Jing Li, Xiaoting Wang, Yang Ma, Wei Han, Kexin Li, Jingtao Li, Yi Wu, Yuehui Zhao, Tao Yan, Xiu Liu, Haolin Shi, Xiaoqing Chen, Yongzhe Zhang
Two-dimensional (2D) ferroelectric field-effect transistors (Fe-FETs) based on p–n junctions are the basic units of future neuromorphic hardware. The In2Se3 semiconductor with ferroelectric, photoelectric, and phase transition properties possesses great application potential for in-sensor computing, but its ferroelectric p–n junction (FePNJ) is not well investigated. Here, we present an optoelectronic synapse made of uniformly full-coverage α-In2Se3/WSe2 FePNJ, achieving ultralow-power classification recognition and multiscale signal processing. Using chemical vapor deposition (CVD), we can obtain β′-In2Se3/WSe2 subferroelectric p–n junctions by direct growth on SiO2/Si substrate and α-In2Se3/WSe2 FePNJ by phase transition. Modulated by the synergistic effect of the polarization electric field and the built-in electric field, the FePNJ exhibits significantly enhanced and highly tunable synaptic effects (memory retention >2500 s and >8 multilevel current states under single optical/electrical pulses), along with power consumption down to atto-joule levels. Utilizing these photoelectric properties, we constructed an all-ferroelectric in-sensor reservoir computing system, comprising both reservoir and readout networks, achieving ultralow-power handwritten digit recognition. We also created a multiscale reservoir computing system through the gate-voltage-modulated relaxation time scale of the FePNJ, which can efficiently detect motions in the 1 to 100 km h–1 speed range.
{"title":"Phase-Engineered In2Se3 Ferroelectric P-N Junctions in Phototransistors for Ultra-Low Power and Multiscale Reservoir Computing","authors":"Jing Li, Xiaoting Wang, Yang Ma, Wei Han, Kexin Li, Jingtao Li, Yi Wu, Yuehui Zhao, Tao Yan, Xiu Liu, Haolin Shi, Xiaoqing Chen, Yongzhe Zhang","doi":"10.1021/acsnano.5c00250","DOIUrl":"https://doi.org/10.1021/acsnano.5c00250","url":null,"abstract":"Two-dimensional (2D) ferroelectric field-effect transistors (Fe-FETs) based on p–n junctions are the basic units of future neuromorphic hardware. The In<sub>2</sub>Se<sub>3</sub> semiconductor with ferroelectric, photoelectric, and phase transition properties possesses great application potential for in-sensor computing, but its ferroelectric p–n junction (FePNJ) is not well investigated. Here, we present an optoelectronic synapse made of uniformly full-coverage α-In<sub>2</sub>Se<sub>3</sub>/WSe<sub>2</sub> FePNJ, achieving ultralow-power classification recognition and multiscale signal processing. Using chemical vapor deposition (CVD), we can obtain β′-In<sub>2</sub>Se<sub>3</sub>/WSe<sub>2</sub> subferroelectric p–n junctions by direct growth on SiO<sub>2</sub>/Si substrate and α-In<sub>2</sub>Se<sub>3</sub>/WSe<sub>2</sub> FePNJ by phase transition. Modulated by the synergistic effect of the polarization electric field and the built-in electric field, the FePNJ exhibits significantly enhanced and highly tunable synaptic effects (memory retention >2500 s and >8 multilevel current states under single optical/electrical pulses), along with power consumption down to atto-joule levels. Utilizing these photoelectric properties, we constructed an all-ferroelectric in-sensor reservoir computing system, comprising both reservoir and readout networks, achieving ultralow-power handwritten digit recognition. We also created a multiscale reservoir computing system through the gate-voltage-modulated relaxation time scale of the FePNJ, which can efficiently detect motions in the 1 to 100 km h<sup>–1</sup> speed range.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"49 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703446","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}
Tensile biaxial strain has been demonstrated to induce in-plane ferroelectricity in SrTiO3 thin films at room temperature. However, out-of-plane ferroelectricity is more favorable for electronic device applications. Here, we report the achievement of room-temperature out-of-plane ferroelectric SrTiO3 thin films with giant tetragonality (c/a ∼ 1.061) and an ultrahigh ferroelectric stablity temperature (>1000 K) through epitaxial strain and defect engineering. Optical second-harmonic generation (SHG) proves that the enhancement of tetragonality enables improved ferroelectricity. Moreover, a combination of scanning transmission electron microscopy (STEM) and X-ray absorption near-edge spectroscopy (XANES) reveals the origin of enhanced tetragonality and strong ferroelectricity in defect- and strain-codriven supertetragonal SrTiO3 thin films. Our findings present an approach to material design that can be extended to other material systems for the enhancement of ferroelectricity and the observation of emergent phenomena.
{"title":"Defect and Strain Engineering Coenhanced Nanoscale Ferroelectricity in SrTiO3 Thin Films","authors":"Chao Chen, Caiwen Li, Jiangxiao Li, Han Gao, Jingtian Zhou, Zhen Wang, Xiangbin Cai, Guofeng Liang, Xiaozhe Yin, Zhibang Shen, Jinhui Yu, Zedong Xu, Minghui Qin, Xubing Lu, Lang Chen, Ning Wang, Ye Zhu, Yu Chen, Guofu Zhou, Xingsen Gao, Yibo Han, Zhenlin Luo, Jun-Ming Liu, Deyang Chen","doi":"10.1021/acsnano.5c03518","DOIUrl":"https://doi.org/10.1021/acsnano.5c03518","url":null,"abstract":"Tensile biaxial strain has been demonstrated to induce in-plane ferroelectricity in SrTiO<sub>3</sub> thin films at room temperature. However, out-of-plane ferroelectricity is more favorable for electronic device applications. Here, we report the achievement of room-temperature out-of-plane ferroelectric SrTiO<sub>3</sub> thin films with giant tetragonality (<i>c</i>/<i>a</i> ∼ 1.061) and an ultrahigh ferroelectric stablity temperature (>1000 K) through epitaxial strain and defect engineering. Optical second-harmonic generation (SHG) proves that the enhancement of tetragonality enables improved ferroelectricity. Moreover, a combination of scanning transmission electron microscopy (STEM) and X-ray absorption near-edge spectroscopy (XANES) reveals the origin of enhanced tetragonality and strong ferroelectricity in defect- and strain-codriven supertetragonal SrTiO<sub>3</sub> thin films. Our findings present an approach to material design that can be extended to other material systems for the enhancement of ferroelectricity and the observation of emergent phenomena.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"61 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713781","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}
Mirudula Mohankumar, Soraia Fernandes, Francesca Cavalieri, Christina Cortez-Jugo, Frank Caruso
The evolution of drug resistance in tumor malignancies has necessitated advancements in anticancer drug therapy. Drug combination therapy, which can burden cancer progression at multiple target sites, has been used to address drug resistance and includes the coencapsulation of synergistic drugs within nanoparticle carriers. However, the use of organic and inorganic carriers can lead to additional material-induced safety concerns, including inflammation and antibody formation. Herein, we report an ultrasound-driven approach to combine synergistic anticancer drugs into carrier-free particles. Venetoclax (Vtx) (as a model anticancer drug) is combined with an anticancer anthracycline drug, doxorubicin (Dox), or a myeloid cell leukemia-1 inhibitor drug (S63845) to form spherical, submicrometer-sized (∼200–1000 nm in diameter) particles, consisting predominantly of the drug molecules stabilized by hydrophobic interactions. The coassembled particles, i.e., nanodrugs (NDs), display comparable and 2-fold higher anticancer activity than the free drugs and the monocomponent NDs, respectively, in Vtx-resistant SKOV-3 cells. The coassembled NDs containing Vtx and Dox increased the survival of SKOV-3 xenograft-bearing mice by at least 6 days in comparison with free Vtx or Vtx NDs and at least 10 days in comparison with saline-treated mice. Microscopy analysis of tumor tissues confirmed greater tissue damage and apoptosis induced by the NDs than those induced by the free drugs. The present findings highlight the potential of sono-driven assembled carrier-free systems in anticancer combination therapy, combining the advantages of a high surface area and slow-release particulate system with the synergistic action of multiple drugs to combat drug resistance.
{"title":"Ultrasound-Driven Coassembly of Anticancer Drugs into Carrier-Free Particles","authors":"Mirudula Mohankumar, Soraia Fernandes, Francesca Cavalieri, Christina Cortez-Jugo, Frank Caruso","doi":"10.1021/acsnano.5c01284","DOIUrl":"https://doi.org/10.1021/acsnano.5c01284","url":null,"abstract":"The evolution of drug resistance in tumor malignancies has necessitated advancements in anticancer drug therapy. Drug combination therapy, which can burden cancer progression at multiple target sites, has been used to address drug resistance and includes the coencapsulation of synergistic drugs within nanoparticle carriers. However, the use of organic and inorganic carriers can lead to additional material-induced safety concerns, including inflammation and antibody formation. Herein, we report an ultrasound-driven approach to combine synergistic anticancer drugs into carrier-free particles. Venetoclax (Vtx) (as a model anticancer drug) is combined with an anticancer anthracycline drug, doxorubicin (Dox), or a myeloid cell leukemia-1 inhibitor drug (S63845) to form spherical, submicrometer-sized (∼200–1000 nm in diameter) particles, consisting predominantly of the drug molecules stabilized by hydrophobic interactions. The coassembled particles, i.e., nanodrugs (NDs), display comparable and 2-fold higher anticancer activity than the free drugs and the monocomponent NDs, respectively, in Vtx-resistant SKOV-3 cells. The coassembled NDs containing Vtx and Dox increased the survival of SKOV-3 xenograft-bearing mice by at least 6 days in comparison with free Vtx or Vtx NDs and at least 10 days in comparison with saline-treated mice. Microscopy analysis of tumor tissues confirmed greater tissue damage and apoptosis induced by the NDs than those induced by the free drugs. The present findings highlight the potential of sono-driven assembled carrier-free systems in anticancer combination therapy, combining the advantages of a high surface area and slow-release particulate system with the synergistic action of multiple drugs to combat drug resistance.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"42 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713778","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}
Vladimir A. Baulin, Denver P. Linklater, Saulius Juodkazis, Elena P. Ivanova
Inspired by the natural defense strategies of insect wings and plant leaves, nanostructured surfaces have emerged as a promising tool in various fields, including engineering, biomedical sciences, and materials science, to combat bacterial contamination and disrupt biofilm formation. However, the development of effective antimicrobial surfaces against fungal and viral pathogens presents distinct challenges, necessitating tailored approaches. Here, we aimed to review the recent advancements of the use of nanostructured surfaces to combat microbial contamination, particularly focusing on their mechano-bactericidal and antifungal properties, as well as their potential in mitigating viral transmission. We comparatively analyzed the diverse geometries and nanoarchitectures of these surfaces and discussed their application in various biomedical contexts, such as dental and orthopedic implants, drug delivery systems, and tissue engineering. Our review highlights the importance of preventing microbial attachment and biofilm formation, especially in the context of rising antimicrobial resistance and the economic impact of biofilms. We also discussed the latest progress in materials science, particularly nanostructured surface engineering, as a promising strategy for reducing viral transmission through surfaces. Overall, our findings underscore the significance of innovative strategies to mitigate microbial attachment and surface-mediated transmission, while also emphasizing the need for further interdisciplinary research in this area to optimize antimicrobial efficacy and address emerging challenges.
{"title":"Exploring Broad-Spectrum Antimicrobial Nanotopographies: Implications for Bactericidal, Antifungal, and Virucidal Surface Design","authors":"Vladimir A. Baulin, Denver P. Linklater, Saulius Juodkazis, Elena P. Ivanova","doi":"10.1021/acsnano.4c15671","DOIUrl":"https://doi.org/10.1021/acsnano.4c15671","url":null,"abstract":"Inspired by the natural defense strategies of insect wings and plant leaves, nanostructured surfaces have emerged as a promising tool in various fields, including engineering, biomedical sciences, and materials science, to combat bacterial contamination and disrupt biofilm formation. However, the development of effective antimicrobial surfaces against fungal and viral pathogens presents distinct challenges, necessitating tailored approaches. Here, we aimed to review the recent advancements of the use of nanostructured surfaces to combat microbial contamination, particularly focusing on their mechano-bactericidal and antifungal properties, as well as their potential in mitigating viral transmission. We comparatively analyzed the diverse geometries and nanoarchitectures of these surfaces and discussed their application in various biomedical contexts, such as dental and orthopedic implants, drug delivery systems, and tissue engineering. Our review highlights the importance of preventing microbial attachment and biofilm formation, especially in the context of rising antimicrobial resistance and the economic impact of biofilms. We also discussed the latest progress in materials science, particularly nanostructured surface engineering, as a promising strategy for reducing viral transmission through surfaces. Overall, our findings underscore the significance of innovative strategies to mitigate microbial attachment and surface-mediated transmission, while also emphasizing the need for further interdisciplinary research in this area to optimize antimicrobial efficacy and address emerging challenges.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"93 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695707","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}
Seol Baek, Salvador Gutierrez-Portocarrero, Rokas Gerulskis, Shelley D. Minteer, Sean R. German, Henry S. White
Many technologies involve immobilizing catalysts such as enzymes on surfaces, and the catalytic activities or functional efficiencies of these surface-bound catalysts can vary depending on orientations, localized binding sites, active sites, and intrinsic molecular nature. Accurate and rapid quantification of reaction products from surface-immobilized catalysts is crucial for understanding the selectivity, mechanisms, and reaction dynamics of catalytic systems and for revealing heterogeneous catalytic activities and reaction sites for applications such as biosensors and energy conversion/generation systems. Here, we demonstrate the feasibility of localized enzymatic activity measurements using microscale carbon dioxide (CO2)-sensitive ion-selective electrode (ISE) pipettes (0.5–2.5 μm tip radius) as a probe, with in situ potentiometric scanning electrochemical microscopy (SECM). We develop carbonate (CO32–) ionophore-incorporated ISEs exhibiting a Nernstian response (26.7 mV/decade) with a detection limit of 1.72 μM and explore surface-immobilized formate dehydrogenase (FDH) activity by detecting CO2 generated by the enzymatic reaction via potentiometric measurements. SECM is used for real-time spatial/temporal investigation of FDH immobilized onto the surface at a micrometer-scale resolution. Moreover, unlike voltammetric techniques based on faradaic reactions, the potentiometric measurements using ISEs allow highly sensitive and selective detection of CO32–, rendering efficient quantification of CO2 without interference from solution composition changes arising from faradaic processes. The total amount of CO2 generated at an FDH-immobilized Au ultramicroelectrode is quantified as a function of coenzyme, i.e., NAD+, and substrate, i.e., formate, concentrations both in constant tip–sample distance mode and variable depth mode. Finally, we demonstrate the use of the ISE to quantify CO2 levels in blood serum.
{"title":"Detection of CO2 Locally Generated by Formate Dehydrogenase Using Carbonate Ion-Selective Micropipette Electrodes","authors":"Seol Baek, Salvador Gutierrez-Portocarrero, Rokas Gerulskis, Shelley D. Minteer, Sean R. German, Henry S. White","doi":"10.1021/acsnano.5c00387","DOIUrl":"https://doi.org/10.1021/acsnano.5c00387","url":null,"abstract":"Many technologies involve immobilizing catalysts such as enzymes on surfaces, and the catalytic activities or functional efficiencies of these surface-bound catalysts can vary depending on orientations, localized binding sites, active sites, and intrinsic molecular nature. Accurate and rapid quantification of reaction products from surface-immobilized catalysts is crucial for understanding the selectivity, mechanisms, and reaction dynamics of catalytic systems and for revealing heterogeneous catalytic activities and reaction sites for applications such as biosensors and energy conversion/generation systems. Here, we demonstrate the feasibility of localized enzymatic activity measurements using microscale carbon dioxide (CO<sub>2</sub>)-sensitive ion-selective electrode (ISE) pipettes (0.5–2.5 μm tip radius) as a probe, with in situ potentiometric scanning electrochemical microscopy (SECM). We develop carbonate (CO<sub>3</sub><sup>2–</sup>) ionophore-incorporated ISEs exhibiting a Nernstian response (26.7 mV/decade) with a detection limit of 1.72 μM and explore surface-immobilized formate dehydrogenase (FDH) activity by detecting CO<sub>2</sub> generated by the enzymatic reaction via potentiometric measurements. SECM is used for real-time spatial/temporal investigation of FDH immobilized onto the surface at a micrometer-scale resolution. Moreover, unlike voltammetric techniques based on faradaic reactions, the potentiometric measurements using ISEs allow highly sensitive and selective detection of CO<sub>3</sub><sup>2–</sup>, rendering efficient quantification of CO<sub>2</sub> without interference from solution composition changes arising from faradaic processes. The total amount of CO<sub>2</sub> generated at an FDH-immobilized Au ultramicroelectrode is quantified as a function of coenzyme, i.e., NAD<sup>+</sup>, and substrate, i.e., formate, concentrations both in constant tip–sample distance mode and variable depth mode. Finally, we demonstrate the use of the ISE to quantify CO<sub>2</sub> levels in blood serum.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"33 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695711","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}
Adriena Jedličková, Daniela Kristeková, Zuzana Husáková, Pavel Coufalík, Lucie Vrlíková, Tereza Smutná, Michaela Capandová, Lukáš Alexa, Denisa Lusková, Kamil Křůmal, Veronika Jakešová, Zbyněk Večeřa, Nikodém Zezula, Viktor Kanický, Aleš Hampl, Tomáš Vaculovič, Pavel Mikuška, Jana Dumková, Marcela Buchtová
Lead nanoparticles (PbNPs) in air pollution pose a significant threat to human health, especially due to their neurotoxic effects. In this study, we exposed mice to lead(II) oxide nanoparticles (PbONPs) in inhalation chambers to mimic real-life exposure and assess their impact on the brain. PbONPs caused the formation of Hirano bodies and pathological changes related to neurodegenerative disorders through cytoskeletal disruptions without the induction of inflammation. Damage to astrocytic endfeet and capillary endothelial cells indicated a compromised blood–brain barrier (BBB), allowing PbONPs to enter the brain. Additionally, NPs were detected along the olfactory pathway, including fila olfactoria, suggesting that at least a proportion of PbNPs enter the brain directly by passing through the olfactory epithelium. PbNP inhalation severely damaged the apical parts of olfactory epithelial cells, including the loss of microtubules in their ciliary distal segments. Inhalation of PbONPs led to the rapid accumulation of lead in the brain, while more soluble lead(II) nitrate NPs did not accumulate significantly until 11 weeks of exposure. PbNPs induced disruption of the BBB at multiple levels, ranging from ultrastructural changes to functional impairments of the barrier; however, they did not induce systemic inflammation in the brain. The clearance ability of the brain to remove Pb was very low for both types of NPs, with significant pathological effects persisting even after a long clearance period. Cation-binding proteins (ZBTB20 and calbindin1) were distributed unevenly in the brain, with the strongest signal located in the hippocampus, which exhibited the greatest defects in nuclear architecture, indicating that this area is the most sensitive structure for PbNP exposure. PbNP exposure also altered the PI3K/Akt/mTOR signaling pathway, and tau phosphorylation in the hippocampus and inhibition of tau phosphorylation by GSK-3 inhibitor rescued the negative effect of PbONPs on the intracellular calcium level in trigeminal ganglion cultures. In zebrafish larvae, PbONPs affected locomotor activity and reduced calcium levels in the medium enhanced negative effect of PbONP on animal mobility, even increasing lethality. These findings suggest that cytoskeletal disruption and calcium dysregulation are key factors in PbNP-induced neurotoxicity, providing potential targets for therapeutic intervention to prevent neurodegenerative changes following PbNP exposure.
{"title":"Inhaled Lead Nanoparticles Enter the Brain through the Olfactory Pathway and Induce Neurodegenerative Changes Resembling Tauopathies","authors":"Adriena Jedličková, Daniela Kristeková, Zuzana Husáková, Pavel Coufalík, Lucie Vrlíková, Tereza Smutná, Michaela Capandová, Lukáš Alexa, Denisa Lusková, Kamil Křůmal, Veronika Jakešová, Zbyněk Večeřa, Nikodém Zezula, Viktor Kanický, Aleš Hampl, Tomáš Vaculovič, Pavel Mikuška, Jana Dumková, Marcela Buchtová","doi":"10.1021/acsnano.4c14571","DOIUrl":"https://doi.org/10.1021/acsnano.4c14571","url":null,"abstract":"Lead nanoparticles (PbNPs) in air pollution pose a significant threat to human health, especially due to their neurotoxic effects. In this study, we exposed mice to lead(II) oxide nanoparticles (PbONPs) in inhalation chambers to mimic real-life exposure and assess their impact on the brain. PbONPs caused the formation of Hirano bodies and pathological changes related to neurodegenerative disorders through cytoskeletal disruptions without the induction of inflammation. Damage to astrocytic endfeet and capillary endothelial cells indicated a compromised blood–brain barrier (BBB), allowing PbONPs to enter the brain. Additionally, NPs were detected along the olfactory pathway, including <i>fila olfactoria</i>, suggesting that at least a proportion of PbNPs enter the brain directly by passing through the olfactory epithelium. PbNP inhalation severely damaged the apical parts of olfactory epithelial cells, including the loss of microtubules in their ciliary distal segments. Inhalation of PbONPs led to the rapid accumulation of lead in the brain, while more soluble lead(II) nitrate NPs did not accumulate significantly until 11 weeks of exposure. PbNPs induced disruption of the BBB at multiple levels, ranging from ultrastructural changes to functional impairments of the barrier; however, they did not induce systemic inflammation in the brain. The clearance ability of the brain to remove Pb was very low for both types of NPs, with significant pathological effects persisting even after a long clearance period. Cation-binding proteins (ZBTB20 and calbindin1) were distributed unevenly in the brain, with the strongest signal located in the hippocampus, which exhibited the greatest defects in nuclear architecture, indicating that this area is the most sensitive structure for PbNP exposure. PbNP exposure also altered the PI3K/Akt/mTOR signaling pathway, and tau phosphorylation in the hippocampus and inhibition of tau phosphorylation by GSK-3 inhibitor rescued the negative effect of PbONPs on the intracellular calcium level in trigeminal ganglion cultures. In zebrafish larvae, PbONPs affected locomotor activity and reduced calcium levels in the medium enhanced negative effect of PbONP on animal mobility, even increasing lethality. These findings suggest that cytoskeletal disruption and calcium dysregulation are key factors in PbNP-induced neurotoxicity, providing potential targets for therapeutic intervention to prevent neurodegenerative changes following PbNP exposure.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"65 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695851","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}
Developing ionotronic interface layers for zinc anodes with superior mechanical integrity is one of the efficient strategies to suppress the growth of zinc dendrites in favor of the cycling stability of aqueous zinc-ion batteries (AZIBs). Herein, we assembled robust 2D MXene-based hydrogel films cross-linked by 1D cellulose nanofibril (CNF) dual networks, acting as interface layers to stabilize Zn anodes. The MXene-CNF hydrogel films integrated multifunctionalities, including a high in-plane toughness of 18.39 MJ m–3, high in-plane/out-of-plane elastic modulus of 0.85 and 3.65 GPa, mixed electronic/ionic (ionotronic) conductivity of 1.53 S cm–1 and 0.52 mS cm–1, and high zincophilicity with a high binding energy (1.33 eV) and low migration energy barrier (0.24 eV) for Zn2+. These integrated multifunctionalities, endowed with coupled multifield effects, including strong stress confinement and uniform ionic/electronic field distributions on Zn anodes, effectively suppressed dendrite growth, as proven by experiments and simulations. An example of the MXene-CNF|Zn showed a reduced nucleation overpotential of 19 mV, an extended cycling life of over 2700 h in Zn||Zn cells, and a high capacity of 323 mAh g–1 in Zn||MnO2 cells, compared with bare Zn. This work offers an approach for exploring mechanically robust 1D/2D ionotronic hydrogel interface layers to stabilize the Zn anodes of AZIBs.
{"title":"Tough MXene-Cellulose Nanofibril Ionotronic Dual-Network Hydrogel Films for Stable Zinc Anodes","authors":"Mengyu Liu, Liming Zhang, Jowan Rostami, Teng Zhang, Kyle Matthews, Sheng Chen, Wenjie Fan, Yue Zhu, Jingwei Chen, Minghua Huang, Jingyi Wu, Huanlei Wang, Mahiar Max Hamedi, Feng Xu, Weiqian Tian, Lars Wågberg, Yury Gogotsi","doi":"10.1021/acsnano.5c01497","DOIUrl":"https://doi.org/10.1021/acsnano.5c01497","url":null,"abstract":"Developing ionotronic interface layers for zinc anodes with superior mechanical integrity is one of the efficient strategies to suppress the growth of zinc dendrites in favor of the cycling stability of aqueous zinc-ion batteries (AZIBs). Herein, we assembled robust 2D MXene-based hydrogel films cross-linked by 1D cellulose nanofibril (CNF) dual networks, acting as interface layers to stabilize Zn anodes. The MXene-CNF hydrogel films integrated multifunctionalities, including a high in-plane toughness of 18.39 MJ m<sup>–3</sup>, high in-plane/out-of-plane elastic modulus of 0.85 and 3.65 GPa, mixed electronic/ionic (ionotronic) conductivity of 1.53 S cm<sup>–1</sup> and 0.52 mS cm<sup>–1</sup>, and high zincophilicity with a high binding energy (1.33 eV) and low migration energy barrier (0.24 eV) for Zn<sup>2+</sup>. These integrated multifunctionalities, endowed with coupled multifield effects, including strong stress confinement and uniform ionic/electronic field distributions on Zn anodes, effectively suppressed dendrite growth, as proven by experiments and simulations. An example of the MXene-CNF|Zn showed a reduced nucleation overpotential of 19 mV, an extended cycling life of over 2700 h in Zn||Zn cells, and a high capacity of 323 mAh g<sup>–1</sup> in Zn||MnO<sub>2</sub> cells, compared with bare Zn. This work offers an approach for exploring mechanically robust 1D/2D ionotronic hydrogel interface layers to stabilize the Zn anodes of AZIBs.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"102 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695713","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}
Serialized lithium traveling on the solid electrolyte interphase (SEI) of the metal anode plays a dominant role in high-energy-density lithium metal batteries. Unsatisfactorily, irregular native SEI suffers from the Li+ local deposition and possesses low inorganic component content, which exacerbates the growth of lithium dendrites and leads to poor battery performance. Purposefully, we fabricated the porphyrin-based covalent organic frameworks (COF-366 and COF-367) as lithium metal anode interfaces. Concretely, heterogenetic segments within COFs nodes allocate electron situations to induce component-selective catalysis, of which electron-rich nitrogen atom sites urge the N–S cleavage of bis(trifluoromethylsulfonyl)azanide (TFSI–) and C–C breakage of 1,2-dimethoxyethane (DME), while electron-deficient benzene sites facilitate the C–O cleavage of 1,3-dioxolane (DOL), constructing a rich Li2O/LiF-rich modification of COFs interface. The well-constructed interface facilitates rapid Li+ migration, distributes charge evenly, and further increases the Li+ flux, which achieves uniform Li+ deposition and suppresses dendrite growth. Consequently, the COF-366@Li anode displayed outstanding capacity stability at a high current density of 5C after 400 cycles with a capacity of 53.37 mAh g–1 (70.99%). The COF-366@Li||LFP pouch cell further validated its practical application with an impressive capacity of 120.37 mAh g–1 and an excellent capacity retention of 92.42% after 43 cycles with a high cathode loading of 295.2 mg. This study demonstrates the feasibility of heterogeneity-segment of customized-type COFs to induce component-selective charge-coupling catalysis toward electrolytes and manipulate SEI inorganic components for stabilizing lithium metal anode.
{"title":"Heterogeneity-Segment Charge-Induced-Coupling Catalysis of Component-Selective-Type Covalent Organic Frameworks Interface toward Stabilizing Lithium Metal Anode","authors":"Zikang Chen, Jiajie Pan, Wenzhi Huang, Kaixiang Shi, Zihao Yang, Hao Wu, Suqing Wei, Guoxing Jiang, Wenwu Zou, Rui Zhang, Xu Li, Quanbing Liu","doi":"10.1021/acsnano.4c18473","DOIUrl":"https://doi.org/10.1021/acsnano.4c18473","url":null,"abstract":"Serialized lithium traveling on the solid electrolyte interphase (SEI) of the metal anode plays a dominant role in high-energy-density lithium metal batteries. Unsatisfactorily, irregular native SEI suffers from the Li<sup>+</sup> local deposition and possesses low inorganic component content, which exacerbates the growth of lithium dendrites and leads to poor battery performance. Purposefully, we fabricated the porphyrin-based covalent organic frameworks (COF-366 and COF-367) as lithium metal anode interfaces. Concretely, heterogenetic segments within COFs nodes allocate electron situations to induce component-selective catalysis, of which electron-rich nitrogen atom sites urge the N–S cleavage of bis(trifluoromethylsulfonyl)azanide (TFSI<sup>–</sup>) and C–C breakage of 1,2-dimethoxyethane (DME), while electron-deficient benzene sites facilitate the C–O cleavage of 1,3-dioxolane (DOL), constructing a rich Li<sub>2</sub>O/LiF-rich modification of COFs interface. The well-constructed interface facilitates rapid Li<sup>+</sup> migration, distributes charge evenly, and further increases the Li<sup>+</sup> flux, which achieves uniform Li<sup>+</sup> deposition and suppresses dendrite growth. Consequently, the COF-366@Li anode displayed outstanding capacity stability at a high current density of 5C after 400 cycles with a capacity of 53.37 mAh g<sup>–1</sup> (70.99%). The COF-366@Li||LFP pouch cell further validated its practical application with an impressive capacity of 120.37 mAh g<sup>–1</sup> and an excellent capacity retention of 92.42% after 43 cycles with a high cathode loading of 295.2 mg. This study demonstrates the feasibility of heterogeneity-segment of customized-type COFs to induce component-selective charge-coupling catalysis toward electrolytes and manipulate SEI inorganic components for stabilizing lithium metal anode.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"9 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695712","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}
Peng Zhang, Jinxiu Han, Xue Kong, Shaojun Liu, Yuqing Chen, Juan Li, Yuanqing Zhang, Chuanxin Wang, Lutao Du
Bacterial infections, especially drug-resistant bacterial infections, are causing increasing harm in clinical practice, and there is an urgent need to develop effective antimicrobial materials. Biomimetic DNA nanomachines have attracted much attention due to their flexible design, precise control, and high biocompatibility, but their use for bacterial inhibition has not been reported. Neutrophil extracellular traps (NETs), a network structure released by neutrophils with good bactericidal function, can be used as a superior biomimetic object for the construction of functional bacterial inhibition materials. In this study, Y-shaped DNA was polymerized using magnesium ions to develop reticulated DNA structures, which were used as templates to synthesize copper nanoclusters, leading to the construction of compositionally well-defined and simple reticulated DNA nanomachines. The nanomachine had a three-dimensional, reticular structure similar to that of NETs and especially had excellent antibacterial activity. More importantly, the NETs-imitated nanomachine had a multimodal bacterial inhibition mechanism. The nanomachine could target and localize around the bacteria and eliminate the biofilm, and then the DNA network structure effectively trapped and aggregated the bacteria and caused damage to the bacterial morphology and membrane structure; at the same time, the reticulated DNA nanomachine could also damage the bacterial membrane, causing the degradation and leakage of the proteins and the cellular contents and breakage of the DNA structure, ultimately causing irreversible inhibition of the bacteria. Importantly, the developed nanomachines with high biocompatibility could be used as antimicrobial biomaterials for the efficient treatment and healing of skin wounds infected with bacteria. This study develops a biomimetic DNA nanomachine that can be an excellent antibacterial biomaterial, which expands the application of DNA nanomachine in bacteriostatic and therapeutic fields; it is also an improved biomimetic NETs biomaterial, which brings distinctive design sources for biomimetic materials.
细菌感染，尤其是耐药细菌感染在临床上造成的危害越来越大，因此迫切需要开发有效的抗菌材料。仿生 DNA 纳米机械因其设计灵活、控制精确、生物相容性高而备受关注，但将其用于抑制细菌的研究尚未见报道。中性粒细胞胞外捕获物（NETs）是中性粒细胞释放的一种网络结构，具有良好的杀菌功能，可作为构建功能性抑菌材料的优良仿生对象。本研究利用镁离子聚合Y型DNA，形成网状DNA结构，并以此为模板合成纳米铜簇，从而构建出成分明确、结构简单的网状DNA纳米机械。该纳米机械具有与 NET 相似的三维网状结构，尤其具有出色的抗菌活性。更重要的是，仿 NET 纳米机械具有多模式抑菌机制。该纳米机械可靶向定位在细菌周围，消除生物膜，然后通过DNA网络结构有效地捕获和聚集细菌，对细菌的形态和膜结构造成破坏；同时，网状DNA纳米机械还可破坏细菌膜，使蛋白质和细胞内容物降解、渗漏，DNA结构断裂，最终对细菌造成不可逆的抑制作用。重要的是，所开发的纳米机械具有很高的生物相容性，可用作抗菌生物材料，有效治疗和愈合受细菌感染的皮肤伤口。本研究开发的生物仿生 DNA 纳米机械可作为一种优良的抗菌生物材料，拓展了 DNA 纳米机械在抑菌和治疗领域的应用；它也是一种改进的生物仿生 NETs 生物材料，为生物仿生材料带来了独特的设计来源。
{"title":"Biomimetic Synthesis of Nanomachine Inspired from Neutrophil Extracellular Traps for Multimodal Antibacterial Application","authors":"Peng Zhang, Jinxiu Han, Xue Kong, Shaojun Liu, Yuqing Chen, Juan Li, Yuanqing Zhang, Chuanxin Wang, Lutao Du","doi":"10.1021/acsnano.4c18948","DOIUrl":"https://doi.org/10.1021/acsnano.4c18948","url":null,"abstract":"Bacterial infections, especially drug-resistant bacterial infections, are causing increasing harm in clinical practice, and there is an urgent need to develop effective antimicrobial materials. Biomimetic DNA nanomachines have attracted much attention due to their flexible design, precise control, and high biocompatibility, but their use for bacterial inhibition has not been reported. Neutrophil extracellular traps (NETs), a network structure released by neutrophils with good bactericidal function, can be used as a superior biomimetic object for the construction of functional bacterial inhibition materials. In this study, <i>Y</i>-shaped DNA was polymerized using magnesium ions to develop reticulated DNA structures, which were used as templates to synthesize copper nanoclusters, leading to the construction of compositionally well-defined and simple reticulated DNA nanomachines. The nanomachine had a three-dimensional, reticular structure similar to that of NETs and especially had excellent antibacterial activity. More importantly, the NETs-imitated nanomachine had a multimodal bacterial inhibition mechanism. The nanomachine could target and localize around the bacteria and eliminate the biofilm, and then the DNA network structure effectively trapped and aggregated the bacteria and caused damage to the bacterial morphology and membrane structure; at the same time, the reticulated DNA nanomachine could also damage the bacterial membrane, causing the degradation and leakage of the proteins and the cellular contents and breakage of the DNA structure, ultimately causing irreversible inhibition of the bacteria. Importantly, the developed nanomachines with high biocompatibility could be used as antimicrobial biomaterials for the efficient treatment and healing of skin wounds infected with bacteria. This study develops a biomimetic DNA nanomachine that can be an excellent antibacterial biomaterial, which expands the application of DNA nanomachine in bacteriostatic and therapeutic fields; it is also an improved biomimetic NETs biomaterial, which brings distinctive design sources for biomimetic materials.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"21 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703444","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}
Yi Xie, Jack Morgenstein, Kameron R. Hansen, Heshan Hewa-Walpitage, Carter M. Shirley, Purusharth Amrut, Daniel Nikiforov, Kathryn Bairley, Junxiang Zhang, Naidel A. M. S. Caturello, Sasa Wang, Trigg Randall, Levi Homer, Garrett Davis, Stephen Barlow, Seth R. Marder, Zeev Valy Vardeny, John S. Colton, Volker Blum, David B. Mitzi
Hybrid perovskite dimensional engineering enables the creation of one- to three-dimensional (1D to 3D) networks of corner-sharing metal halide octahedra interspersed by organic cations, offering opportunities to tailor semiconducting properties through quantum- and dielectric-confinement effects. Beyond the discrete options, intermediate dimensionality has been introduced in the form of quasi-2D phases with inorganic layers of varying thickness. The current study extends this approach to quasi-1D lead-iodide systems with variable ribbon widths from 2 to 6 octahedra, stabilized by flexible molecular configurations, cation mixing of organic cations, or guest molecule selection. This family of quasi-1D structures adopts characteristic well-like configurations, with intraoctahedral distortion increasing from the core to the edges. First-principles density-functional theory (DFT) calculations and optical characterizations─i.e., temperature-dependent UV–visible absorption, electro-absorption, photoluminescence, and circular dichroism─collectively demonstrate lower bandgap and exciton binding energy with increased ribbon width due to tailorable quantum confinement and structural distortions. Access to two ribbon widths within a single well-ordered structure yields distinguishable bandgaps and excitonic properties, demonstrating a class of dual-quantum confinement materials within the perovskite family. Our study serves as a starting point, showcasing a paradigm to stabilize increased ribbon widths through further tuning of organic templating effects. This continuum between 2D and 1D structures offers promise for fine-tuning the dimensionality and optoelectronic properties of hybrid perovskites.
混合包晶尺寸工程能够创建由有机阳离子穿插的分角金属卤化物八面体组成的一维至三维（1D 至 3D ）网络，从而提供了通过量子和介电坍缩效应定制半导体特性的机会。除了离散选项外，还引入了具有不同厚度无机层的准 2D 相形式的中间维度。目前的研究将这种方法扩展到了具有 2 到 6 个八面体的可变带状宽度的准一维碘化铅系统，该系统通过灵活的分子构型、有机阳离子的阳离子混合或客体分子选择来稳定。该系列准一维结构采用特征性的井状构型，八面体内畸变从核心向边缘逐渐增大。第一原理密度泛函理论（DFT）计算和光学表征（即随温度变化的紫外可见吸收、电吸收、光致发光和圆二色性）共同表明，由于可定制的量子禁锢和结构畸变，随着色带宽度的增加，带隙和激子结合能也随之降低。在单一的有序结构中获得两种带宽可产生不同的带隙和激子特性，从而在过氧化物家族中展示了一类双量子约束材料。我们的研究是一个起点，展示了通过进一步调整有机模板效应来稳定增加色带宽度的范例。这种介于二维和一维结构之间的连续性为微调混合包晶的尺寸和光电特性带来了希望。
{"title":"Dimensionality-Controlled Confinement Effects for Tunable Optoelectronic Properties in Quasi-1D Hybrid Perovskites","authors":"Yi Xie, Jack Morgenstein, Kameron R. Hansen, Heshan Hewa-Walpitage, Carter M. Shirley, Purusharth Amrut, Daniel Nikiforov, Kathryn Bairley, Junxiang Zhang, Naidel A. M. S. Caturello, Sasa Wang, Trigg Randall, Levi Homer, Garrett Davis, Stephen Barlow, Seth R. Marder, Zeev Valy Vardeny, John S. Colton, Volker Blum, David B. Mitzi","doi":"10.1021/acsnano.4c16359","DOIUrl":"https://doi.org/10.1021/acsnano.4c16359","url":null,"abstract":"Hybrid perovskite dimensional engineering enables the creation of one- to three-dimensional (1D to 3D) networks of corner-sharing metal halide octahedra interspersed by organic cations, offering opportunities to tailor semiconducting properties through quantum- and dielectric-confinement effects. Beyond the discrete options, intermediate dimensionality has been introduced in the form of quasi-2D phases with inorganic layers of varying thickness. The current study extends this approach to quasi-1D lead-iodide systems with variable ribbon widths from 2 to 6 octahedra, stabilized by flexible molecular configurations, cation mixing of organic cations, or guest molecule selection. This family of quasi-1D structures adopts characteristic well-like configurations, with intraoctahedral distortion increasing from the core to the edges. First-principles density-functional theory (DFT) calculations and optical characterizations─i.e., temperature-dependent UV–visible absorption, electro-absorption, photoluminescence, and circular dichroism─collectively demonstrate lower bandgap and exciton binding energy with increased ribbon width due to tailorable quantum confinement and structural distortions. Access to two ribbon widths within a single well-ordered structure yields distinguishable bandgaps and excitonic properties, demonstrating a class of dual-quantum confinement materials within the perovskite family. Our study serves as a starting point, showcasing a paradigm to stabilize increased ribbon widths through further tuning of organic templating effects. This continuum between 2D and 1D structures offers promise for fine-tuning the dimensionality and optoelectronic properties of hybrid perovskites.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"22 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703451","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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