ACS Nano最新文献

英文中文

Solid-State Nanopore Real-Time Assay for Monitoring Cas9 Endonuclease Reactivity

IF 17.1 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

ACS Nano

Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c15173

Chalmers C. C. Chau, Nicole E. Weckman, Emma E. Thomson, Paolo Actis

The field of nanopore sensing is now moving beyond nucleic acid sequencing. An exciting avenue is the use of nanopore platforms for the monitoring of biochemical reactions. Biological nanopores have been used for this application, but solid-state nanopore approaches have lagged. This is due to the necessity of using higher salt conditions (e.g., 4 M LiCl) to improve the signal-to-noise ratio which completely abolish the activities of many biochemical reactions. We pioneered a polymer electrolyte solid-state nanopore approach that maintains a high signal-to-noise ratio even at a physiologically relevant salt concentration. Here, we report the monitoring of the restriction enzyme SwaI and CRISPR-Cas9 endonuclease activities under physiological salt conditions and in real time. We investigated the dsDNA cleavage activity of these enzymes in a range of digestion buffers and elucidated the off-target activity of CRISPR-Cas9 ribonucleoprotein endonuclease in the presence of single base pair mismatches. This approach enables the application of solid-state nanopores for the dynamic monitoring of biochemical reactions under physiological salt conditions.

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引用次数: 0

Deciphering the Sulfur-Involved Bonding Interactions in Sulfurized Polyacrylonitrile: The Formation Thermodynamics and the Roles in Electrochemical Characteristics

IF 17.1 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

ACS Nano

Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c16728

Jingyi Xie, Junxiong Chen, Lingling Guo, Yande Li, Yibo Wang, Shun Zheng, Nian Zhang, Jianwei Meng, Kaiyu Zhang, Qinghao Li, Tsu-Chien Weng, Pengfei Yu, Xiaosong Liu

Sulfurized polyacrylonitrile (SPAN) exhibits a very high cycle stability by overcoming the shuttle effect of conventional Li–S batteries. However, there are still controversies in SPAN about the bonding types of sulfur with the matrix, their critical synthesis temperature regions, and their roles in the electrochemical lithium storage reaction, seriously hindering the economical synthesis of SPAN, the optimization of performances, and the exploration of other SPAN-like alternatives. The key to solving the above problems lies in accurate measurements of the thermodynamic evolution of bonding interactions in the synthesis process as well as in the electrochemical process. In this study, soft and tender X-ray absorption spectroscopy (XAS) is utilized to achieve a fine resolution of specific bonding interactions through the selective excitation of C, N, and S. Sulfur-involved bonding interactions have been elucidated, including the bonding type, critical temperature region, linking site, and their interplays. Furthermore, their contributions to lithium storage and their regulations on electrochemical performances are discussed. This study demonstrates the resolving capability of XAS for organic electrode materials and provides insights for further analyzing the cyclability of SPAN and rationally designing alternatives from the perspective of bonding interactions.

{"title":"Deciphering the Sulfur-Involved Bonding Interactions in Sulfurized Polyacrylonitrile: The Formation Thermodynamics and the Roles in Electrochemical Characteristics","authors":"Jingyi Xie, Junxiong Chen, Lingling Guo, Yande Li, Yibo Wang, Shun Zheng, Nian Zhang, Jianwei Meng, Kaiyu Zhang, Qinghao Li, Tsu-Chien Weng, Pengfei Yu, Xiaosong Liu","doi":"10.1021/acsnano.4c16728","DOIUrl":"https://doi.org/10.1021/acsnano.4c16728","url":null,"abstract":"Sulfurized polyacrylonitrile (SPAN) exhibits a very high cycle stability by overcoming the shuttle effect of conventional Li–S batteries. However, there are still controversies in SPAN about the bonding types of sulfur with the matrix, their critical synthesis temperature regions, and their roles in the electrochemical lithium storage reaction, seriously hindering the economical synthesis of SPAN, the optimization of performances, and the exploration of other SPAN-like alternatives. The key to solving the above problems lies in accurate measurements of the thermodynamic evolution of bonding interactions in the synthesis process as well as in the electrochemical process. In this study, soft and tender X-ray absorption spectroscopy (XAS) is utilized to achieve a fine resolution of specific bonding interactions through the selective excitation of C, N, and S. Sulfur-involved bonding interactions have been elucidated, including the bonding type, critical temperature region, linking site, and their interplays. Furthermore, their contributions to lithium storage and their regulations on electrochemical performances are discussed. This study demonstrates the resolving capability of XAS for organic electrode materials and provides insights for further analyzing the cyclability of SPAN and rationally designing alternatives from the perspective of bonding interactions.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"14 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986151","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

Multifunctional Nanomedicine for Targeted Atherosclerosis Therapy: Activating Plaque Clearance Cascade and Suppressing Inflammation

IF 17.1 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

ACS Nano

Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c12131

Cui Tang, Hui Wang, Lina Guo, Yimin Cui, Chan Zou, Jianming Hu, Hanyong Zhang, Guoping Yang, Wenhu Zhou

Atherosclerosis (AS) is a prevalent inflammatory vascular disease characterized by plaque formation, primarily composed of foam cells laden with lipids. Despite lipid-lowering therapies, effective plaque clearance remains challenging due to the overexpression of the CD47 molecule on apoptotic foam cells, inhibiting macrophage-mediated cellular efferocytosis and plaque resolution. Moreover, AS lesions are often associated with severe inflammation and oxidative stress, exacerbating disease progression. Herein, we introduce a multifunctional nanomedicine (CEZP) targeting AS pathogenesis via a “cell efferocytosis–lipid degradation–cholesterol efflux” paradigm, with additional anti-inflammatory properties. CEZP comprises poly(lactic-co-glycolic acid) nanoparticles encapsulated within a metal–organic framework shell coordinated with zinc ions (Zn²⁺) and epigallocatechin gallate (EGCG), enabling CpG encapsulation. Upon intravenous administration, CEZP accumulates at AS plaque sites, facilitating macrophage uptake and orchestrating AS treatment through synergistic mechanisms. CpG enhances cellular efferocytosis, Zn²⁺ promotes intracellular lipid degradation, and EGCG upregulates adenosine 5′-triphosphate-binding cassette transporters for cholesterol efflux while also exhibiting antioxidant and anti-inflammatory effects. In vivo validation confirms CEZP’s ability to stabilize plaques, reduce lipid burden, and modulate the macrophage phenotype. Moreover, CEZP is excreted from the body without safety concerns, offering a low-toxicity nonsurgical strategy for AS plaque eradication.

{"title":"Multifunctional Nanomedicine for Targeted Atherosclerosis Therapy: Activating Plaque Clearance Cascade and Suppressing Inflammation","authors":"Cui Tang, Hui Wang, Lina Guo, Yimin Cui, Chan Zou, Jianming Hu, Hanyong Zhang, Guoping Yang, Wenhu Zhou","doi":"10.1021/acsnano.4c12131","DOIUrl":"https://doi.org/10.1021/acsnano.4c12131","url":null,"abstract":"Atherosclerosis (AS) is a prevalent inflammatory vascular disease characterized by plaque formation, primarily composed of foam cells laden with lipids. Despite lipid-lowering therapies, effective plaque clearance remains challenging due to the overexpression of the CD47 molecule on apoptotic foam cells, inhibiting macrophage-mediated cellular efferocytosis and plaque resolution. Moreover, AS lesions are often associated with severe inflammation and oxidative stress, exacerbating disease progression. Herein, we introduce a multifunctional nanomedicine (CEZP) targeting AS pathogenesis via a “cell efferocytosis–lipid degradation–cholesterol efflux” paradigm, with additional anti-inflammatory properties. CEZP comprises poly(lactic-co-glycolic acid) nanoparticles encapsulated within a metal–organic framework shell coordinated with zinc ions (Zn2+) and epigallocatechin gallate (EGCG), enabling CpG encapsulation. Upon intravenous administration, CEZP accumulates at AS plaque sites, facilitating macrophage uptake and orchestrating AS treatment through synergistic mechanisms. CpG enhances cellular efferocytosis, Zn2+ promotes intracellular lipid degradation, and EGCG upregulates adenosine 5′-triphosphate-binding cassette transporters for cholesterol efflux while also exhibiting antioxidant and anti-inflammatory effects. In vivo validation confirms CEZP’s ability to stabilize plaques, reduce lipid burden, and modulate the macrophage phenotype. Moreover, CEZP is excreted from the body without safety concerns, offering a low-toxicity nonsurgical strategy for AS plaque eradication.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"7 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981568","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

The Road to Commercializing Optical Metasurfaces: Current Challenges and Future Directions

IF 17.1 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

ACS Nano

Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c15474

Younghwan Yang, Eunji Lee, Yujin Park, Junhwa Seong, Hongyoon Kim, Hyunjung Kang, Dohyun Kang, Doohyuk Han, Junsuk Rho

Optical metasurfaces, components composed of artificial nanostructures, are recognized for pushing boundaries of wavefront manipulation while maintaining a lightweight, compact design that surpasses conventional optics. Such advantages align with the current trends in optical systems, which demand compact communication devices and immersive holographic projectors, driving significant investment from the industry. Although interest in commercialization of optical metasurfaces has steadily grown since the initial breakthrough with diffraction-limited focusing, their practical applications have remained limited by challenges such as, massive-production yield, absence of standardized evaluation methods, and constrained design methodology. Here, this Perspective addresses the challenges in commercialization of optical metasurfaces, particularly focused on mass production, fabrication tolerance, performance evaluation, and integration into commercial systems. Additionally, we select the fields where metasurfaces may soon play significant roles and provide a perspective on their potentials. By addressing the challenges and exploring the solutions, this Perspective aims to foster discussions that will accelerate the utilization of optical metasurfaces and further build near-future metaphotonics platforms.

{"title":"The Road to Commercializing Optical Metasurfaces: Current Challenges and Future Directions","authors":"Younghwan Yang, Eunji Lee, Yujin Park, Junhwa Seong, Hongyoon Kim, Hyunjung Kang, Dohyun Kang, Doohyuk Han, Junsuk Rho","doi":"10.1021/acsnano.4c15474","DOIUrl":"https://doi.org/10.1021/acsnano.4c15474","url":null,"abstract":"Optical metasurfaces, components composed of artificial nanostructures, are recognized for pushing boundaries of wavefront manipulation while maintaining a lightweight, compact design that surpasses conventional optics. Such advantages align with the current trends in optical systems, which demand compact communication devices and immersive holographic projectors, driving significant investment from the industry. Although interest in commercialization of optical metasurfaces has steadily grown since the initial breakthrough with diffraction-limited focusing, their practical applications have remained limited by challenges such as, massive-production yield, absence of standardized evaluation methods, and constrained design methodology. Here, this Perspective addresses the challenges in commercialization of optical metasurfaces, particularly focused on mass production, fabrication tolerance, performance evaluation, and integration into commercial systems. Additionally, we select the fields where metasurfaces may soon play significant roles and provide a perspective on their potentials. By addressing the challenges and exploring the solutions, this Perspective aims to foster discussions that will accelerate the utilization of optical metasurfaces and further build near-future metaphotonics platforms.","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":"142981574","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

Exploring the Activation of Atomically Precise [Pt17(CO)12(PPh3)8]2+ Clusters: Mechanism and Energetics in Gas Phase and on an Inert Surface

IF 17.1 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

ACS Nano

Pub Date : 2025-01-15 DOI: 10.1021/acsnano.4c13954

Papri Chakraborty, Marco Neumaier, Johannes Seibel, Nicola Da Roit, Artur Böttcher, Christian Schmitt, Di Wang, Christian Kübel, Silke Behrens, Manfred M. Kappes

Atomically precise clusters such as [Pt₁₇(CO)₁₂(PPh₃)₈]^x+ (x = 1,2) (PPh₃ is triphenylphosphine) are known as precursors for making oxidation catalysts. However, the changes occurring to the cluster upon thermal activation during the formation of the active catalyst are poorly understood. We have used a combination of hybrid mass spectrometry and surface science to map the thermal decomposition of [Pt₁₇(CO)₁₂(PPh₃)₈](NO₃)₂. High-resolution mass and ion mobility spectrometry together with DFT-based modeling were used to probe the sequence of fragmentation reactions and fragment structures generated upon collisional excitation of [Pt₁₇(CO)₁₂(PPh₃)₈]²⁺. This was compared with thermal desorption spectroscopy of [Pt₁₇(CO)₁₂(PPh₃)₈](NO₃)₂ dropcast onto an inert graphite surface. In both cases, a characteristic sequence of CO and benzene desorption steps is observed followed at higher excitation energy by H₂ loss. This behavior is indicative of Pt-catalyzed C–H activation of phenyl groups during partial stripping of the ligand shell while the Pt₁₇P₈ cluster core is retained.

{"title":"Exploring the Activation of Atomically Precise [Pt17(CO)12(PPh3)8]2+ Clusters: Mechanism and Energetics in Gas Phase and on an Inert Surface","authors":"Papri Chakraborty, Marco Neumaier, Johannes Seibel, Nicola Da Roit, Artur Böttcher, Christian Schmitt, Di Wang, Christian Kübel, Silke Behrens, Manfred M. Kappes","doi":"10.1021/acsnano.4c13954","DOIUrl":"https://doi.org/10.1021/acsnano.4c13954","url":null,"abstract":"Atomically precise clusters such as [Pt17(CO)12(PPh3)8]x+ (x = 1,2) (PPh3 is triphenylphosphine) are known as precursors for making oxidation catalysts. However, the changes occurring to the cluster upon thermal activation during the formation of the active catalyst are poorly understood. We have used a combination of hybrid mass spectrometry and surface science to map the thermal decomposition of [Pt17(CO)12(PPh3)8](NO3)2. High-resolution mass and ion mobility spectrometry together with DFT-based modeling were used to probe the sequence of fragmentation reactions and fragment structures generated upon collisional excitation of [Pt17(CO)12(PPh3)8]2+. This was compared with thermal desorption spectroscopy of [Pt17(CO)12(PPh3)8](NO3)2 dropcast onto an inert graphite surface. In both cases, a characteristic sequence of CO and benzene desorption steps is observed followed at higher excitation energy by H2 loss. This behavior is indicative of Pt-catalyzed C–H activation of phenyl groups during partial stripping of the ligand shell while the Pt17P8 cluster core is retained.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"94 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986145","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

Innovative Heating for the Nano Age: Exploring the Potentials of Carbothermal Shock.

IF 15.8 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

ACS Nano

Pub Date : 2025-01-14 Epub Date: 2025-01-02 DOI: 10.1021/acsnano.4c12350

Jingyun Zou, Lei Tang, Lixing Kang

Heating techniques have underpinned the progress of the material and manufacturing industries. However, the explosive development of nanomaterials and micro/nanodevices has raised more requirements for the heating technique, including but not limited to high efficiency, low cost, high controllability, good usability, scalability, universality, and eco-friendliness. Carbothermal shock (CTS), a heating technique derived from traditional electrical heating, meets these requirements and is advancing at a high rate. In this review, the CTS technique, including the material to support CTS, the power supply to generate CTS, and the method to monitor CTS, is introduced, followed by an overview of the progress achieved in the application of CTS, including the modification and fabrication of nanomaterials as well as many other interesting applications, e.g., soldering/welding of micro- and macroscopic carbon materials, sintering of ceramic electrolytes, recycling of Li-ion battery, thermal tips, actuators, and artificial muscle. Problems and challenges in this area are also pointed out, and future developing directions and prospects are presented.

引用次数: 0

Oxygen-Passivated Sulfur Vacancies in Monolayer MoS₂ for Enhanced Piezoelectricity.

IF 15.8 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

ACS Nano

Pub Date : 2025-01-14 DOI: 10.1021/acsnano.4c13037

Ajay Kumar Verma, Md Ataur Rahman, Pargam Vashishtha, Xiangyang Guo, Manoj Sehrawat, Rahul Mitra, Sindhu P Giridhar, Moaz Waqar, Ankit Bhoriya, Billy J Murdoch, Chenglong Xu, Ali Zavabeti, Wei Qian Song, Yongxiang Li, Sanjay R Dhakate, Bhasker Gahtori, Taimur Ahmed, Irfan H Abidi, Sumeet Walia

Modern-day applications demand onboard electricity generation that can be achieved using piezoelectric phenomena. Reducing the dimensionality of materials is a pathway to enhancing the piezoelectric properties. Transition-metal dichalcogenides have been shown to exhibit high piezoelectricity. Monolayer MoS₂ possesses strong piezoelectricity that is otherwise negligible in its bulk form. The presence of sulfur vacancy defects in two-dimensional MoS₂ can starkly reduce piezoelectric output due to enhanced charge screening. Oxygen passivation offers thermodynamically favorable and superior vacancy passivation. Here, we demonstrate an in situ oxygen passivation of sulfur vacancies achieved by performing chemical vapor deposition in atmospheric pressure conditions, resulting in a dramatically enhanced piezoelectric output. We achieved an out-of-plane effective piezoelectric coefficient d₃₃^eff 0.54 pm/V for the MoS₂ monolayer with sulfur vacancies (S_V-MoS₂) and 0.94 pm/V where sulfur vacancies are passivated by oxygen (O_P-MoS₂). The piezoelectric device (PED) based on O_P-MoS₂ exhibits 26% higher output voltage than S_V-MoS₂ with the maximum peak-to-peak value of 0.95 V. Additionally, we show that the O_P-MoS₂-based PED can charge a 330 nF capacitor 30% faster than the S_V-MoS₂ PED for up to 50 mV in 0.5 s by repetitive finger tapping. The evolution of piezoelectricity in MoS₂ with sulfur vacancy defect manipulation promises an avenue for scalable defect engineering for next-generation applications in miniaturized self-powered electronics and sensors across computing, healthcare, and size-, weight-, and power-constrained environments.

现代应用需要利用压电现象实现车载发电。降低材料的尺寸是增强压电特性的一条途径。过渡金属二卤化物已被证明具有很高的压电性。单层 MoS2 具有很强的压电性，而在其块状形态下，这种压电性几乎可以忽略不计。二维 MoS2 中硫空位缺陷的存在会增强电荷屏蔽，从而显著降低压电输出。氧钝化在热力学上提供了有利和优越的空位钝化。在此，我们展示了在常压条件下通过化学气相沉积实现的硫空位原位氧钝化，从而显著提高了压电输出。硫空位的 MoS2 单层（SV-MoS2）的面外有效压电系数 d33eff 为 0.54 pm/V，而硫空位被氧钝化的 MoS2 单层（OP-MoS2）的面外有效压电系数 d33eff 为 0.94 pm/V。基于 OP-MoS2 的压电器件 (PED) 的输出电压比 SV-MoS2 高 26%，最大峰峰值为 0.95 V。此外，我们还展示了基于 OP-MoS2 的 PED 对 330 nF 电容器充电的速度比 SV-MoS2 PED 快 30%。利用硫空位缺陷操纵 MoS2 中压电性的演变，有望为微型化自供电电子器件和传感器的下一代应用提供可扩展的缺陷工程设计途径，应用于计算、医疗保健以及尺寸、重量和功率受限的环境中。

{"title":"Oxygen-Passivated Sulfur Vacancies in Monolayer MoS2 for Enhanced Piezoelectricity.","authors":"Ajay Kumar Verma, Md Ataur Rahman, Pargam Vashishtha, Xiangyang Guo, Manoj Sehrawat, Rahul Mitra, Sindhu P Giridhar, Moaz Waqar, Ankit Bhoriya, Billy J Murdoch, Chenglong Xu, Ali Zavabeti, Wei Qian Song, Yongxiang Li, Sanjay R Dhakate, Bhasker Gahtori, Taimur Ahmed, Irfan H Abidi, Sumeet Walia","doi":"10.1021/acsnano.4c13037","DOIUrl":"10.1021/acsnano.4c13037","url":null,"abstract":"Modern-day applications demand onboard electricity generation that can be achieved using piezoelectric phenomena. Reducing the dimensionality of materials is a pathway to enhancing the piezoelectric properties. Transition-metal dichalcogenides have been shown to exhibit high piezoelectricity. Monolayer MoS2 possesses strong piezoelectricity that is otherwise negligible in its bulk form. The presence of sulfur vacancy defects in two-dimensional MoS2 can starkly reduce piezoelectric output due to enhanced charge screening. Oxygen passivation offers thermodynamically favorable and superior vacancy passivation. Here, we demonstrate an in situ oxygen passivation of sulfur vacancies achieved by performing chemical vapor deposition in atmospheric pressure conditions, resulting in a dramatically enhanced piezoelectric output. We achieved an out-of-plane effective piezoelectric coefficient d33eff 0.54 pm/V for the MoS2 monolayer with sulfur vacancies (SV-MoS2) and 0.94 pm/V where sulfur vacancies are passivated by oxygen (OP-MoS2). The piezoelectric device (PED) based on OP-MoS2 exhibits 26% higher output voltage than SV-MoS2 with the maximum peak-to-peak value of 0.95 V. Additionally, we show that the OP-MoS2-based PED can charge a 330 nF capacitor 30% faster than the SV-MoS2 PED for up to 50 mV in 0.5 s by repetitive finger tapping. The evolution of piezoelectricity in MoS2 with sulfur vacancy defect manipulation promises an avenue for scalable defect engineering for next-generation applications in miniaturized self-powered electronics and sensors across computing, healthcare, and size-, weight-, and power-constrained environments.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":" ","pages":""},"PeriodicalIF":15.8,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142976770","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

Creation of Piezoelectricity in Quadruple Perovskite Oxides by Harnessing Cation Defects and Their Application in Piezo-Photocatalysis

IF 17.1 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

ACS Nano

Pub Date : 2025-01-14 DOI: 10.1021/acsnano.4c14974

Kai Wang, Xiangyu Guo, Chen Han, Lihong Liu, Zhiliang Wang, Lars Thomsen, Peng Chen, Zongping Shao, Xudong Wang, Fang Xie, Gang Liu, Lianzhou Wang, Shaomin Liu

Quadruple perovskite oxides have received extensive attention in electronics and catalysis, owing to their cation-ordering structure and intriguing physical properties. However, their repertoires still remain limited. In particular, piezoelectricity from quadruple perovskites has been rarely reported due to the frustrated symmetry-breaking transition in A-site-ordered perovskite structures, disabling their piezoelectric applications. Herein, we report a feasible strategy to achieve piezoelectricity in CaCu₃Ti₄O₁₂ (CCTO) quadruple perovskite via cation defect engineering, specifically through a thermal-driven selective cation exsolution strategy to introduce Cu vacancies. The introduction of Cu point defects in CCTO locally destabilizes the constrained tilted TiO₆ octahedra framework, relaxing the octahedral tilting and inducing structural heterogeneity which, in turn, disrupts the high symmetry of the pristine cubic phase. As a result, the defective CCTO with localized asymmetry exhibits intense polarization and a robust piezoelectricity of 7 pC N^–1. The created piezoelectricity is further validated by its application as a piezo-photocatalyst, enabling efficient charge separation and transfer with a 2.5-times increment in the lifetime of photoexcitations. This enhancement leads to a 3.86- and 31-fold increase in the production of hydrogen peroxide and reactive oxygen species compared with individual piezocatalysis and photocatalysis, respectively. This study establishes a pathway to engineer piezoelectricity in quadruple perovskites, potentially unlocking a wide range of applications in modern microelectronics beyond the demonstrated piezo-photocatalysis.

{"title":"Creation of Piezoelectricity in Quadruple Perovskite Oxides by Harnessing Cation Defects and Their Application in Piezo-Photocatalysis","authors":"Kai Wang, Xiangyu Guo, Chen Han, Lihong Liu, Zhiliang Wang, Lars Thomsen, Peng Chen, Zongping Shao, Xudong Wang, Fang Xie, Gang Liu, Lianzhou Wang, Shaomin Liu","doi":"10.1021/acsnano.4c14974","DOIUrl":"https://doi.org/10.1021/acsnano.4c14974","url":null,"abstract":"Quadruple perovskite oxides have received extensive attention in electronics and catalysis, owing to their cation-ordering structure and intriguing physical properties. However, their repertoires still remain limited. In particular, piezoelectricity from quadruple perovskites has been rarely reported due to the frustrated symmetry-breaking transition in A-site-ordered perovskite structures, disabling their piezoelectric applications. Herein, we report a feasible strategy to achieve piezoelectricity in CaCu3Ti4O12 (CCTO) quadruple perovskite via cation defect engineering, specifically through a thermal-driven selective cation exsolution strategy to introduce Cu vacancies. The introduction of Cu point defects in CCTO locally destabilizes the constrained tilted TiO6 octahedra framework, relaxing the octahedral tilting and inducing structural heterogeneity which, in turn, disrupts the high symmetry of the pristine cubic phase. As a result, the defective CCTO with localized asymmetry exhibits intense polarization and a robust piezoelectricity of 7 pC N–1. The created piezoelectricity is further validated by its application as a piezo-photocatalyst, enabling efficient charge separation and transfer with a 2.5-times increment in the lifetime of photoexcitations. This enhancement leads to a 3.86- and 31-fold increase in the production of hydrogen peroxide and reactive oxygen species compared with individual piezocatalysis and photocatalysis, respectively. This study establishes a pathway to engineer piezoelectricity in quadruple perovskites, potentially unlocking a wide range of applications in modern microelectronics beyond the demonstrated piezo-photocatalysis.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"4 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981577","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

Olfactory-Inspired Separation-Sensing Nanochannel-Based Electronics for Wireless Sweat Monitoring 用于无线汗液监测的嗅觉启发式分离传感纳米电子器件

IF 17.1 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

ACS Nano

Pub Date : 2025-01-14 DOI: 10.1021/acsnano.4c14660

Yuge Wu, Qi Wang, Xin Li, Ke Li, Dehua Huang, Kehan Zou, Zhehua Zhang, Yongchao Qian, Congcong Zhu, Xiang-Yu Kong, Liping Wen

Human sweat has the potential to be sufficiently utilized for noninvasive monitoring. Given the complexity of sweat secretion, the sensitivity and selectivity of sweat monitoring should be further improved. Here, we developed an olfactory-inspired separation-sensing nanochannel-based electronic for sensitive and selective sweat monitoring, which was simultaneously endowed with interferent separation and target detection performances. The special separation-sensing strategy imparts functional composite membranes with a high sensitivity of 113 mV dec^–1 for potassium detection. The excellent mechanical properties and conformability of the Kevlar aramid nanofiber layer bring well-wearing performances to realize continuous wireless sweat monitoring. The recognition between functional molecules and target ions is proved at the molecular level in detail in the article. The replacement of functional molecules proves the universality of the strategy for performance enhancement in intricate biofluid analysis systems.

引用次数: 0

Revealing Multistep Phase Separation in Metal Alloy Nanoparticles with In Situ Transmission Electron Microscopy

IF 17.1 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

ACS Nano

Pub Date : 2025-01-14 DOI: 10.1021/acsnano.4c16095

Yingying Jiang, Zicong Marvin Wong, Hongwei Yan, Teck Leong Tan, Utkur Mirsaidov

Phase separation plays a crucial role in many natural and industrial processes, such as the formation of clouds and minerals and the distillation of crude oil. In metals and alloys, phase separation is an important approach often utilized to improve their mechanical strength for use in construction, automobile, and aerospace manufacturing. Despite its importance in many processes, the atomic details of phase separation are largely unknown. In particular, it is unclear how a different crystal phase emerges from the parent alloy. Here, using real-time in situ transmission electron microscopy, we describe the stages of the phase separation in face-centered cubic (fcc) AuRu alloy nanoparticles, resulting in a Ru phase with a hexagonal close-packed (hcp) crystal structure. Our observation reveals that the hcp Ru phase forms in two steps: the spinodal decomposition of the alloy produces metastable fcc Ru clusters, and as they grow larger, these clusters transform into hcp Ru domains. Our calculations indicate that the primary reason for the fcc-to-hcp transformation is the size-dependent competition between the interfacial and bulk energies of Ru domains. These insights into elusive, transient steps in the phase separation of alloys can aid in engineering nanomaterials with unconventional phases.

相分离在许多自然和工业过程中都起着至关重要的作用，例如云和矿物的形成以及原油的蒸馏。在金属和合金中，相分离是一种重要的方法，通常用来提高它们的机械强度，以用于建筑、汽车和航空航天制造。尽管相分离在许多工艺中都很重要，但相分离的原子细节在很大程度上仍不为人所知。尤其是，人们还不清楚不同的晶相是如何从母体合金中产生的。在这里，我们利用实时原位透射电子显微镜，描述了面心立方（fcc）AuRu 合金纳米粒子相分离的各个阶段，从而产生了具有六方紧密堆积（hcp）晶体结构的 Ru 相。我们的观察结果表明，hcp Ru 相的形成分为两个步骤：合金的旋光分解产生了可转移的 fcc Ru 簇，随着簇的增大，这些簇转变为 hcp Ru 域。我们的计算表明，从 fcc 到 hcp 转变的主要原因是 Ru 结构域的界面能和体能之间的竞争与尺寸有关。这些对合金相分离过程中难以捉摸的瞬态步骤的深入了解有助于采用非常规相的纳米材料的工程设计。

{"title":"Revealing Multistep Phase Separation in Metal Alloy Nanoparticles with In Situ Transmission Electron Microscopy","authors":"Yingying Jiang, Zicong Marvin Wong, Hongwei Yan, Teck Leong Tan, Utkur Mirsaidov","doi":"10.1021/acsnano.4c16095","DOIUrl":"https://doi.org/10.1021/acsnano.4c16095","url":null,"abstract":"Phase separation plays a crucial role in many natural and industrial processes, such as the formation of clouds and minerals and the distillation of crude oil. In metals and alloys, phase separation is an important approach often utilized to improve their mechanical strength for use in construction, automobile, and aerospace manufacturing. Despite its importance in many processes, the atomic details of phase separation are largely unknown. In particular, it is unclear how a different crystal phase emerges from the parent alloy. Here, using real-time in situ transmission electron microscopy, we describe the stages of the phase separation in face-centered cubic (fcc) AuRu alloy nanoparticles, resulting in a Ru phase with a hexagonal close-packed (hcp) crystal structure. Our observation reveals that the hcp Ru phase forms in two steps: the spinodal decomposition of the alloy produces metastable fcc Ru clusters, and as they grow larger, these clusters transform into hcp Ru domains. Our calculations indicate that the primary reason for the fcc-to-hcp transformation is the size-dependent competition between the interfacial and bulk energies of Ru domains. These insights into elusive, transient steps in the phase separation of alloys can aid in engineering nanomaterials with unconventional phases.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"61 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975569","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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