Christopher Leist,Sadegh Ghaderzadeh,Emerson C Kohlrausch,Johannes Biskupek,Luke T Norman,Ilya Popov,Jesum Alves Fernandes,Ute Kaiser,Elena Besley,Andrei N Khlobystov
According to common understanding, the primary difference between a liquid and a solid metal lies in atomic motion─atoms move rapidly in liquids, while they remain stationary in a solid lattice. The solidification process involves a transition from random atomic motion to an ordered crystalline structure, with nucleation playing a crucial role. However, our research indicates that the boundary between these two phases is not as distinct as previously believed: liquid metal nanoparticles can contain stationary atoms, and the number and positions of these atoms influence the solidification pathway upon cooling. Using spherical and chromatic aberration-corrected high-resolution transmission electron microscopy (HRTEM) at low accelerating voltages, we studied the solidification of platinum, palladium, and gold. We have developed a methodology that enables imaging of metal particles over a wide temperature range, from 20 to 800 °C, without compromising atomic resolution. When a nanoparticle melts, the contrast contribution of the fast-moving atoms vanishes in the HRTEM images, allowing stationary atoms to be visualized through the liquid layer as distinct atomic points of contrast that remain fixed in position on the imaging time scale (1 s or longer). These atoms are pinned at vacancy defect sites on graphene. By conducting HRTEM image contrast analysis during time-series imaging of individual 3-6 nm particles while changing the temperature from 800 to 20 °C, we uncover the mechanisms behind classical crystal nucleation, amorphous solidification, and the formation of supercooled liquid platinum. If the number of stationary platinum atoms is small (approximately fewer than 10) and positioned randomly, liquid-to-crystal nucleation can occur. However, if the number is higher, these stationary atoms can disrupt the crystallization process, particularly if they align along the perimeter of the liquid nanoparticle. We found that liquid nanodroplets, corralled by stationary atoms, remain liquid down to 200-300 °C, which is several hundred degrees below the bulk metal crystallization temperature. In these cases, supercooled liquid metal transforms into a metastable amorphous solid instead of crystallizing. Our results highlight the significance of stationary atoms in liquids, influenced by the local environment, which may hold significant implications for the use of metal nanoparticles on carbon in heterogeneous catalysis and other thermally activated processes.
{"title":"Stationary Atoms in Liquid Metals and Their Role in Solidification Mechanisms.","authors":"Christopher Leist,Sadegh Ghaderzadeh,Emerson C Kohlrausch,Johannes Biskupek,Luke T Norman,Ilya Popov,Jesum Alves Fernandes,Ute Kaiser,Elena Besley,Andrei N Khlobystov","doi":"10.1021/acsnano.5c08201","DOIUrl":"https://doi.org/10.1021/acsnano.5c08201","url":null,"abstract":"According to common understanding, the primary difference between a liquid and a solid metal lies in atomic motion─atoms move rapidly in liquids, while they remain stationary in a solid lattice. The solidification process involves a transition from random atomic motion to an ordered crystalline structure, with nucleation playing a crucial role. However, our research indicates that the boundary between these two phases is not as distinct as previously believed: liquid metal nanoparticles can contain stationary atoms, and the number and positions of these atoms influence the solidification pathway upon cooling. Using spherical and chromatic aberration-corrected high-resolution transmission electron microscopy (HRTEM) at low accelerating voltages, we studied the solidification of platinum, palladium, and gold. We have developed a methodology that enables imaging of metal particles over a wide temperature range, from 20 to 800 °C, without compromising atomic resolution. When a nanoparticle melts, the contrast contribution of the fast-moving atoms vanishes in the HRTEM images, allowing stationary atoms to be visualized through the liquid layer as distinct atomic points of contrast that remain fixed in position on the imaging time scale (1 s or longer). These atoms are pinned at vacancy defect sites on graphene. By conducting HRTEM image contrast analysis during time-series imaging of individual 3-6 nm particles while changing the temperature from 800 to 20 °C, we uncover the mechanisms behind classical crystal nucleation, amorphous solidification, and the formation of supercooled liquid platinum. If the number of stationary platinum atoms is small (approximately fewer than 10) and positioned randomly, liquid-to-crystal nucleation can occur. However, if the number is higher, these stationary atoms can disrupt the crystallization process, particularly if they align along the perimeter of the liquid nanoparticle. We found that liquid nanodroplets, corralled by stationary atoms, remain liquid down to 200-300 °C, which is several hundred degrees below the bulk metal crystallization temperature. In these cases, supercooled liquid metal transforms into a metastable amorphous solid instead of crystallizing. Our results highlight the significance of stationary atoms in liquids, influenced by the local environment, which may hold significant implications for the use of metal nanoparticles on carbon in heterogeneous catalysis and other thermally activated processes.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"11 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704392","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}
Janus transition metal dichalcogenides, such as MoSSe, are potential materials for advanced electronics, yet their real-world device performance often fails to meet theoretical expectations. The origin of this discrepancy, rooted in atomic-scale imperfections, has remained critically unexplored. Here, using scanning tunneling microscopy and spectroscopy, this work provides atomic-scale insights into the complex electronic structures of monolayer Janus MoSSe, revealing distinct defect species that govern device performance. The residual sulfur dopants are found to introduce a broad band (≈0.5 eV) of shallow in-gap states near the valence band with spatially inhomogeneous distribution. Moreover, this work unveils two distinct native charge defects with spatially electronic influence extending ≈2.5 nm: conductive charge traps that reduce the local effective bandgap by more than half and insulating scattering centers that impede carrier transport. This microscopic understanding of defect-induced electronic modifications explains how atomic-scale imperfections influence macroscopic device limitations, providing fundamental design criteria for the engineering of Janus devices.
{"title":"Atomically Resolved Defects Modulate Electronic Structure in Plasma-Assisted 2D Janus MoSSe Monolayers.","authors":"Zi-Liang Yang,Yu-Chieh Lin,Mayur Chaudhary,Li-Sheng Lin,Chih-Yang Huang,You-Jie Lin,Jyh-Pin Chou,Li-Chyong Chen,Kuei-Hsien Chen,Yu-Lun Chueh,Ya-Ping Chiu","doi":"10.1021/acsnano.5c14446","DOIUrl":"https://doi.org/10.1021/acsnano.5c14446","url":null,"abstract":"Janus transition metal dichalcogenides, such as MoSSe, are potential materials for advanced electronics, yet their real-world device performance often fails to meet theoretical expectations. The origin of this discrepancy, rooted in atomic-scale imperfections, has remained critically unexplored. Here, using scanning tunneling microscopy and spectroscopy, this work provides atomic-scale insights into the complex electronic structures of monolayer Janus MoSSe, revealing distinct defect species that govern device performance. The residual sulfur dopants are found to introduce a broad band (≈0.5 eV) of shallow in-gap states near the valence band with spatially inhomogeneous distribution. Moreover, this work unveils two distinct native charge defects with spatially electronic influence extending ≈2.5 nm: conductive charge traps that reduce the local effective bandgap by more than half and insulating scattering centers that impede carrier transport. This microscopic understanding of defect-induced electronic modifications explains how atomic-scale imperfections influence macroscopic device limitations, providing fundamental design criteria for the engineering of Janus devices.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"5 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704393","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 development of out-of-equilibrium supramolecular hydrogels, inspired by biological systems, has attracted considerable interest due to their potential applications in nanotechnology. Despite this, these transient hydrogels' (opto-)electronic properties remain elusive. This study introduces a bioinspired dissipative hydrogel powered by a chemical fuel, exhibiting tunable conducting and photoelectronic functionalities. A bio-organic bolaamphiphile (PA) was designed and synthesized, integrating the optoelectronic characteristics of perylene diimide (P) with the reversible gel-triggered switching capabilities of l-aspartic acid (A). Precise temporal control over the supramolecular self-assembly and disassembly of the PA hydrogel was achieved by regulating the chemical fuel dimethyl sulfate (DMS). Results demonstrate that the PA-based dissipative self-assembly can reversibly switch between an insulating sol state and a conductive gel state, accompanied by nanostructural, fluorescence, and chiroptical switching. Furthermore, a thin film derived from the hydrogel exhibited photoresponsive conductivity switching capability. PA's transient structural, chemical, and functional properties were extensively characterized using spectroscopic, microscopic, computational, and device fabrication techniques. This study not only elucidates the structure-property relationships in dissipative hydrogels but also contributes to the development of adaptive, life-like functional nanomaterials with promising applications in optoelectronics, nanotechnology, and soft robotics.
{"title":"Bioinspired Out-of-Equilibrium Conductive Hydrogels: Unlocking Fuel and Light-Responsive Transient Conducting Properties.","authors":"Ruchi Shukla,Rajarshi Chakraborty,Vijay Kumar Patel,Subrat Vishwakarma,Bhola Nath Pal,Divya B Korlepara,Pandeeswar Makam","doi":"10.1021/acsnano.5c14077","DOIUrl":"https://doi.org/10.1021/acsnano.5c14077","url":null,"abstract":"The development of out-of-equilibrium supramolecular hydrogels, inspired by biological systems, has attracted considerable interest due to their potential applications in nanotechnology. Despite this, these transient hydrogels' (opto-)electronic properties remain elusive. This study introduces a bioinspired dissipative hydrogel powered by a chemical fuel, exhibiting tunable conducting and photoelectronic functionalities. A bio-organic bolaamphiphile (PA) was designed and synthesized, integrating the optoelectronic characteristics of perylene diimide (P) with the reversible gel-triggered switching capabilities of l-aspartic acid (A). Precise temporal control over the supramolecular self-assembly and disassembly of the PA hydrogel was achieved by regulating the chemical fuel dimethyl sulfate (DMS). Results demonstrate that the PA-based dissipative self-assembly can reversibly switch between an insulating sol state and a conductive gel state, accompanied by nanostructural, fluorescence, and chiroptical switching. Furthermore, a thin film derived from the hydrogel exhibited photoresponsive conductivity switching capability. PA's transient structural, chemical, and functional properties were extensively characterized using spectroscopic, microscopic, computational, and device fabrication techniques. This study not only elucidates the structure-property relationships in dissipative hydrogels but also contributes to the development of adaptive, life-like functional nanomaterials with promising applications in optoelectronics, nanotechnology, and soft robotics.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"1 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704346","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}
Elucidating nanoparticle (NP) tumor accumulation mechanisms is crucial for advancing chemotherapeutic nanomedicines. While the Enhanced Permeability and Retention (EPR) effect constitutes the cornerstone of passive tumor targeting, the efficacy of most EPR-driven nanomedicines is limited by low tumor accumulation (<1%). Recently, endothelial macropinocytosis has emerged as another major mechanism. Critically, both mechanisms depend on sustained plasma concentrations of NPs. However, we observed a paradoxical phenomenon unexplained by existing paradigms: persistent late-phase tumor accumulation occurring when plasma NPs decline to undetectable levels. Resolving this, we identified neutrophil hitchhiking as the dominant intermediate-to-late phase mechanism. Tumor burden substantially enhanced late-phase neutrophil-hitchhiked NPs. Intravital imaging directly visualized neutrophil-mediated NP delivery via adhesion, aggregation, and transendothelial transport during late-phase. Furthermore, we observed that neutrophil hitchhiking mechanism governs late-phase splenic accumulation as well. By modulating NP surface properties to achieve differential neutrophil-hitchhiking affinity, we demonstrated that enhanced neutrophil-hitchhiked NP delivery directly correlates with superior late-phase spleen-targeting efficiency. Thus, neutrophil hitchhiking drives sustained tumor and spleen redistribution of NPs amidst systemic NP clearance. These findings propose distinct design principles for nanomedicine leveraging peripheral blood immune cell interactions for organ-selective targeting.
{"title":"Transporting via Neutrophil as a Key Mechanism for Nanoparticle Redistribution to Tumor and Spleen.","authors":"Sijie Wang,Mei Pang,Jiaxin Huang,Xiaoqi Zhao,Yuena Zhang,Xuemeng Guo,Huanli Zhou,Ying Zhu,Xu Liu,Zhaolei Jin,Zhenyu Luo,Jiapeng Mao,Junlei Zhang,Jian Liu,Junchao Qian,Lihua Luo,Jian You","doi":"10.1021/acsnano.5c14907","DOIUrl":"https://doi.org/10.1021/acsnano.5c14907","url":null,"abstract":"Elucidating nanoparticle (NP) tumor accumulation mechanisms is crucial for advancing chemotherapeutic nanomedicines. While the Enhanced Permeability and Retention (EPR) effect constitutes the cornerstone of passive tumor targeting, the efficacy of most EPR-driven nanomedicines is limited by low tumor accumulation (<1%). Recently, endothelial macropinocytosis has emerged as another major mechanism. Critically, both mechanisms depend on sustained plasma concentrations of NPs. However, we observed a paradoxical phenomenon unexplained by existing paradigms: persistent late-phase tumor accumulation occurring when plasma NPs decline to undetectable levels. Resolving this, we identified neutrophil hitchhiking as the dominant intermediate-to-late phase mechanism. Tumor burden substantially enhanced late-phase neutrophil-hitchhiked NPs. Intravital imaging directly visualized neutrophil-mediated NP delivery via adhesion, aggregation, and transendothelial transport during late-phase. Furthermore, we observed that neutrophil hitchhiking mechanism governs late-phase splenic accumulation as well. By modulating NP surface properties to achieve differential neutrophil-hitchhiking affinity, we demonstrated that enhanced neutrophil-hitchhiked NP delivery directly correlates with superior late-phase spleen-targeting efficiency. Thus, neutrophil hitchhiking drives sustained tumor and spleen redistribution of NPs amidst systemic NP clearance. These findings propose distinct design principles for nanomedicine leveraging peripheral blood immune cell interactions for organ-selective targeting.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"28 3 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704388","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 pro-energy synthesis strategy has been considered a promising approach for addressing degenerative disorders, including osteoarthritis (OA). However, the physiologically low oxygen tension in articular cartilage limits aerobic respiration and energy production. In this study, a hemoglobin (Hb)-loaded zeolitic imidazolate framework-8 (ZIF-8) nanopump was developed for efficient oxygen delivery. This nanopump was further functionalized with cartilage-targeting peptides (CZIF@Hb) and specifically guided to aggregate on chondrocytes. In response to active (ultrasonic driving) and passive stimuli (acidic microenvironment), CZIF@Hb underwent responsive disassembly. ZIF-8 drove CO2 adsorption, while Hb facilitated O2 release. These processes synergistically enhanced the tricarboxylic acid (TCA) cycle and subsequent oxidative phosphorylation (OXPHOS), thereby promoting adenosine triphosphate (ATP) generation. Mechanistically, in addition to direct oxygen supply, CZIF@Hb nanopump indirectly facilitated the incorporation of α-KG into the TCA cycle by activating the solute carrier family 1 member 5 (SLC1A5)/solute carrier family 38 member 2 (SLC38A2)-glutamate dehydrogenase 1 (GLUD1)-glutaminase (GLS) axis. The enhanced energy metabolism mitigated free radical-induced damage and concurrently promoted the formation of hyaline cartilage instead of fibrocartilage. Administration of CZIF@Hb nanopump exerted therapeutic effects on cartilage degeneration, subchondral bone sclerosis, and synovial inflammation. Overall, the oxygen-carrying nanoplatform offers a feasible strategy for overcoming energy deficits in hypometabolic organs.
{"title":"A Remote-Controlled Nanopump Delivers Oxygen to Boost Energy Production in Osteoarthritis.","authors":"Xiaowei Xia,Wu Xu,Zhiyuan He,Yingjie Lu,Yong Zhang,Huilin Yang,Lixin Huang,Dinghua Jiang,Lisong Li,Yijian Zhang,Xuesong Zhu","doi":"10.1021/acsnano.5c15534","DOIUrl":"https://doi.org/10.1021/acsnano.5c15534","url":null,"abstract":"The pro-energy synthesis strategy has been considered a promising approach for addressing degenerative disorders, including osteoarthritis (OA). However, the physiologically low oxygen tension in articular cartilage limits aerobic respiration and energy production. In this study, a hemoglobin (Hb)-loaded zeolitic imidazolate framework-8 (ZIF-8) nanopump was developed for efficient oxygen delivery. This nanopump was further functionalized with cartilage-targeting peptides (CZIF@Hb) and specifically guided to aggregate on chondrocytes. In response to active (ultrasonic driving) and passive stimuli (acidic microenvironment), CZIF@Hb underwent responsive disassembly. ZIF-8 drove CO2 adsorption, while Hb facilitated O2 release. These processes synergistically enhanced the tricarboxylic acid (TCA) cycle and subsequent oxidative phosphorylation (OXPHOS), thereby promoting adenosine triphosphate (ATP) generation. Mechanistically, in addition to direct oxygen supply, CZIF@Hb nanopump indirectly facilitated the incorporation of α-KG into the TCA cycle by activating the solute carrier family 1 member 5 (SLC1A5)/solute carrier family 38 member 2 (SLC38A2)-glutamate dehydrogenase 1 (GLUD1)-glutaminase (GLS) axis. The enhanced energy metabolism mitigated free radical-induced damage and concurrently promoted the formation of hyaline cartilage instead of fibrocartilage. Administration of CZIF@Hb nanopump exerted therapeutic effects on cartilage degeneration, subchondral bone sclerosis, and synovial inflammation. Overall, the oxygen-carrying nanoplatform offers a feasible strategy for overcoming energy deficits in hypometabolic organs.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"122 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704390","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}
Zimeng Li, Hongxiang Zhang, Yuhang Ye, Jing Xu, Xiaojun Li, Hanwen Chu, Jianxiang Zhang, Qiaojie Luo, Xiaodong Li
Conventional hydrogels exhibit inadequate performance in oral applications due to poor bioadhesion and uncontrolled drug release in saliva-rich dynamic environments, compromising their antimicrobial and anti-inflammatory effects. To address these limitations, we propose a nanotherapy-reinforced multifunctional hydrogel strategy. Curcumin (CUR)/polyaminopropyl biguanide (PAPB) nanoparticles (CP NPs) are first prepared by electrostatic interaction-mediated self-assembly of the anti-inflammatory/antioxidant drug CUR and the antibacterial polymer PAPB. This multibioactive nanotherapy shows ultrahigh loading contents for both therapeutic agents (47% CUR, 42% PAPB). Further integrating CP NPs into a photo-cross-linkable hydrogel based on gelatin methacryloyl and oxidized hyaluronic acid affords functionally multifaceted networks reinforced by hydrogen bonding, electrostatic force, and Schiff base, enabling dynamical modulation of hydrogel properties. The resultant hybrid hydrogel exhibits programmable mechanical adaptability, including tunable viscoelasticity, shear-thinning behavior, and controllable swelling/degradation, along with robust tissue adhesion (∼80 kPa) for in situ barrier formation on irregular defects. Additionally, it provides sustained codelivery of CUR/PAPB (>72 h) with synergistic antibiofilm and immunomodulatory functions. In vivo evaluations across skin wound, oral ulcer, and periodontitis models demonstrate prolonged microbial defense, significant inflammation resolution, and accelerated tissue regeneration. This nanotherapy-mediated multi-interaction reinforcement strategy can serve as a versatile approach for engineering self-adaptive hydrogels to address complex challenges in oral regenerative medicine.
{"title":"Dual-Functional Nanotherapy-Reinforced Hydrogel for Synergistic Antimicrobial and Immunomodulatory Oral Tissue Repair","authors":"Zimeng Li, Hongxiang Zhang, Yuhang Ye, Jing Xu, Xiaojun Li, Hanwen Chu, Jianxiang Zhang, Qiaojie Luo, Xiaodong Li","doi":"10.1021/acsnano.5c13401","DOIUrl":"https://doi.org/10.1021/acsnano.5c13401","url":null,"abstract":"Conventional hydrogels exhibit inadequate performance in oral applications due to poor bioadhesion and uncontrolled drug release in saliva-rich dynamic environments, compromising their antimicrobial and anti-inflammatory effects. To address these limitations, we propose a nanotherapy-reinforced multifunctional hydrogel strategy. Curcumin (CUR)/polyaminopropyl biguanide (PAPB) nanoparticles (CP NPs) are first prepared by electrostatic interaction-mediated self-assembly of the anti-inflammatory/antioxidant drug CUR and the antibacterial polymer PAPB. This multibioactive nanotherapy shows ultrahigh loading contents for both therapeutic agents (47% CUR, 42% PAPB). Further integrating CP NPs into a photo-cross-linkable hydrogel based on gelatin methacryloyl and oxidized hyaluronic acid affords functionally multifaceted networks reinforced by hydrogen bonding, electrostatic force, and Schiff base, enabling dynamical modulation of hydrogel properties. The resultant hybrid hydrogel exhibits programmable mechanical adaptability, including tunable viscoelasticity, shear-thinning behavior, and controllable swelling/degradation, along with robust tissue adhesion (∼80 kPa) for <i>in situ</i> barrier formation on irregular defects. Additionally, it provides sustained codelivery of CUR/PAPB (>72 h) with synergistic antibiofilm and immunomodulatory functions. <i>In vivo</i> evaluations across skin wound, oral ulcer, and periodontitis models demonstrate prolonged microbial defense, significant inflammation resolution, and accelerated tissue regeneration. This nanotherapy-mediated multi-interaction reinforcement strategy can serve as a versatile approach for engineering self-adaptive hydrogels to address complex challenges in oral regenerative medicine.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"1 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711468","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}
Biomimetic nanoparticles such as cell membrane-coated nanoparticles (CMNPs) are widely used for the in vivo treatment of various diseases because they offer a high targeting efficiency, excellent biocompatibility, immune evasion capability, and longer circulation times. However, current noninvasive delivery strategies for CMNPs often face limitations regarding maintaining optimal coating stability and distribution efficiency. In this study, we develop a platform for the transdermal delivery of CMNPs as a noninvasive alternative to injections. Specifically, an antiaggregation transdermal delivery tool (AATDT) was developed using biocompatible beeswax and hyaluronic acid. The proposed system reduced the surface energy of the CMNPs, thus preventing aggregation in the liquid phase and promoting skin permeation via enhanced hydration effects. The CMNPs were delivered to a depth of over 500 μm into the skin tissue without aggregation or systemic toxicity. The proposed AATDT thus offers a versatile, clinically translatable strategy for enhancing the stability and delivery efficiency of CMNPs in noninvasive therapeutic applications.
{"title":"Anti-Aggregation System for the Enhanced Transdermal Delivery of Cell Membrane-Coated Nanoparticles.","authors":"Bumgyu Choi,Yoojin Lee,Dahae Kim,Taihyun Kim,Sungwon Jung,Woojin Choi,Won-Gun Koh,Sangmin Lee,Sang-Jun Ha,Jinkee Hong","doi":"10.1021/acsnano.5c15139","DOIUrl":"https://doi.org/10.1021/acsnano.5c15139","url":null,"abstract":"Biomimetic nanoparticles such as cell membrane-coated nanoparticles (CMNPs) are widely used for the in vivo treatment of various diseases because they offer a high targeting efficiency, excellent biocompatibility, immune evasion capability, and longer circulation times. However, current noninvasive delivery strategies for CMNPs often face limitations regarding maintaining optimal coating stability and distribution efficiency. In this study, we develop a platform for the transdermal delivery of CMNPs as a noninvasive alternative to injections. Specifically, an antiaggregation transdermal delivery tool (AATDT) was developed using biocompatible beeswax and hyaluronic acid. The proposed system reduced the surface energy of the CMNPs, thus preventing aggregation in the liquid phase and promoting skin permeation via enhanced hydration effects. The CMNPs were delivered to a depth of over 500 μm into the skin tissue without aggregation or systemic toxicity. The proposed AATDT thus offers a versatile, clinically translatable strategy for enhancing the stability and delivery efficiency of CMNPs in noninvasive therapeutic applications.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"35 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145710747","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}
Phase-change perfluorocarbon nanodroplets (PFCnDs) have shown potential for controlled, image-guided drug delivery. However, their clinical translation is limited by the poor encapsulation of hydrophilic therapeutics and unintended cargo release during ultrasound (US) or photoacoustic (PA) imaging. In this study, we present the development of double-emulsion perfluorocarbon nanodroplets (dePFCnDs) designed to encapsulate hydrophilic payloads while enabling efficient, real-time, focused ultrasound (FUS) triggered release. Cryo-transmission electron microscopy revealed that the dePFCnDs consist of a hydrophilic inner core surrounded by a perfluorocarbon layer that supports US/PA imaging. Compared to conventional single-emulsion PFCnDs, the double-emulsion structure significantly enhanced the loading efficiency tested using the fluorescent hydrophilic model drug, calcein. Furthermore, improved stability was demonstrated showing minimal calcein leakage under imaging conditions. Release studies demonstrated selective responsiveness of dePFCnDs to FUS stimulation, with negligible response to thermal or laser triggers. Optimizing focused ultrasound parameters further enhances release efficiency, enabling precise spatial and temporal control. In vitro and in vivo experiments confirmed the feasibility of utilizing real-time US/PA tracking of droplet localization, and changes in US/PA signal as a proxy for payload release. This proof-of-concept study demonstrates the potential of dePFCnDs as a hydrophilic therapeutics carrier that provides a robust, safe, and effective platform for ultrasound-mediated, image-guided delivery and release.
{"title":"Double-Emulsion Perfluorocarbon Nanodroplets for Ultrasound and Photoacoustic Image-Guided Drug Delivery and Release.","authors":"Euisuk Chung,Andrew X Zhao,Stanislav Y Emelianov","doi":"10.1021/acsnano.5c12290","DOIUrl":"https://doi.org/10.1021/acsnano.5c12290","url":null,"abstract":"Phase-change perfluorocarbon nanodroplets (PFCnDs) have shown potential for controlled, image-guided drug delivery. However, their clinical translation is limited by the poor encapsulation of hydrophilic therapeutics and unintended cargo release during ultrasound (US) or photoacoustic (PA) imaging. In this study, we present the development of double-emulsion perfluorocarbon nanodroplets (dePFCnDs) designed to encapsulate hydrophilic payloads while enabling efficient, real-time, focused ultrasound (FUS) triggered release. Cryo-transmission electron microscopy revealed that the dePFCnDs consist of a hydrophilic inner core surrounded by a perfluorocarbon layer that supports US/PA imaging. Compared to conventional single-emulsion PFCnDs, the double-emulsion structure significantly enhanced the loading efficiency tested using the fluorescent hydrophilic model drug, calcein. Furthermore, improved stability was demonstrated showing minimal calcein leakage under imaging conditions. Release studies demonstrated selective responsiveness of dePFCnDs to FUS stimulation, with negligible response to thermal or laser triggers. Optimizing focused ultrasound parameters further enhances release efficiency, enabling precise spatial and temporal control. In vitro and in vivo experiments confirmed the feasibility of utilizing real-time US/PA tracking of droplet localization, and changes in US/PA signal as a proxy for payload release. This proof-of-concept study demonstrates the potential of dePFCnDs as a hydrophilic therapeutics carrier that provides a robust, safe, and effective platform for ultrasound-mediated, image-guided delivery and release.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"29 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704389","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}
Alfred Akinlalu, Komila Rasuleva, Emmanuel Ogberefor, Tommy Gao, Haiyong Han, Pankaj K Singh, Christopher H. Lieu, Christina Coughlan, Todd M. Pitts, Dali Sun
Pancreatic ductal adenocarcinoma (PDAC) remains one of the most challenging cancers to detect, with significant limitations compared to screening methods for lung, breast, colon, and cervical cancers. Current methods are often plagued by high false-positive rates, necessitating costly, complex, and invasive confirmatory procedures. These challenges arise from the low incidence of PDAC and the need for highly specific and sensitive screening methods. To address these limitations, we developed EV-FRET, a fluorescence resonance energy transfer (FRET)-based assay designed as a rapid, specific, noninvasive, single-step, and low-cost detection method for PDAC. EV-FRET targets extracellular vesicles (EVs), small vesicles secreted by cells, including tumor cells, leveraging their unique size (∼160 nm) and composition for cancer detection. The EV-FRET assay targets two key markers: β-sheet-rich tumorous proteins (pan-cancer) and N-acetyl-d-galactosamine on epithelial cells (pancreas-specific), using thioflavin T and Dolichos biflorus agglutinin conjugated with fluorescein isothiocyanate fluorophores, which generate a FRET signal exclusively in PDAC-derived EVs within the circulating system. EV-FRET demonstrated superior diagnostic accuracy, achieving an area under the curve of 0.95 compared to 0.72 for CA19–9, the current clinical standard for PDAC detection. The assay offers additional advantages, including high reproducibility (coefficient of variation <4%), fast processing time (<15 min), low cost (estimated reagent cost < $15/test), and a simple, single-step operation that eliminates the need for EV enrichment or isolation. By integrating organ-specific markers and a tumor-specific biomarker, EV-FRET provides a scalable and highly specific diagnostic solution for pancreatic cancer. These features position EV-FRET as a transformative tool in cancer diagnostics, with the potential to significantly improve patient outcomes through more precise detection.
{"title":"A Fluorescence Resonance Energy Transfer-Based Assay Targeting Tumor-Derived Extracellular Vesicles for Highly Specific Pancreatic Cancer Detection","authors":"Alfred Akinlalu, Komila Rasuleva, Emmanuel Ogberefor, Tommy Gao, Haiyong Han, Pankaj K Singh, Christopher H. Lieu, Christina Coughlan, Todd M. Pitts, Dali Sun","doi":"10.1021/acsnano.5c10607","DOIUrl":"https://doi.org/10.1021/acsnano.5c10607","url":null,"abstract":"Pancreatic ductal adenocarcinoma (PDAC) remains one of the most challenging cancers to detect, with significant limitations compared to screening methods for lung, breast, colon, and cervical cancers. Current methods are often plagued by high false-positive rates, necessitating costly, complex, and invasive confirmatory procedures. These challenges arise from the low incidence of PDAC and the need for highly specific and sensitive screening methods. To address these limitations, we developed EV-FRET, a fluorescence resonance energy transfer (FRET)-based assay designed as a rapid, specific, noninvasive, single-step, and low-cost detection method for PDAC. EV-FRET targets extracellular vesicles (EVs), small vesicles secreted by cells, including tumor cells, leveraging their unique size (∼160 nm) and composition for cancer detection. The EV-FRET assay targets two key markers: β-sheet-rich tumorous proteins (pan-cancer) and <i>N</i>-acetyl-<span>d</span>-galactosamine on epithelial cells (pancreas-specific), using thioflavin T and <i>Dolichos biflorus</i> agglutinin conjugated with fluorescein isothiocyanate fluorophores, which generate a FRET signal exclusively in PDAC-derived EVs within the circulating system. EV-FRET demonstrated superior diagnostic accuracy, achieving an area under the curve of 0.95 compared to 0.72 for CA19–9, the current clinical standard for PDAC detection. The assay offers additional advantages, including high reproducibility (coefficient of variation <4%), fast processing time (<15 min), low cost (estimated reagent cost < $15/test), and a simple, single-step operation that eliminates the need for EV enrichment or isolation. By integrating organ-specific markers and a tumor-specific biomarker, EV-FRET provides a scalable and highly specific diagnostic solution for pancreatic cancer. These features position EV-FRET as a transformative tool in cancer diagnostics, with the potential to significantly improve patient outcomes through more precise detection.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"142 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711467","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 information era imposes increasing demands on speed and energy efficiency, pushing conventional electronics to its physical limits. Silicon photonics offers a promising path forward, particularly when integrated with electro-optic ferroelectric materials, which can overcome fundamental bottlenecks in data rate and power consumption. With pronounced electro-optic activity and controllable ferroelectric domain orientation, thin-film barium titanate (BTO) presents a promising platform for advanced photonic integration. Here, we fabricate epitaxial BTO films on MgO substrates and use precise structural design to realize silicon nitride-BTO (SiN-BTO) hybrid microring devices. Through co-optimization of material synthesis and device architecture, we achieve a record-low power consumption of 0.0015 nW/pm─among the best reported values for electro-optic tuners and exhibiting the highest effective electro-optic coefficient for BTO-on-MgO platforms. Furthermore, we demonstrate nonvolatile tuning enabled by ferroelectric domain control, achieving an eight-level photonic device stable for over 12 h and optically readable switching energy of 0.191 pJ. This work establishes a versatile platform integrating the multifunctionality of ferroelectric BTO with energy-efficient photonic operation, providing a foundation for scalable circuits in next-generation communication, sensing, and computing systems.
{"title":"Ultralow-Power Tuning and Nonvolatile Operation on a Hybrid Silicon Nitride/Barium Titanate Integrated Photonics Platform.","authors":"Xin Wang,Jie Tu,Min Sun,Wenfeng Zhou,Zhibo Cheng,Yikai Su,Binbin Chen,Yong Zhang","doi":"10.1021/acsnano.5c13131","DOIUrl":"https://doi.org/10.1021/acsnano.5c13131","url":null,"abstract":"The information era imposes increasing demands on speed and energy efficiency, pushing conventional electronics to its physical limits. Silicon photonics offers a promising path forward, particularly when integrated with electro-optic ferroelectric materials, which can overcome fundamental bottlenecks in data rate and power consumption. With pronounced electro-optic activity and controllable ferroelectric domain orientation, thin-film barium titanate (BTO) presents a promising platform for advanced photonic integration. Here, we fabricate epitaxial BTO films on MgO substrates and use precise structural design to realize silicon nitride-BTO (SiN-BTO) hybrid microring devices. Through co-optimization of material synthesis and device architecture, we achieve a record-low power consumption of 0.0015 nW/pm─among the best reported values for electro-optic tuners and exhibiting the highest effective electro-optic coefficient for BTO-on-MgO platforms. Furthermore, we demonstrate nonvolatile tuning enabled by ferroelectric domain control, achieving an eight-level photonic device stable for over 12 h and optically readable switching energy of 0.191 pJ. This work establishes a versatile platform integrating the multifunctionality of ferroelectric BTO with energy-efficient photonic operation, providing a foundation for scalable circuits in next-generation communication, sensing, and computing systems.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"110 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704391","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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