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A Thermally Robust Biopolymeric Separator Conveys K+ Transport and Interfacial Chemistry for Longevous Potassium Metal Batteries
IF 17.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c16664
Yuyuan Wang, Liang Xu, Xiaopeng Chen, Ziang Chen, Xinhua Li, Wenyi Guo, Tao Cheng, Yuyang Yi, Jingyu Sun
Potassium metal batteries (KMBs) hold promise for stationary energy storage with certain cost and resource merits. Nevertheless, their practicability is greatly handicapped by dendrite-related anodes, and the target design of specialized separators to boost anode safety is in its nascent stage. Here, we develop a thermally robust biopolymeric separator customized via a solvent-exchange and amino-siloxane decoration strategy to render durable and safe KMBs. Through experimental investigation and theoretical computation, we reveal that the optimized porosity and surface functionalization could manage ion transport and interfacial chemistry, thereby enabling efficient K+ diffusion and a favorable solid electrolyte interphase to achieve prolonged cycling stability (over 3000 h). The thus-assembled full cell retains 80% of its initial capacity after 400 cycles at 0.5 A g–1. The heat-proof property of the designed separator is further demonstrated. Our biopolymeric separator, affording multifunctional features, provides an appealing solution to circumvent instability and safety issues associated with potassium metal batteries.
{"title":"A Thermally Robust Biopolymeric Separator Conveys K+ Transport and Interfacial Chemistry for Longevous Potassium Metal Batteries","authors":"Yuyuan Wang, Liang Xu, Xiaopeng Chen, Ziang Chen, Xinhua Li, Wenyi Guo, Tao Cheng, Yuyang Yi, Jingyu Sun","doi":"10.1021/acsnano.4c16664","DOIUrl":"https://doi.org/10.1021/acsnano.4c16664","url":null,"abstract":"Potassium metal batteries (KMBs) hold promise for stationary energy storage with certain cost and resource merits. Nevertheless, their practicability is greatly handicapped by dendrite-related anodes, and the target design of specialized separators to boost anode safety is in its nascent stage. Here, we develop a thermally robust biopolymeric separator customized via a solvent-exchange and amino-siloxane decoration strategy to render durable and safe KMBs. Through experimental investigation and theoretical computation, we reveal that the optimized porosity and surface functionalization could manage ion transport and interfacial chemistry, thereby enabling efficient K<sup>+</sup> diffusion and a favorable solid electrolyte interphase to achieve prolonged cycling stability (over 3000 h). The thus-assembled full cell retains 80% of its initial capacity after 400 cycles at 0.5 A g<sup>–1</sup>. The heat-proof property of the designed separator is further demonstrated. Our biopolymeric separator, affording multifunctional features, provides an appealing solution to circumvent instability and safety issues associated with potassium metal batteries.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"22 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986150","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}
引用次数: 0
Advances, Challenges, and Opportunities in Plasmonic Nanogap-Enhanced Raman Scattering with Nanoparticles
IF 17.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c14557
Gyeong-Hwan Kim, Jiwoong Son, Jwa-Min Nam
Surface-enhanced Raman scattering has been widely used for molecular/material characterization and chemical and biological sensing and imaging applications. In particular, plasmonic nanogap-enhanced Raman scattering (NERS) is based on the highly localized electric field formed within the nanogap between closely spaced metallic surfaces to more strongly amplify Raman signals than the cases with molecules on metal surfaces. Nanoparticle-based NERS offers extraordinarily strong Raman signals and a plethora of opportunities in sensing, imaging and many different types of biomedical applications. Despite its potential, several challenges still remain for NERS to be widely useful in real-world applications. This Perspective introduces various plasmonic nanogap configurations with nanoparticles, discusses key advances and critical challenges while addressing possible misunderstandings in this field, and provides future directions for NERS to generate stronger, more uniform, and stable signals over a large number of structures for practical applications.
{"title":"Advances, Challenges, and Opportunities in Plasmonic Nanogap-Enhanced Raman Scattering with Nanoparticles","authors":"Gyeong-Hwan Kim, Jiwoong Son, Jwa-Min Nam","doi":"10.1021/acsnano.4c14557","DOIUrl":"https://doi.org/10.1021/acsnano.4c14557","url":null,"abstract":"Surface-enhanced Raman scattering has been widely used for molecular/material characterization and chemical and biological sensing and imaging applications. In particular, plasmonic nanogap-enhanced Raman scattering (NERS) is based on the highly localized electric field formed within the nanogap between closely spaced metallic surfaces to more strongly amplify Raman signals than the cases with molecules on metal surfaces. Nanoparticle-based NERS offers extraordinarily strong Raman signals and a plethora of opportunities in sensing, imaging and many different types of biomedical applications. Despite its potential, several challenges still remain for NERS to be widely useful in real-world applications. This Perspective introduces various plasmonic nanogap configurations with nanoparticles, discusses key advances and critical challenges while addressing possible misunderstandings in this field, and provides future directions for NERS to generate stronger, more uniform, and stable signals over a large number of structures for practical applications.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"1 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981569","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}
引用次数: 0
Parameter Pool-Assisted Centrifugation Sorter for Multiscale Higher-Order DNA Nanomaterials
IF 17.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c15100
Lilin Ouyang, Junke Wang, Bing Liu, Mo Xie, Lianhui Wang, Chunhai Fan, Jie Chao
Higher-order DNA nanomaterials have emerged as programmable tools for probing biological processes, constructing metamaterials, and manipulating mechanically active nanodevices with the multifunctionality and high-performance attributes. However, their utility is limited by intricate mixtures formed during hierarchical multistage assembly, as standard techniques like gel electrophoresis lack the resolution and applicability needed for precise characterization and enrichment. Thus, it is urgent to develop a sorter that provides high separation resolution, broad scope, and bioactive functionality. Here, we present a versatile and scalable sorting pipeline based on a centrifugation parameter pool capable of distinguishing DNA nanomaterials across multiple scales. By tuning parameters, we achieved high-throughput classification of nanostructures, spanning from DNA tile-based constructs to DNA origami-based assemblies (∼50 MDa, 75,000 bp), surpassing conventional methods. Furthermore, we optimized the separation resolution to less than 78 kDa (∼120 bp) at a large scale by sorting DNA tetrahedron structures using this systematic parameter pool-assisted centrifugation strategy. This sorter maintains the integrity and functionality of bioactive materials, facilitating a seamless transition from assembly to application, allowing for integration with proteins and other components to achieve the fabrication of complex functional materials and programmable molecular machines across interdisciplinary fields within the nanotechnology community.
{"title":"Parameter Pool-Assisted Centrifugation Sorter for Multiscale Higher-Order DNA Nanomaterials","authors":"Lilin Ouyang, Junke Wang, Bing Liu, Mo Xie, Lianhui Wang, Chunhai Fan, Jie Chao","doi":"10.1021/acsnano.4c15100","DOIUrl":"https://doi.org/10.1021/acsnano.4c15100","url":null,"abstract":"Higher-order DNA nanomaterials have emerged as programmable tools for probing biological processes, constructing metamaterials, and manipulating mechanically active nanodevices with the multifunctionality and high-performance attributes. However, their utility is limited by intricate mixtures formed during hierarchical multistage assembly, as standard techniques like gel electrophoresis lack the resolution and applicability needed for precise characterization and enrichment. Thus, it is urgent to develop a sorter that provides high separation resolution, broad scope, and bioactive functionality. Here, we present a versatile and scalable sorting pipeline based on a centrifugation parameter pool capable of distinguishing DNA nanomaterials across multiple scales. By tuning parameters, we achieved high-throughput classification of nanostructures, spanning from DNA tile-based constructs to DNA origami-based assemblies (∼50 MDa, 75,000 bp), surpassing conventional methods. Furthermore, we optimized the separation resolution to less than 78 kDa (∼120 bp) at a large scale by sorting DNA tetrahedron structures using this systematic parameter pool-assisted centrifugation strategy. This sorter maintains the integrity and functionality of bioactive materials, facilitating a seamless transition from assembly to application, allowing for integration with proteins and other components to achieve the fabrication of complex functional materials and programmable molecular machines across interdisciplinary fields within the nanotechnology community.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"118 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981573","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}
引用次数: 0
Robust and Regular Micronano Binary Texture on the Complex Curved Surface for Enhanced Reendothelialization and Antithrombotic Performance
IF 17.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c14191
Jing Zhang, Wenyuan Yu, Guoqiang Li, Guiling Li, Baolan Chen, Luwen Wang, Yang Yu, Zhiyuan Liu, Donghai Li
Blood-contacting medical devices can easily trigger immune responses, leading to thrombosis and hyperblastosis. Constructing microtexture that provides efficient antithrombotic and rapid reendothelialization performance on complex curved surfaces remains a pressing challenge. In this work, we present a robust and regular micronano binary texture on the titanium surface, characterized by exceptional mechanical strength and precisely controlled wettability to achieve excellent hemocompatibility. Systematic in vitro and in vivo investigations confirmed that the micronano binary texture with superhydrophilic modification effectively suppressed the adhesion and activation of plasma proteins and blood cells, thereby mitigating the subsequent coagulation cascade and thrombosis. Meanwhile, the modified surface significantly upregulated the gene expression involving cell–matrix adhesion, growth factor synthesis, and calcium-mediated cytoskeleton remodeling and then accelerated the formation of a healthy and stable endothelial cell layer. This enhancement of re-endothelialization was not observed with pure titanium and superhydrophobic surfaces. Hence, superhydrophilic micronano binary texture not only significantly inhibits thrombosis but also selectively enhances the integrity and viability of the endothelial cell layer, making it a promising strategy for improving the long-term anticoagulation performance of vascular implants.
{"title":"Robust and Regular Micronano Binary Texture on the Complex Curved Surface for Enhanced Reendothelialization and Antithrombotic Performance","authors":"Jing Zhang, Wenyuan Yu, Guoqiang Li, Guiling Li, Baolan Chen, Luwen Wang, Yang Yu, Zhiyuan Liu, Donghai Li","doi":"10.1021/acsnano.4c14191","DOIUrl":"https://doi.org/10.1021/acsnano.4c14191","url":null,"abstract":"Blood-contacting medical devices can easily trigger immune responses, leading to thrombosis and hyperblastosis. Constructing microtexture that provides efficient antithrombotic and rapid reendothelialization performance on complex curved surfaces remains a pressing challenge. In this work, we present a robust and regular micronano binary texture on the titanium surface, characterized by exceptional mechanical strength and precisely controlled wettability to achieve excellent hemocompatibility. Systematic in vitro and in vivo investigations confirmed that the micronano binary texture with superhydrophilic modification effectively suppressed the adhesion and activation of plasma proteins and blood cells, thereby mitigating the subsequent coagulation cascade and thrombosis. Meanwhile, the modified surface significantly upregulated the gene expression involving cell–matrix adhesion, growth factor synthesis, and calcium-mediated cytoskeleton remodeling and then accelerated the formation of a healthy and stable endothelial cell layer. This enhancement of re-endothelialization was not observed with pure titanium and superhydrophobic surfaces. Hence, superhydrophilic micronano binary texture not only significantly inhibits thrombosis but also selectively enhances the integrity and viability of the endothelial cell layer, making it a promising strategy for improving the long-term anticoagulation performance of vascular implants.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"12 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986146","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}
引用次数: 0
Moisture-Electric Generators Working in Subzero Environments Based on Laser-Engraved Hygroscopic Hydrogel Arrays 基于激光雕刻吸湿水凝胶阵列的可在零度以下环境中工作的湿气-电力发生器
IF 17.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c14996
Fei Yu, Liying Wang, Xijia Yang, Yue Yang, Xuesong Li, Yang Gao, Yi Jiang, Ke Jiang, Wei Lü, Xiaojuan Sun, Dabing Li
Moisture-electric generators (MEGs) generate power by adsorbing water from the air. However, their performance at low temperatures is hindered due to icing. In the present work, MEG arrays are developed by laser engraving techniques and a modulated low-temperature hydrogel as the absorbent material. LTH effectively captures moisture and maintains ion dissociation and migration even at subzero temperatures. Based on the double electric layer pseudocapacitance model, the oscillating circuit theory is introduced to explain the effects of moisture absorption, evaporation, and ion migration on the output current of the MEG, and the circuit calculations are matched with the experimental results. Molecular dynamics simulations indicate that LTH’s low-temperature stability results from preferential hydrogen bonding between glycerol molecules and H2O, which disrupts H2O–H2O hydrogen bonds and slows water crystallization. A single MEG unit (0.25 cm2) can produce up to ∼0.8 V and ∼21.2 μW/cm2 at room temperature, and at −35 °C with 16% RH, it generates ∼0.58 V and ∼14.35 μA. MEG realizes the following applications: MEG successfully drives electronic devices in snow; arrays of 16 MEGs can power portable electronics, and 384 MEGs can achieve up to 210 V; MEG absorbs moisture in water and drives LEDs by blowing up; MEG has a flexible wearable nature; MEG is used for respiratory monitoring and photoelectric sensors.
{"title":"Moisture-Electric Generators Working in Subzero Environments Based on Laser-Engraved Hygroscopic Hydrogel Arrays","authors":"Fei Yu, Liying Wang, Xijia Yang, Yue Yang, Xuesong Li, Yang Gao, Yi Jiang, Ke Jiang, Wei Lü, Xiaojuan Sun, Dabing Li","doi":"10.1021/acsnano.4c14996","DOIUrl":"https://doi.org/10.1021/acsnano.4c14996","url":null,"abstract":"Moisture-electric generators (MEGs) generate power by adsorbing water from the air. However, their performance at low temperatures is hindered due to icing. In the present work, MEG arrays are developed by laser engraving techniques and a modulated low-temperature hydrogel as the absorbent material. LTH effectively captures moisture and maintains ion dissociation and migration even at subzero temperatures. Based on the double electric layer pseudocapacitance model, the oscillating circuit theory is introduced to explain the effects of moisture absorption, evaporation, and ion migration on the output current of the MEG, and the circuit calculations are matched with the experimental results. Molecular dynamics simulations indicate that LTH’s low-temperature stability results from preferential hydrogen bonding between glycerol molecules and H<sub>2</sub>O, which disrupts H<sub>2</sub>O–H<sub>2</sub>O hydrogen bonds and slows water crystallization. A single MEG unit (0.25 cm<sup>2</sup>) can produce up to ∼0.8 V and ∼21.2 μW/cm<sup>2</sup> at room temperature, and at −35 °C with 16% RH, it generates ∼0.58 V and ∼14.35 μA. MEG realizes the following applications: MEG successfully drives electronic devices in snow; arrays of 16 MEGs can power portable electronics, and 384 MEGs can achieve up to 210 V; MEG absorbs moisture in water and drives LEDs by blowing up; MEG has a flexible wearable nature; MEG is used for respiratory monitoring and photoelectric sensors.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"8 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981571","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}
引用次数: 0
Induction of Antigen-Specific Tolerance in a Multiple Sclerosis Model without Broad Immunosuppression
IF 17.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c14698
Rebeca T. Stiepel, Sean R. Simpson, Nicole Rose Lukesh, Denzel D. Middleton, Dylan A. Hendy, Luis Ontiveros-Padilla, Stephen A. Ehrenzeller, Md Jahirul Islam, Erik S. Pena, Michael A. Carlock, Ted M. Ross, Eric M. Bachelder, Kristy M. Ainslie
Multiple sclerosis (MS) is a severe autoimmune disorder that wreaks havoc on the central nervous system, leading to a spectrum of motor and cognitive impairments. There is no cure, and current treatment strategies rely on broad immunosuppression, leaving patients vulnerable to infections. To address this problem, our approach aims to induce antigen-specific tolerance, a much-needed shift in MS therapy. We have engineered a tolerogenic therapy consisting of spray-dried particles made of a degradable biopolymer, acetalated dextran, and loaded with an antigenic peptide and tolerizing drug, rapamycin (Rapa). After initial characterization and optimization, particles were tested in a myelin oligodendrocyte glycoprotein (MOG)-induced experimental autoimmune encephalomyelitis model of MS. Representing the earliest possible time of diagnosis, mice were treated at symptom onset in an early therapeutic model, where particles containing MOG and particles containing Rapa+MOG evoked significant reductions in clinical score. Particles were then applied to a highly clinically relevant late therapeutic model during peak disease, where MOG particles and Rapa+MOG particles each elicited a dramatic therapeutic effect, reversing hind limb paralysis and restoring fully functional limbs. To confirm the antigen specificity of our therapy, we immunized mice against the influenza antigen hemagglutinin (HA) and treated them with MOG particles or Rapa+MOG particles. The particles did not suppress antibody responses against HA. Our findings underscore the potential of this particle-based therapy to reverse autoimmunity in disease-relevant models without compromising immune competence, setting it apart from existing treatments.
{"title":"Induction of Antigen-Specific Tolerance in a Multiple Sclerosis Model without Broad Immunosuppression","authors":"Rebeca T. Stiepel, Sean R. Simpson, Nicole Rose Lukesh, Denzel D. Middleton, Dylan A. Hendy, Luis Ontiveros-Padilla, Stephen A. Ehrenzeller, Md Jahirul Islam, Erik S. Pena, Michael A. Carlock, Ted M. Ross, Eric M. Bachelder, Kristy M. Ainslie","doi":"10.1021/acsnano.4c14698","DOIUrl":"https://doi.org/10.1021/acsnano.4c14698","url":null,"abstract":"Multiple sclerosis (MS) is a severe autoimmune disorder that wreaks havoc on the central nervous system, leading to a spectrum of motor and cognitive impairments. There is no cure, and current treatment strategies rely on broad immunosuppression, leaving patients vulnerable to infections. To address this problem, our approach aims to induce antigen-specific tolerance, a much-needed shift in MS therapy. We have engineered a tolerogenic therapy consisting of spray-dried particles made of a degradable biopolymer, acetalated dextran, and loaded with an antigenic peptide and tolerizing drug, rapamycin (Rapa). After initial characterization and optimization, particles were tested in a myelin oligodendrocyte glycoprotein (MOG)-induced experimental autoimmune encephalomyelitis model of MS. Representing the earliest possible time of diagnosis, mice were treated at symptom onset in an early therapeutic model, where particles containing MOG and particles containing Rapa+MOG evoked significant reductions in clinical score. Particles were then applied to a highly clinically relevant late therapeutic model during peak disease, where MOG particles and Rapa+MOG particles each elicited a dramatic therapeutic effect, reversing hind limb paralysis and restoring fully functional limbs. To confirm the antigen specificity of our therapy, we immunized mice against the influenza antigen hemagglutinin (HA) and treated them with MOG particles or Rapa+MOG particles. The particles did not suppress antibody responses against HA. Our findings underscore the potential of this particle-based therapy to reverse autoimmunity in disease-relevant models without compromising immune competence, setting it apart from existing treatments.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"1 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981570","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}
引用次数: 0
Atomic-Level Stoichiometry Control of Ferroelectric HfxZryOz Thin Films by Understanding Molecular-Level Chemical Physical Reactions
IF 17.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c13595
Ngoc Le Trinh, Bonwook Gu, Kun Yang, Chi Thang Nguyen, Byungchan Lee, Hyun-Mi Kim, Hyeongkeun Kim, Youngho Kang, Min Hyuk Park, Han-Bo-Ram Lee
HfO2-based thin films have garnered significant interest for integrating robust ferroelectricity into next-generation memory and logic chips, owing to their applicability with modern Si device technology. While numerous studies have focused on enhancing ferroelectric properties and understanding their fundamentals, the fabrication of ultrathin HfO2-based ferroelectric films has seldom been reported. This study presents the concept of atomic-level stoichiometry control of ferroelectric HfxZryOz films by examining the molecular-level interactions of precursor molecules in the atomic layer deposition (ALD) process through theoretical calculations. Atomic layer modulation (ALM) employs sequential precursor pulses, and the stoichiometries of HfxZryOz films are determined by the chemical and physical reactions predicted by theoretical simulations. The HfxZryOz ALM films demonstrate superior crystallinity and ferroelectricity compared to conventional HfxZryOz ALD films, with large polarization values reaching 2Pr = 48.8 μC/cm2 at a thickness of 4.5 nm. Because the ALM concept combines experimental and theoretical approaches, it can be applied to other applications that require multicomponent thin films with atomic-level stoichiometry control.
{"title":"Atomic-Level Stoichiometry Control of Ferroelectric HfxZryOz Thin Films by Understanding Molecular-Level Chemical Physical Reactions","authors":"Ngoc Le Trinh, Bonwook Gu, Kun Yang, Chi Thang Nguyen, Byungchan Lee, Hyun-Mi Kim, Hyeongkeun Kim, Youngho Kang, Min Hyuk Park, Han-Bo-Ram Lee","doi":"10.1021/acsnano.4c13595","DOIUrl":"https://doi.org/10.1021/acsnano.4c13595","url":null,"abstract":"HfO<sub>2</sub>-based thin films have garnered significant interest for integrating robust ferroelectricity into next-generation memory and logic chips, owing to their applicability with modern Si device technology. While numerous studies have focused on enhancing ferroelectric properties and understanding their fundamentals, the fabrication of ultrathin HfO<sub>2</sub>-based ferroelectric films has seldom been reported. This study presents the concept of atomic-level stoichiometry control of ferroelectric Hf<sub><i>x</i></sub>Zr<sub><i>y</i></sub>O<sub><i>z</i></sub> films by examining the molecular-level interactions of precursor molecules in the atomic layer deposition (ALD) process through theoretical calculations. Atomic layer modulation (ALM) employs sequential precursor pulses, and the stoichiometries of Hf<sub><i>x</i></sub>Zr<sub><i>y</i></sub>O<sub><i>z</i></sub> films are determined by the chemical and physical reactions predicted by theoretical simulations. The Hf<sub><i>x</i></sub>Zr<sub><i>y</i></sub>O<sub><i>z</i></sub> ALM films demonstrate superior crystallinity and ferroelectricity compared to conventional Hf<sub><i>x</i></sub>Zr<sub><i>y</i></sub>O<sub><i>z</i></sub> ALD films, with large polarization values reaching 2<i>P</i><sub>r</sub> = 48.8 μC/cm<sup>2</sup> at a thickness of 4.5 nm. Because the ALM concept combines experimental and theoretical approaches, it can be applied to other applications that require multicomponent thin films with atomic-level stoichiometry control.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"24 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986144","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}
引用次数: 0
Capillary-Assisted Confinement Assembly for Advanced Sensor Fabrication: From Superwetting Interfaces to Capillary Bridge Patterning
IF 17.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c17499
Zhihao Zhao, Weijie Wang, Gongmo Xiang, Lei Jiang, Xiangyu Jiang
Precise patterning of sensing materials, particularly the long-range-ordered assembly of micro/nanostructures, is pivotal for improving sensor performance, facilitating miniaturization, and enabling seamless integration. This paper examines the importance of interfacial confined assembly in sensor patterning, including gas–liquid and liquid–liquid confined assembly, wettability-assisted or microstructure-assisted solid–liquid interfacial confined assembly, and tip-induced confined assembly. The application of capillary bridge confined assembly technology in chemical sensors, flexible electronics, and optoelectronics is highlighted. The advantages of capillary bridge confined assembly technology include the ability to achieve high-resolution patterning, scalability, and material arrangement in long-range order. It is, therefore, an ideal processing platform for next-generation sensors. Finally, the broad prospects of this technology in the miniaturization and integration of high-performance multifunctional sensors are discussed.
{"title":"Capillary-Assisted Confinement Assembly for Advanced Sensor Fabrication: From Superwetting Interfaces to Capillary Bridge Patterning","authors":"Zhihao Zhao, Weijie Wang, Gongmo Xiang, Lei Jiang, Xiangyu Jiang","doi":"10.1021/acsnano.4c17499","DOIUrl":"https://doi.org/10.1021/acsnano.4c17499","url":null,"abstract":"Precise patterning of sensing materials, particularly the long-range-ordered assembly of micro/nanostructures, is pivotal for improving sensor performance, facilitating miniaturization, and enabling seamless integration. This paper examines the importance of interfacial confined assembly in sensor patterning, including gas–liquid and liquid–liquid confined assembly, wettability-assisted or microstructure-assisted solid–liquid interfacial confined assembly, and tip-induced confined assembly. The application of capillary bridge confined assembly technology in chemical sensors, flexible electronics, and optoelectronics is highlighted. The advantages of capillary bridge confined assembly technology include the ability to achieve high-resolution patterning, scalability, and material arrangement in long-range order. It is, therefore, an ideal processing platform for next-generation sensors. Finally, the broad prospects of this technology in the miniaturization and integration of high-performance multifunctional sensors are discussed.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"37 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986152","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}
引用次数: 0
Anchoring of Probiotic-Membrane Vesicles in Hydrogels Facilitates Wound Vascularization
IF 17.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c11986
Chen Zhou, Hongfu Cao, Yuxiang Wang, Chong Yao, Yaping Zou, Jingyi Liu, Na Li, Tun Yuan, Jie Liang, Qiguang Wang, Yujiang Fan, Xingdong Zhang
Inadequate vascularization significantly hampers wound recovery by limiting nutrient delivery. To address this challenge, we extracted membrane vesicles from Lactobacillus reuteri (LMVs) and identified their angiogenic potential via transcriptomic analysis. We further developed a composite hydrogel system (Gel-LMVs) by anchoring LMVs within carboxylated chitosan and cross-linking it with oxidized hyaluronic acid through a Schiff base reaction. The resulting Gel-LMVs exhibit good biocompatibility and retain the bioactivity of LMVs, which are released in a controlled manner to stimulate cell proliferation, migration, and angiogenesis in vitro by modulating gene expression in critical signaling pathways. Moreover, in an in vivo model, Gel-LMVs upregulate vascular endothelial growth factor (VEGF) and platelet endothelial cell adhesion molecule (CD31), leading to accelerated vascularization in early healing stages, while concurrently reducing inflammation and augmenting collagen deposition to enhance wound healing quality. This approach to functionalizing biomaterials with probiotic-MVs offers an advanced strategy for wound healing.
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引用次数: 0
Enormous Out-of-Plane Charge Rectification and Conductance through Two-Dimensional Monolayers
IF 17.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c15271
Anthony Cabanillas, Simran Shahi, Maomao Liu, Hemendra Nath Jaiswal, Sichen Wei, Yu Fu, Anindita Chakravarty, Asma Ahmed, Xiaochi Liu, Jian Sun, Cheng Yang, Won Jong Yoo, Theresia Knobloch, Vasili Perebeinos, Antonio Di Bartolomeo, Tibor Grasser, Fei Yao, Huamin Li
Heterogeneous integration of emerging two-dimensional (2D) materials with mature three-dimensional (3D) silicon-based semiconductor technology presents a promising approach for the future development of energy-efficient, function-rich nanoelectronic devices. In this study, we designed a mixed-dimensional junction structure in which a 2D monolayer (e.g., graphene, MoS2, and h-BN) is sandwiched between a metal (e.g., Ti, Au, and Pd) and a 3D semiconductor (e.g., p-Si) to investigate charge transport properties exclusively in an out-of-plane (OoP) direction. The role of 2D monolayers as either an OoP metal-to-semiconductor charge injection barrier or an OoP semiconductor-to-metal charge collection barrier was comparatively evaluated. Compared to monolayer graphene, monolayer MoS2 and h-BN effectively modulate OoP metal-to-semiconductor charge injection through a barrier tunneling effect. Their effective OoP resistance and resistivity were extracted using a resistors-in-series model. Intriguingly, when functioning as a semiconductor-to-metal charge collection barrier, all 2D monolayers become electronically “transparent” (close to zero resistance) when a high OoP voltage (greater than the built-in voltage) is applied. As a mixed-dimensional integrated diode, the Ti/MoS2/p-Si and Au/MoS2/p-Si configurations exhibit both high OoP rectification ratios (5.4 × 104) and conductance (1.3 × 105 S/m2). Our work demonstrates the tunable OoP charge transport characteristics at a 2D/3D interface, suggesting the opportunity for 2D/3D heterogeneous integration, even with sub-1 nm thick 2D monolayers, to enhance modern Si-based electronic devices.
{"title":"Enormous Out-of-Plane Charge Rectification and Conductance through Two-Dimensional Monolayers","authors":"Anthony Cabanillas, Simran Shahi, Maomao Liu, Hemendra Nath Jaiswal, Sichen Wei, Yu Fu, Anindita Chakravarty, Asma Ahmed, Xiaochi Liu, Jian Sun, Cheng Yang, Won Jong Yoo, Theresia Knobloch, Vasili Perebeinos, Antonio Di Bartolomeo, Tibor Grasser, Fei Yao, Huamin Li","doi":"10.1021/acsnano.4c15271","DOIUrl":"https://doi.org/10.1021/acsnano.4c15271","url":null,"abstract":"Heterogeneous integration of emerging two-dimensional (2D) materials with mature three-dimensional (3D) silicon-based semiconductor technology presents a promising approach for the future development of energy-efficient, function-rich nanoelectronic devices. In this study, we designed a mixed-dimensional junction structure in which a 2D monolayer (e.g., graphene, MoS<sub>2</sub>, and h-BN) is sandwiched between a metal (e.g., Ti, Au, and Pd) and a 3D semiconductor (e.g., p-Si) to investigate charge transport properties exclusively in an out-of-plane (OoP) direction. The role of 2D monolayers as either an OoP metal-to-semiconductor charge injection barrier or an OoP semiconductor-to-metal charge collection barrier was comparatively evaluated. Compared to monolayer graphene, monolayer MoS<sub>2</sub> and h-BN effectively modulate OoP metal-to-semiconductor charge injection through a barrier tunneling effect. Their effective OoP resistance and resistivity were extracted using a resistors-in-series model. Intriguingly, when functioning as a semiconductor-to-metal charge collection barrier, all 2D monolayers become electronically “transparent” (close to zero resistance) when a high OoP voltage (greater than the built-in voltage) is applied. As a mixed-dimensional integrated diode, the Ti/MoS<sub>2</sub>/p-Si and Au/MoS<sub>2</sub>/p-Si configurations exhibit both high OoP rectification ratios (5.4 × 10<sup>4</sup>) and conductance (1.3 × 10<sup>5</sup> S/m<sup>2</sup>). Our work demonstrates the tunable OoP charge transport characteristics at a 2D/3D interface, suggesting the opportunity for 2D/3D heterogeneous integration, even with sub-1 nm thick 2D monolayers, to enhance modern Si-based electronic devices.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"53 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986148","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}
引用次数: 0
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ACS Nano
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