Owing to its negligible biological background and high magnetic resonance sensitivity, 19F magnetic resonance imaging (MRI) has emerged as a competitive complement for 1H MRI, which is already widely used in biomedical research and clinical practice. The performance of 19F MRI is greatly reliant on imaging probes, the development of which poses considerable demands on 19F sources. Fluorinated ionic liquids (FILs) have recently attracted increasing attention as alternative 19F sources because of their good aqueous solubility, ease of chemical modification, and high fluorine contents. However, the imaging performance of FIL-based probes is significantly restricted by their unfavorable 19F relaxation times. Herein, we developed a strategy to modulate the 19F relaxation times (including both T1 and T2) of FILs by exploiting the paramagnetic relaxation enhancement effect of Mn2+ ions to promote their imaging capacity. The 19F relaxation times of three FILs including EMIMBF4, BMIMOTf, and BMIMPF6 are appropriately tuned with paramagnetic Mn2+ ions at optimized concentrations, resulting in significant signal enhancement over 5-fold. We further utilized liposils to encapsulate these FILs with Mn2+ ions to construct 19F MRI probes, which enables fast and clear 19F MRI as illustrated by a series of in vivo experiments. Moreover, we made a 19F MRI probe containing all three FILs and Mn2+ ions at the optimized concentration, whose capacity for multiplexed 19F MRI is also validated with in vivo experiments. Our study demonstrates the promising potential of paramagnetic FIL-based probes for in vivo “hot spot” 19F MRI, and more importantly, the feasibility of relaxation modulation for the construction of high-performance 19F MRI probes.
{"title":"Sensitive Multichannel 19F Magnetic Resonance Imaging Enabled by Paramagnetic Fluorinated Ionic Liquid-Based Probes","authors":"Limin Chen, Yuhang Jiang, Nan Xiong, Yifan Fan, Hongyu Lin, Jinhao Gao","doi":"10.1021/acsnano.4c17959","DOIUrl":"https://doi.org/10.1021/acsnano.4c17959","url":null,"abstract":"Owing to its negligible biological background and high magnetic resonance sensitivity, <sup>19</sup>F magnetic resonance imaging (MRI) has emerged as a competitive complement for <sup>1</sup>H MRI, which is already widely used in biomedical research and clinical practice. The performance of <sup>19</sup>F MRI is greatly reliant on imaging probes, the development of which poses considerable demands on <sup>19</sup>F sources. Fluorinated ionic liquids (FILs) have recently attracted increasing attention as alternative <sup>19</sup>F sources because of their good aqueous solubility, ease of chemical modification, and high fluorine contents. However, the imaging performance of FIL-based probes is significantly restricted by their unfavorable <sup>19</sup>F relaxation times. Herein, we developed a strategy to modulate the <sup>19</sup>F relaxation times (including both <i>T</i><sub>1</sub> and <i>T</i><sub>2</sub>) of FILs by exploiting the paramagnetic relaxation enhancement effect of Mn<sup>2+</sup> ions to promote their imaging capacity. The <sup>19</sup>F relaxation times of three FILs including EMIMBF<sub>4</sub>, BMIMOTf, and BMIMPF<sub>6</sub> are appropriately tuned with paramagnetic Mn<sup>2+</sup> ions at optimized concentrations, resulting in significant signal enhancement over 5-fold. We further utilized liposils to encapsulate these FILs with Mn<sup>2+</sup> ions to construct <sup>19</sup>F MRI probes, which enables fast and clear <sup>19</sup>F MRI as illustrated by a series of <i>in vivo</i> experiments. Moreover, we made a <sup>19</sup>F MRI probe containing all three FILs and Mn<sup>2+</sup> ions at the optimized concentration, whose capacity for multiplexed <sup>19</sup>F MRI is also validated with <i>in vivo</i> experiments. Our study demonstrates the promising potential of paramagnetic FIL-based probes for <i>in vivo</i> “hot spot” <sup>19</sup>F MRI, and more importantly, the feasibility of relaxation modulation for the construction of high-performance <sup>19</sup>F MRI probes.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"1 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526328","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}
We identified an error in the original version of this article. Specifically, one photograph of rat spinal cord tissues was erroneously uploaded in the AhCeO2-Gel group of Figure S27 of the Supporting Information. The corrected Figure S27 is included in the associated Supporting Information. This error does not alter any of the reported results, interpretations, or conclusions of the study. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsnano.5c02489. Same description as in the original article (PDF) Correction to “Nitric Oxide-Releasing Mesoporous Hollow Cerium Oxide Nanozyme-Based Hydrogel Synergizes with Neural Stem Cells for Spinal Cord Injury Repair” 0 views 0 shares 0 downloads Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. This article has not yet been cited by other publications.
{"title":"Correction to “Nitric Oxide-Releasing Mesoporous Hollow Cerium Oxide Nanozyme-Based Hydrogel Synergizes with Neural Stem Cells for Spinal Cord Injury Repair”","authors":"Dun Liu, Runyan Niu, Siliang Wang, Lihua Shao, Xian Yang, Xuexue Liu, Xiaolong Ma, Zezhang Zhu, Jinping Zhang, Benlong Shi, Huanyu Ni, Xiao Du","doi":"10.1021/acsnano.5c02489","DOIUrl":"https://doi.org/10.1021/acsnano.5c02489","url":null,"abstract":"We identified an error in the original version of this article. Specifically, one photograph of rat spinal cord tissues was erroneously uploaded in the AhCeO<sub>2</sub>-Gel group of Figure S27 of the Supporting Information. The corrected Figure S27 is included in the associated Supporting Information. This error does not alter any of the reported results, interpretations, or conclusions of the study. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsnano.5c02489. Same description as in the original article (PDF) Correction to “Nitric\u0000Oxide-Releasing Mesoporous\u0000Hollow Cerium Oxide Nanozyme-Based Hydrogel Synergizes with Neural\u0000Stem Cells for Spinal Cord Injury Repair” <span> 0 </span><span> views </span> <span> 0 </span><span> shares </span> <span> 0 </span><span> downloads </span> Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. This article has not yet been cited by other publications.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"152 4 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526329","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}
Yiting Song, Wei-Chiao Huang, Danton Ivanochko, Carole Long, Qinzhe Li, Luwen Zhou, Jean-Philippe Julien, Kazutoyo Miura, Jonathan F. Lovell
Displaying soluble vaccine protein antigens onto the surface of adjuvanted nanoliposomes can enhance the magnitude of elicited antibody responses. In this study, we examine this approach with respect to dose sparing, for not only the antigen component but also the adjuvant dose in the vaccine. Using a structurally stabilized Pfs48/45 derived malarial protein as a model antigen, we confirmed the protein rapidly displayed on the surface of immunogenic liposomes containing cobalt porphyrin phospholipid (CoPoP; for antigen display via His-tag interaction) along with the immunostimulatory adjuvants monophosphoryl lipid A (MPLA) and QS-21. Mice were immunized with a fixed protein antigen dose with varying adjuvant doses to estimate the extent of adjuvant sparing. In mice vaccinated at a fixed protein antigen dose, liposome-bound Pfs48/45 achieved superior antibody IgG titers compared to the soluble (nonbound) form at all assessed adjuvant doses, reflecting MPLA and QS-21 adjuvant dose sparing of at least 50-fold. The primary driver of adjuvant sparing in these conditions was presentation of the antigen in a nanoparticle format, and potent responses were achieved even without co-delivery of antigen and adjuvant within the same particle, provided that adjuvant and liposome-displayed antigen were co-administered to the same injection site. By keeping the adjuvant dose fixed and varying the antigen dose in a comparable experimental design, ∼20-fold antigen dose sparing was observed with liposome display. This case study illustrates the potential of antigen-display nanotechnologies, such as CoPoP nanoliposomes, to achieve substantial adjuvant and antigen dose sparing, which could theoretically facilitate the deployment of future vaccines.
{"title":"50-Fold Adjuvant and 20-Fold Antigen Vaccine Dose Sparing from Nanoliposome Display of a Stabilized Malarial Protein Antigen","authors":"Yiting Song, Wei-Chiao Huang, Danton Ivanochko, Carole Long, Qinzhe Li, Luwen Zhou, Jean-Philippe Julien, Kazutoyo Miura, Jonathan F. Lovell","doi":"10.1021/acsnano.4c16865","DOIUrl":"https://doi.org/10.1021/acsnano.4c16865","url":null,"abstract":"Displaying soluble vaccine protein antigens onto the surface of adjuvanted nanoliposomes can enhance the magnitude of elicited antibody responses. In this study, we examine this approach with respect to dose sparing, for not only the antigen component but also the adjuvant dose in the vaccine. Using a structurally stabilized Pfs48/45 derived malarial protein as a model antigen, we confirmed the protein rapidly displayed on the surface of immunogenic liposomes containing cobalt porphyrin phospholipid (CoPoP; for antigen display via His-tag interaction) along with the immunostimulatory adjuvants monophosphoryl lipid A (MPLA) and QS-21. Mice were immunized with a fixed protein antigen dose with varying adjuvant doses to estimate the extent of adjuvant sparing. In mice vaccinated at a fixed protein antigen dose, liposome-bound Pfs48/45 achieved superior antibody IgG titers compared to the soluble (nonbound) form at all assessed adjuvant doses, reflecting MPLA and QS-21 adjuvant dose sparing of at least 50-fold. The primary driver of adjuvant sparing in these conditions was presentation of the antigen in a nanoparticle format, and potent responses were achieved even without co-delivery of antigen and adjuvant within the same particle, provided that adjuvant and liposome-displayed antigen were co-administered to the same injection site. By keeping the adjuvant dose fixed and varying the antigen dose in a comparable experimental design, ∼20-fold antigen dose sparing was observed with liposome display. This case study illustrates the potential of antigen-display nanotechnologies, such as CoPoP nanoliposomes, to achieve substantial adjuvant and antigen dose sparing, which could theoretically facilitate the deployment of future vaccines.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"11 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526327","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}
Interfacial solar vapor generation (ISVG) technology has been considered a promising and sustainable strategy for seawater desalination and wastewater treatment. However, its practical application is greatly limited due to severe salt accumulation and poor long-term evaporation stability. Herein, an all-cellulose-based wicking fabric (CB@CA/CF) is fabricated via a breath figure template (BFT) method for high-performance and stable desalination. The abundant porous structure of carbon black@cellulose acetate (CB@CA) endows the evaporator with high light absorption (∼96.9%) and rapid steam escape. The hydrophilic CA network also changes the hydration state and greatly reduces the water evaporation enthalpy. More importantly, the unique double-layer porous structure of CB@CA and cotton fabric (CF) produces a rapid antigravitational wicking effect, providing sufficient water supply for vapor generation and preventing salt accumulation on the evaporator surface. As a result, the CB@CA/CF evaporator can achieve high evaporation rates of 2.08 kg m–2 h–1 in pure water and 1.98 kg m–2 h–1 in a 3.5 wt % NaCl solution under one-sun irradiation, without any salt accumulation over 8 h. Moreover, the designed floating evaporation system can obtain a high freshwater collection of 8.39 kg m–2per day under natural environmental conditions. This work provides an effective path for developing stable and highly efficient freshwater acquisition and shows great prospects in the field of seawater desalination and wastewater treatment.
{"title":"Architecting of All-Cellulose-Based Wicking Fabric for a Large-Scale, Low-Cost, and Highly Efficient Solar Desalination Evaporator","authors":"Feng Xia, Yankuan Tian, Xinyue Zhang, Yifei Gong, Xin Yang, Xinqi Guo, Shukang Yang, Yan Hu, Xue Xu, Rong Zhou, Xueli Wang, Faxue Li, Jianyong Yu, Tingting Gao","doi":"10.1021/acsnano.4c14352","DOIUrl":"https://doi.org/10.1021/acsnano.4c14352","url":null,"abstract":"Interfacial solar vapor generation (ISVG) technology has been considered a promising and sustainable strategy for seawater desalination and wastewater treatment. However, its practical application is greatly limited due to severe salt accumulation and poor long-term evaporation stability. Herein, an all-cellulose-based wicking fabric (CB@CA/CF) is fabricated via a breath figure template (BFT) method for high-performance and stable desalination. The abundant porous structure of carbon black@cellulose acetate (CB@CA) endows the evaporator with high light absorption (∼96.9%) and rapid steam escape. The hydrophilic CA network also changes the hydration state and greatly reduces the water evaporation enthalpy. More importantly, the unique double-layer porous structure of CB@CA and cotton fabric (CF) produces a rapid antigravitational wicking effect, providing sufficient water supply for vapor generation and preventing salt accumulation on the evaporator surface. As a result, the CB@CA/CF evaporator can achieve high evaporation rates of 2.08 kg m<sup>–2</sup> h<sup>–1</sup> in pure water and 1.98 kg m<sup>–2</sup> h<sup>–1</sup> in a 3.5 wt % NaCl solution under one-sun irradiation, without any salt accumulation over 8 h. Moreover, the designed floating evaporation system can obtain a high freshwater collection of 8.39 kg m<sup>–2</sup> <i>per day</i> under natural environmental conditions. This work provides an effective path for developing stable and highly efficient freshwater acquisition and shows great prospects in the field of seawater desalination and wastewater treatment.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"1 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526300","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}
Andrea Auer, Franz J. Giessibl, Julia Kunze-Liebhäuser
All electrochemical and electrocatalytic processes occur at the boundary between an electrode and an electrolyte. Progress in the field of electrochemistry requires a detailed microscopic understanding of these complex solid–liquid interfaces, making this a captivating field for in situ surface-sensitive microscopic techniques, such as scanning probe microscopy. In this Perspective, we outline the roadmap of electrochemical scanning probe microscopy and explore its most recent developments in fundamental research on interface characterization and electrocatalysis. Most importantly, we introduce the reader to the simultaneous operation of electrochemical scanning tunneling microscopy and force microscopy using a qPlus sensor, highlighting its potential to provide high precision, enhanced flexibility and versatility, particularly as a combined approach to interface characterization. Additionally, we identify key future opportunities and challenges.
{"title":"Combining Electrochemical Scanning Tunneling Microscopy with Force Microscopy","authors":"Andrea Auer, Franz J. Giessibl, Julia Kunze-Liebhäuser","doi":"10.1021/acsnano.5c00591","DOIUrl":"https://doi.org/10.1021/acsnano.5c00591","url":null,"abstract":"All electrochemical and electrocatalytic processes occur at the boundary between an electrode and an electrolyte. Progress in the field of electrochemistry requires a detailed microscopic understanding of these complex solid–liquid interfaces, making this a captivating field for in situ surface-sensitive microscopic techniques, such as scanning probe microscopy. In this Perspective, we outline the roadmap of electrochemical scanning probe microscopy and explore its most recent developments in fundamental research on interface characterization and electrocatalysis. Most importantly, we introduce the reader to the simultaneous operation of electrochemical scanning tunneling microscopy and force microscopy using a qPlus sensor, highlighting its potential to provide high precision, enhanced flexibility and versatility, particularly as a combined approach to interface characterization. Additionally, we identify key future opportunities and challenges.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"33 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526331","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}
Yutong Nong, Xiaowei Wang, Minghuang Li, Jingyi Zhang, Weijie Ji, Yi Zhao, Lei Cheng, Xing Ou, Lei Ming, Xiaoming Yuan, Jiafeng Zhang, Bao Zhang, Lei Dong, Jianmin Feng, Ruirui Zhao, Zhiyuan Sang, Ji Liang
O3-type layered oxides are promising cathode materials for sodium-ion batteries due to their easy synthesis and high sodium content. However, complex phase transitions and poor air stability limit their practical applications. Introducing sodium deficiency suppresses reactions with air and improves phase stability, but often at the cost of significantly compromising the sodium storage capacity. Herein, we present a hierarchical composition regulation strategy to achieve radial concentration control of sodium in the O3-type layered oxides, constructing radially distributed sodium gradients. The gradient Na content structure not only can alleviate the volume changes caused by the O3–P3 phase transition, which minimizes the degradation of electrochemical performance during cycling, but also suppresses Na+/H+ exchange. This ensures enhanced air stability, improved kinetic performance, and cycling stability. The modified cathode material exhibits a capacity retention rate of 93.37% after 400 cycles at 5 C. When exposed to 82% relative humidity, CO2 concentration of 3044 ppm for 10 h, it still maintains a specific capacity of 84.9 mA h g–1 after 300 cycles at 1 C, with a capacity retention rate of 77.27%. This work provides a strategy for radial sodium concentration control, contributing to the development of high-performance and air-stable O3-type sodium-ion battery cathode materials.
{"title":"Gradient Sodium Deficiency Optimization in O3-Type Cathode Materials for Superior Performance and Air Stability","authors":"Yutong Nong, Xiaowei Wang, Minghuang Li, Jingyi Zhang, Weijie Ji, Yi Zhao, Lei Cheng, Xing Ou, Lei Ming, Xiaoming Yuan, Jiafeng Zhang, Bao Zhang, Lei Dong, Jianmin Feng, Ruirui Zhao, Zhiyuan Sang, Ji Liang","doi":"10.1021/acsnano.4c16523","DOIUrl":"https://doi.org/10.1021/acsnano.4c16523","url":null,"abstract":"O3-type layered oxides are promising cathode materials for sodium-ion batteries due to their easy synthesis and high sodium content. However, complex phase transitions and poor air stability limit their practical applications. Introducing sodium deficiency suppresses reactions with air and improves phase stability, but often at the cost of significantly compromising the sodium storage capacity. Herein, we present a hierarchical composition regulation strategy to achieve radial concentration control of sodium in the O3-type layered oxides, constructing radially distributed sodium gradients. The gradient Na content structure not only can alleviate the volume changes caused by the O3–P3 phase transition, which minimizes the degradation of electrochemical performance during cycling, but also suppresses Na<sup>+</sup>/H<sup>+</sup> exchange. This ensures enhanced air stability, improved kinetic performance, and cycling stability. The modified cathode material exhibits a capacity retention rate of 93.37% after 400 cycles at 5 C. When exposed to 82% relative humidity, CO<sub>2</sub> concentration of 3044 ppm for 10 h, it still maintains a specific capacity of 84.9 mA h g<sup>–1</sup> after 300 cycles at 1 C, with a capacity retention rate of 77.27%. This work provides a strategy for radial sodium concentration control, contributing to the development of high-performance and air-stable O3-type sodium-ion battery cathode materials.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"1 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518439","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}
Seunghwan Bang, Byeongmin Park, Jae Chul Park, Harin Jin, Ji Sung Shim, Jahyun Koo, Kwan Hyi Lee, Man Kyu Shim, Hojun Kim
The extracellular matrix (ECM) is a complex network of biomolecules with varying pore sizes, posing a challenge for the effective penetration of lipid nanoparticles. In contrast, cell-derived lipid nanoparticles, such as exosomes, have demonstrated the ability to travel to distant organs, indicating their capacity to penetrate the ECM. Here, we designed exosome-like vesicles (ELVs) inspired by exosomes’ distinct transport phenomena. Specifically, we integrated three exosomal components (anionic lipid, cholesterol, and aquaporin-1) associated with transport into our ELVs to mimic the superior diffusion behavior of exosomes over synthetic lipid nanoparticles. Surprisingly, both bulk- and single-particle-diffusion studies revealed a more than 33 times increase in the effective diffusion coefficient within model ECM compared to conventional lipid nanoparticles. Furthermore, ELVs show an 80% increase in the effective diffusion coefficient within biological tissues. The excellent transport behavior of ELVs was further validated in vivo, where intratumoral injection showcased their superior transport. These findings provide insights into lipid nanoparticle design for improved tissue penetration.
{"title":"Exosome-Inspired Lipid Nanoparticles for Enhanced Tissue Penetration","authors":"Seunghwan Bang, Byeongmin Park, Jae Chul Park, Harin Jin, Ji Sung Shim, Jahyun Koo, Kwan Hyi Lee, Man Kyu Shim, Hojun Kim","doi":"10.1021/acsnano.4c16629","DOIUrl":"https://doi.org/10.1021/acsnano.4c16629","url":null,"abstract":"The extracellular matrix (ECM) is a complex network of biomolecules with varying pore sizes, posing a challenge for the effective penetration of lipid nanoparticles. In contrast, cell-derived lipid nanoparticles, such as exosomes, have demonstrated the ability to travel to distant organs, indicating their capacity to penetrate the ECM. Here, we designed exosome-like vesicles (ELVs) inspired by exosomes’ distinct transport phenomena. Specifically, we integrated three exosomal components (anionic lipid, cholesterol, and aquaporin-1) associated with transport into our ELVs to mimic the superior diffusion behavior of exosomes over synthetic lipid nanoparticles. Surprisingly, both bulk- and single-particle-diffusion studies revealed a more than 33 times increase in the effective diffusion coefficient within model ECM compared to conventional lipid nanoparticles. Furthermore, ELVs show an 80% increase in the effective diffusion coefficient within biological tissues. The excellent transport behavior of ELVs was further validated <i>in vivo</i>, where intratumoral injection showcased their superior transport. These findings provide insights into lipid nanoparticle design for improved tissue penetration.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"43 2 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518440","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}
Zhongyu Liu, Yitong Wang, Weijie Ji, Xiaowei Ma, Christopher G. Gianopoulos, Sebastian Calderon, Timothy Ma, Lianshun Luo, Abhrojyoti Mazumder, Kristin Kirschbaum, Elizabeth C. Dickey, Linda A. Peteanu, Dominic Alfonso, Rongchao Jin
For the majority of gold nanoclusters (NCs), their water insolubility, low photoluminescence (PL) intensity, and less understood photostability are three critical factors that limit their application in the biomedical and photocatalysis fields. In this study, we report a polymer wrapping method for phase transfer of organic soluble NCs into aqueous phase without degrading the electronic and optical properties, and such materials are further demonstrated for robust photocatalysis in water. We first synthesized a Au18(DMBT)14 NC (DMBT = 2,4-dimethylbenzenethiolate) and found that the aromatic ligands confer a greatly enhanced antioxidation capability of the NC compared to the Au18(CHT)14 counterpart (CHT = cyclohexanethiolate), with the critical role of aromatic ligand interactions identified by X-ray crystallography. The organic soluble Au18(DMBT)14 was successfully transferred into the aqueous phase by an amphiphilic polymer (Pluronic F127, abbrev. F127) wrapping method, producing Au18-D@F127 nanoparticles [each containing a few NCs; Au18-D is an abbreviation for Au18(DMBT)14] with a 10-fold enhancement in PL intensity, and similar results were also obtained for Au18(CHT)14. This method is broadly applicable to various NCs, rendering their water solubility and significantly enhancing the PL intensity of otherwise weakly emissive gold NCs. The exceptional antioxidation stability of Au18(DMBT)14 enables the application of Au18-D@F127 NPs for the photocatalytic activation of persulfate ions and subsequent photodegradation of water pollutants efficiently.
{"title":"Generalizable Organic-to-Aqueous Phase Transfer of a Au18 Nanocluster with Luminescence Enhancement and Robust Photocatalysis in Water","authors":"Zhongyu Liu, Yitong Wang, Weijie Ji, Xiaowei Ma, Christopher G. Gianopoulos, Sebastian Calderon, Timothy Ma, Lianshun Luo, Abhrojyoti Mazumder, Kristin Kirschbaum, Elizabeth C. Dickey, Linda A. Peteanu, Dominic Alfonso, Rongchao Jin","doi":"10.1021/acsnano.4c18197","DOIUrl":"https://doi.org/10.1021/acsnano.4c18197","url":null,"abstract":"For the majority of gold nanoclusters (NCs), their water insolubility, low photoluminescence (PL) intensity, and less understood photostability are three critical factors that limit their application in the biomedical and photocatalysis fields. In this study, we report a polymer wrapping method for phase transfer of organic soluble NCs into aqueous phase without degrading the electronic and optical properties, and such materials are further demonstrated for robust photocatalysis in water. We first synthesized a Au<sub>18</sub>(DMBT)<sub>14</sub> NC (DMBT = 2,4-dimethylbenzenethiolate) and found that the aromatic ligands confer a greatly enhanced antioxidation capability of the NC compared to the Au<sub>18</sub>(CHT)<sub>14</sub> counterpart (CHT = cyclohexanethiolate), with the critical role of aromatic ligand interactions identified by X-ray crystallography. The organic soluble Au<sub>18</sub>(DMBT)<sub>14</sub> was successfully transferred into the aqueous phase by an amphiphilic polymer (Pluronic F127, abbrev. F127) wrapping method, producing Au<sub>18</sub>-D@F127 nanoparticles [each containing a few NCs; Au<sub>18</sub>-D is an abbreviation for Au<sub>18</sub>(DMBT)<sub>14</sub>] with a 10-fold enhancement in PL intensity, and similar results were also obtained for Au<sub>18</sub>(CHT)<sub>14</sub>. This method is broadly applicable to various NCs, rendering their water solubility and significantly enhancing the PL intensity of otherwise weakly emissive gold NCs. The exceptional antioxidation stability of Au<sub>18</sub>(DMBT)<sub>14</sub> enables the application of Au<sub>18</sub>-D@F127 NPs for the photocatalytic activation of persulfate ions and subsequent photodegradation of water pollutants efficiently.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"22 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518441","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–sulfur (Na–S) batteries provide lithium-free alternatives to lithium–sulfur (Li–S) batteries. Na–S chemistry has been less studied. Thus, the types of polysulfides (PS) and their evolution during charge–discharge of Na–S batteries are not as well understood as those in the Li–S system. We, therefore, study the formation of different PS in tetraethylene glycol dimethyl ether-based electrolyte during battery operation using in situ Raman and ex situ ultraviolet–visible (UV–vis) spectroscopies. We start by making reference solutions with different ratios of sodium sulfide (Na2S) to sulfur, ranging from pure Na2S to Na2S:7S, with the sulfur ratio increasing by one integer per solution. We then correlate the UV–vis and Raman peaks to PS species. Our galvanostatic charge–discharge (GCD) and cyclic voltammetry measurements show a total of ten features. Using ex situ UV–vis on aliquots and in situ Raman spectra from PS solutions at GCD voltage plateaus, we map out sodium polysulfide (NaPS) species at key stages of the charge–discharge cycle. We identify Na2S8, Na2S4, and Na2S2 as intermediates and Na2S as the final product. We find that intermediate Na2S6 forms from disproportionation of Na2S8 and Na2S4. We also observe that intermediate PS can also dissociate into S3•– radical species, which contributes to loss of active material. Our results provide detailed insights into Na–S chemistry that will be helpful for the development of high performance and stable batteries.
{"title":"Mapping Polysulfides in Sodium–Sulfur Batteries","authors":"Esther Lilian Gray, Jung-In Lee, Zhuangnan Li, James Moloney, Ziwei Jeffrey Yang, Manish Chhowalla","doi":"10.1021/acsnano.4c16941","DOIUrl":"https://doi.org/10.1021/acsnano.4c16941","url":null,"abstract":"Sodium–sulfur (Na–S) batteries provide lithium-free alternatives to lithium–sulfur (Li–S) batteries. Na–S chemistry has been less studied. Thus, the types of polysulfides (PS) and their evolution during charge–discharge of Na–S batteries are not as well understood as those in the Li–S system. We, therefore, study the formation of different PS in tetraethylene glycol dimethyl ether-based electrolyte during battery operation using <i>in situ</i> Raman and <i>ex situ</i> ultraviolet–visible (UV–vis) spectroscopies. We start by making reference solutions with different ratios of sodium sulfide (Na<sub>2</sub>S) to sulfur, ranging from pure Na<sub>2</sub>S to Na<sub>2</sub>S:7S, with the sulfur ratio increasing by one integer per solution. We then correlate the UV–vis and Raman peaks to PS species. Our galvanostatic charge–discharge (GCD) and cyclic voltammetry measurements show a total of ten features. Using <i>ex situ</i> UV–vis on aliquots and <i>in situ</i> Raman spectra from PS solutions at GCD voltage plateaus, we map out sodium polysulfide (NaPS) species at key stages of the charge–discharge cycle. We identify Na<sub>2</sub>S<sub>8</sub>, Na<sub>2</sub>S<sub>4</sub>, and Na<sub>2</sub>S<sub>2</sub> as intermediates and Na<sub>2</sub>S as the final product. We find that intermediate Na<sub>2</sub>S<sub>6</sub> forms from disproportionation of Na<sub>2</sub>S<sub>8</sub> and Na<sub>2</sub>S<sub>4</sub>. We also observe that intermediate PS can also dissociate into S<sub>3</sub><sup>•–</sup> radical species, which contributes to loss of active material. Our results provide detailed insights into Na–S chemistry that will be helpful for the development of high performance and stable batteries.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"130 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526330","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}
Younseong Song, Hyunji Park, Prudhvi Thirumalaraju, Niveditha Kovilakath, Joseph Michael Hardie, Arafeh Bigdeli, Yueying Bai, Sukbeom Chang, Jungmin Yoo, Manoj Kumar Kanakasabapathy, Sungwan Kim, Juhyeon Chun, Hui Chen, Jonathan Z. Li, Athe M. Tsibris, Daniel R. Kuritzkes, Hadi Shafiee
Digital nucleic acid assays, known for their high sensitivity and specificity, typically rely on fluorescent readouts and expensive and complex nanowell manufacturing, which constrain their broader use in point-of-care (POC) application. Here, we introduce an alternative digital molecular diagnostics, termed dCRISTOR, by seamlessly integrating deactivated Cas9 (dCas9)-engineered micromotors, extraction-free loop-mediated isothermal amplification (LAMP), low-cost bright field microscopy, and deep learning-enabled image processing. The micromotor, composed of a polystyrene sphere attached to a magnetic bead, incorporates a dCas9 ribonucleoprotein complex. The presence of human immunodeficiency virus-1 (HIV-1) RNA in a sample results in the formation of large-sized amplicons that can be specifically captured by the micromotors, reducing their velocity induced by an external magnetic field. The micromotor is propelled by an external magnetic field, which eliminates the need for chemical fuels, reducing system complexity, and allowing for precise control over micromotor movement, enhancing accuracy and reliability. A convolutional neural network classification-based multiobject tracking algorithm, CNN-MOT, accurately measures the change in micromotor motion, facilitating the binary digital assay format (“1” or “0”) for simplified result interpretation without user bias. Incorporating an extraction-free LAMP assay streamlines the dCRISTOR workflow, enabling qualitative HIV-1 detection in spiked plasma (n = 21) that demonstrates 100% sensitivity and specificity and achieves a limit of detection (LOD) of 0.96 copies/μL. The assay also achieved 100% correlation with reverse transcription-quantitative polymerase chain reaction (RT-qPCR) in clinical patient samples (n = 9). The dCRISTOR assay, a label-free digital nucleic acid testing system that eliminates the need for fluorescence readouts, absorbance measurements, or expensive manufacturing processes, represents a substantial advancement in digital viral RNA diagnostics.
{"title":"Deactivated Cas9-Engineered Magnetic Micromotors toward a Point-of-Care Digital Viral RNA Assay","authors":"Younseong Song, Hyunji Park, Prudhvi Thirumalaraju, Niveditha Kovilakath, Joseph Michael Hardie, Arafeh Bigdeli, Yueying Bai, Sukbeom Chang, Jungmin Yoo, Manoj Kumar Kanakasabapathy, Sungwan Kim, Juhyeon Chun, Hui Chen, Jonathan Z. Li, Athe M. Tsibris, Daniel R. Kuritzkes, Hadi Shafiee","doi":"10.1021/acsnano.4c14913","DOIUrl":"https://doi.org/10.1021/acsnano.4c14913","url":null,"abstract":"Digital nucleic acid assays, known for their high sensitivity and specificity, typically rely on fluorescent readouts and expensive and complex nanowell manufacturing, which constrain their broader use in point-of-care (POC) application. Here, we introduce an alternative digital molecular diagnostics, termed dCRISTOR, by seamlessly integrating deactivated Cas9 (dCas9)-engineered micromotors, extraction-free loop-mediated isothermal amplification (LAMP), low-cost bright field microscopy, and deep learning-enabled image processing. The micromotor, composed of a polystyrene sphere attached to a magnetic bead, incorporates a dCas9 ribonucleoprotein complex. The presence of human immunodeficiency virus-1 (HIV-1) RNA in a sample results in the formation of large-sized amplicons that can be specifically captured by the micromotors, reducing their velocity induced by an external magnetic field. The micromotor is propelled by an external magnetic field, which eliminates the need for chemical fuels, reducing system complexity, and allowing for precise control over micromotor movement, enhancing accuracy and reliability. A convolutional neural network classification-based multiobject tracking algorithm, CNN-MOT, accurately measures the change in micromotor motion, facilitating the binary digital assay format (“1” or “0”) for simplified result interpretation without user bias. Incorporating an extraction-free LAMP assay streamlines the dCRISTOR workflow, enabling qualitative HIV-1 detection in spiked plasma (<i>n</i> = 21) that demonstrates 100% sensitivity and specificity and achieves a limit of detection (LOD) of 0.96 copies/μL. The assay also achieved 100% correlation with reverse transcription-quantitative polymerase chain reaction (RT-qPCR) in clinical patient samples (<i>n</i> = 9). The dCRISTOR assay, a label-free digital nucleic acid testing system that eliminates the need for fluorescence readouts, absorbance measurements, or expensive manufacturing processes, represents a substantial advancement in digital viral RNA diagnostics.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"11 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518438","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：