chondrogenic-promoting effect of Exos (G-Exos). In addition, we demonstrated that G-Exos rich in miR-383-3p increased the chondrogenic potential of SMSCs by activating the Kdm2a/SOX2 signaling pathway. On this basis, G-Exos were loaded into a glycyrrhizic acid/methacrylate-acylated hyaluronic acid (GA/HA/G-Exos) scaffold via digital light processing (DLP) bioprinting to maintain bioactivity and sustained release. The GA/HA/G-Exos scaffolds not only presented significant biological properties in vitro but also significantly promoted the remodeling of the joint cavity regenerative microenvironment and the regeneration of articular cartilage in Sprague–Dawley rats. This study provides a promising cell-free regenerative strategy for cartilage defect repair via the use of engineered exofunctionalized biological scaffolds.
{"title":"Three-Dimensional Bioprinting of Growth Differentiation Factor 5-Preconditioned Mesenchymal Stem Cell-Derived Exosomes Facilitates Articular Cartilage Endogenous Regeneration","authors":"Yazhe Zheng, Liwei Fu, Zhichao Zhang, Jiang Wu, Xun Yuan, Zhengang Ding, Chao Ning, Xiang Sui, Shuyun Liu, Quanyi Guo","doi":"10.1021/acsnano.4c13492","DOIUrl":"https://doi.org/10.1021/acsnano.4c13492","url":null,"abstract":"The repair of articular cartilage defects remains a major regenerative and clinical challenge. Exosomes (Exos) derived from mesenchymal stem cells (MSCs) have good application potential in cartilage tissue engineering. Numerous studies have indicated that appropriate preconditioning methods can promote the therapeutic effect of Exos. Growth differentiation factor 5 (GDF-5) plays a critical role in chondrogenesis and regeneration. In this study, GDF-5 was used to precondition synovial mesenchymal stem cells (SMSCs) to increase the chondrogenic-promoting effect of Exos (G-Exos). In addition, we demonstrated that G-Exos rich in miR-383-3p increased the chondrogenic potential of SMSCs by activating the Kdm2a/SOX2 signaling pathway. On this basis, G-Exos were loaded into a glycyrrhizic acid/methacrylate-acylated hyaluronic acid (GA/HA/G-Exos) scaffold via digital light processing (DLP) bioprinting to maintain bioactivity and sustained release. The GA/HA/G-Exos scaffolds not only presented significant biological properties in vitro but also significantly promoted the remodeling of the joint cavity regenerative microenvironment and the regeneration of articular cartilage in Sprague–Dawley rats. This study provides a promising cell-free regenerative strategy for cartilage defect repair via the use of engineered exofunctionalized biological scaffolds.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"108 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846803","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}
Lupeng Zeng, Wanhua Shi, Kewen Chen, Kun Wang, Yaping Dai, Xin Cheng, Shi Lu, Dandan Gao, Weiming Sun, Xi Zhang, Jing Zhang, Jinghua Chen
As ubiquitous transport nanovesicles in cell biology, plant exosome-like vesicles (PELVs) have enormous potential to deliver drugs safely and effectively. Drug encapsulation and mechanical stability of vesicles are key limitations influencing their delivery efficiency. However, common methods (i.e., ultrasound, electroporation) for drug loading inevitably affect the inherent vesicle characteristics, which influence their stability, leakproof nature, cellular internalization, and tumor penetration. Herein, in order to balance this contradiction, we put forward a strategy to skillfully remodel aloe exosome-like vesicles (AELVs) through indocyanine green (ICG)-induced hypotonic stress during endogenous drug loading. We observe that the rigidity of AELVs is enhanced with the accumulation of long hydrocarbon chain lipids under ICG-induced hypotonic stress. Synchronously, ICG is also loaded into AELVs (ICG/AELVs, IAs), which effectively prevents secondary damage during drug loading. More interestingly, we find that hypotonic stress promotes IA secretion with less intravesicular protein, which is beneficial to enlarge their inner space for more drug loading. The IAs show great storage stability, leakproof, and antidegradation performance. Compared with control AELVs, IAs with higher rigidity are more liable to penetrate into the tumor. IAs further modifying with the AS1411 aptamer (AS1411-IAs, AIAs) exhibit high tumor targeting in vivo. After intravenous administration, the 4T1 tumor is obviously inhibited by AIAs plus NIR irradiation, which effectively improves the survival rate of tumor-bearing mice. Overall, we systematically explore the effects of drug-induced osmotic stress on PELVs during endogenous drug loading and achieve efficient tumor therapy. This work simplifies the process of drug loading in PELVs and enhances their plasticity, which provides a promising perspective for PELV-based drug delivery and clinical application.
{"title":"Indocyanine Green Aggregation-Induced Hypotonic Stress to Remodel Aloe Exosome-like Vesicles for Enhanced Tumor Penetration and Phototherapy","authors":"Lupeng Zeng, Wanhua Shi, Kewen Chen, Kun Wang, Yaping Dai, Xin Cheng, Shi Lu, Dandan Gao, Weiming Sun, Xi Zhang, Jing Zhang, Jinghua Chen","doi":"10.1021/acsnano.4c15440","DOIUrl":"https://doi.org/10.1021/acsnano.4c15440","url":null,"abstract":"As ubiquitous transport nanovesicles in cell biology, plant exosome-like vesicles (PELVs) have enormous potential to deliver drugs safely and effectively. Drug encapsulation and mechanical stability of vesicles are key limitations influencing their delivery efficiency. However, common methods (i.e., ultrasound, electroporation) for drug loading inevitably affect the inherent vesicle characteristics, which influence their stability, leakproof nature, cellular internalization, and tumor penetration. Herein, in order to balance this contradiction, we put forward a strategy to skillfully remodel aloe exosome-like vesicles (AELVs) through indocyanine green (ICG)-induced hypotonic stress during endogenous drug loading. We observe that the rigidity of AELVs is enhanced with the accumulation of long hydrocarbon chain lipids under ICG-induced hypotonic stress. Synchronously, ICG is also loaded into AELVs (ICG/AELVs, IAs), which effectively prevents secondary damage during drug loading. More interestingly, we find that hypotonic stress promotes IA secretion with less intravesicular protein, which is beneficial to enlarge their inner space for more drug loading. The IAs show great storage stability, leakproof, and antidegradation performance. Compared with control AELVs, IAs with higher rigidity are more liable to penetrate into the tumor. IAs further modifying with the AS1411 aptamer (AS1411-IAs, AIAs) exhibit high tumor targeting <i>in vivo</i>. After intravenous administration, the 4T1 tumor is obviously inhibited by AIAs plus NIR irradiation, which effectively improves the survival rate of tumor-bearing mice. Overall, we systematically explore the effects of drug-induced osmotic stress on PELVs during endogenous drug loading and achieve efficient tumor therapy. This work simplifies the process of drug loading in PELVs and enhances their plasticity, which provides a promising perspective for PELV-based drug delivery and clinical application.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"111 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842084","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}
Duy Van Nguyen, Pingan Song, Farid Manshaii, John Bell, Jun Chen, Toan Dinh
1. In the original version of this paper, the information about the affiliation of two authors is not completely accurate (page 6697). The correct affiliation for Jun Chen and Farid Manshaii is Department of Bioengineering, University of California, Los Angeles, Los Angeles, California 90095, United States. The changes are reflected in the authorship of this Correction. 2. The title “Pressure Sensors Insensitive to Off-Axis Mechanical Deformations” (page 6684) should be the same heading level as the title “STRAIN SENSORS INSENSITIVE TO OFF-AXIS MECHANICAL DEFORMATIONS” (page 6687). 3. The format of Table 1, Table 3, and Table 4 may cause confusion for reading due to the formatting process. Corrected Table 1, Table 3, and Table 4 are below: This article has not yet been cited by other publications.
{"title":"Correction to “Advances in Soft Strain and Pressure Sensors”","authors":"Duy Van Nguyen, Pingan Song, Farid Manshaii, John Bell, Jun Chen, Toan Dinh","doi":"10.1021/acsnano.5c02658","DOIUrl":"https://doi.org/10.1021/acsnano.5c02658","url":null,"abstract":"1. In the original version of this paper, the information about the affiliation of two authors is not completely accurate (page 6697). The correct affiliation for Jun Chen and Farid Manshaii is Department of Bioengineering, University of California, Los Angeles, Los Angeles, California 90095, United States. The changes are reflected in the authorship of this Correction. 2. The title “Pressure Sensors Insensitive to Off-Axis Mechanical Deformations” (page 6684) should be the same heading level as the title “STRAIN SENSORS INSENSITIVE TO OFF-AXIS MECHANICAL DEFORMATIONS” (page 6687). 3. The format of Table 1, Table 3, and Table 4 may cause confusion for reading due to the formatting process. Corrected Table 1, Table 3, and Table 4 are below: This article has not yet been cited by other publications.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"22 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842088","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}
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