Reverse water–gas shift (RWGS) reaction is a promising strategy for the effective valorization of CO2. Because of its endothermic nature, a high-performance catalyst with high durability at high temperatures has been required. Herein, we reveal the dynamic structural changes of platinum-loaded molybdenum suboxide catalysts (Pt/MoOx) in RWGS reaction by multiple operando and in situ measurements, and the catalyst exhibits high activity and CO selectivity, as well as high stability at 500 °C due to the emergence of contiguous Mo species (Mo--Mo) and the strong metal–support interaction (SMSI) effect in MoOx. In situ X-ray absorption fine structure (XAFS) measurements demonstrated that the RWGS reaction is driven by reversible redox of in situ-formed MoOx suboxide, where the contiguous Mo--Mo species in MoOx act as activation sites for CO2. Comprehensive analysis revealed that the MoOx shell surrounding the Pt nanoparticles (NPs) suppresses CO adsorption, thereby resulting in high CO selectivity. Furthermore, the catalyst exhibited a continuous activity increase in the earlier stage of operation at 500 °C, which was attributed to the partial carburization of MoOx during the reaction and the associated increase in the electron density of the Mo species. These findings advance the understanding of RWGS reaction mechanism and suggest innovative strategies for the development of high-performance oxide catalysts with enhanced stability.
{"title":"Contiguous Mo Species and SMSI Effect in MoOx Reinforce Catalytic Performance in Reverse Water–Gas Shift Reaction","authors":"Takehiro Yamada, Yasutaka Kuwahara, Hiromi Yamashita","doi":"10.1021/acsami.4c22713","DOIUrl":"https://doi.org/10.1021/acsami.4c22713","url":null,"abstract":"Reverse water–gas shift (RWGS) reaction is a promising strategy for the effective valorization of CO<sub>2</sub>. Because of its endothermic nature, a high-performance catalyst with high durability at high temperatures has been required. Herein, we reveal the dynamic structural changes of platinum-loaded molybdenum suboxide catalysts (Pt/MoO<sub><i>x</i></sub>) in RWGS reaction by multiple <i>operando</i> and <i>in situ</i> measurements, and the catalyst exhibits high activity and CO selectivity, as well as high stability at 500 °C due to the emergence of contiguous Mo species (Mo--Mo) and the strong metal–support interaction (SMSI) effect in MoO<sub><i>x</i></sub>. <i>In situ</i> X-ray absorption fine structure (XAFS) measurements demonstrated that the RWGS reaction is driven by reversible redox of <i>in situ</i>-formed MoO<sub><i>x</i></sub> suboxide, where the contiguous Mo--Mo species in MoO<sub><i>x</i></sub> act as activation sites for CO<sub>2</sub>. Comprehensive analysis revealed that the MoO<sub><i>x</i></sub> shell surrounding the Pt nanoparticles (NPs) suppresses CO adsorption, thereby resulting in high CO selectivity. Furthermore, the catalyst exhibited a continuous activity increase in the earlier stage of operation at 500 °C, which was attributed to the partial carburization of MoO<sub><i>x</i></sub> during the reaction and the associated increase in the electron density of the Mo species. These findings advance the understanding of RWGS reaction mechanism and suggest innovative strategies for the development of high-performance oxide catalysts with enhanced stability.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"7 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Photoimmunotherapy has emerged as a promising strategy for cancer therapy due to its increased therapeutic effect, ability to reverse drug resistance, and enhanced immune activation. But there is still a lack of effective nanomaterial-based photothermal therapy (PTT) or photodynamic therapy (PDT) agents in photoimmunotherapy. In this study, photosensitizer hematoporphyrin-modified G5 PAMAM (G5-HP) nanomaterials are synthesized, which exhibit excellent photothermal conversion capability and photodynamic effects under 660 nm irradiation, effectively inducing tumor cell ablation and immunogenic cell death (ICD). Besides, ICD induced by G5-HP can generate tumor-associated antigens, thereby enhancing dendritic cell (DC) maturation and subsequent T cell activation. In addition, G5-HP polymers can bind to Toll-like receptor (TLR) agonists CpG-ODN through electrostatic interaction, forming stable G5-HP/CpG nanoparticles. The incorporation of CpG-ODN as an immunoadjuvant further amplified DC maturation, synergizing with phototherapy to strengthen antitumor immunity. Notably, in vivo studies confirmed that G5-HP/CpG nanoparticles significantly suppressed colorectal tumor growth under laser irradiation, while maintaining excellent biocompatibility. Taken together, the synthesized G5-HP polymers perform excellent PTT and PDT efficacy, and the formed G5-HP/CpG nanoparticles effectively integrate phototherapy with DC-mediated immunotherapy. This study offers a promising strategy for colorectal cancer treatment, leveraging the synergistic effects of phototherapy and immunotherapy to achieve superior antitumor outcomes.
{"title":"Hematoporphyrin-Modified Dendrimers Combined Immunoadjuvants for Enhanced Photoimmunotherapy of Colorectal Cancer","authors":"Hao Zhong, Jing Liang, Ximo Xu, Chengsheng Ding, Mengqin Yu, Naijipu Abuduaini, Jingyi Liu, Xiaohan Wang, Sen Zhang, Fei Wang, Bo Feng","doi":"10.1021/acsami.5c02413","DOIUrl":"https://doi.org/10.1021/acsami.5c02413","url":null,"abstract":"Photoimmunotherapy has emerged as a promising strategy for cancer therapy due to its increased therapeutic effect, ability to reverse drug resistance, and enhanced immune activation. But there is still a lack of effective nanomaterial-based photothermal therapy (PTT) or photodynamic therapy (PDT) agents in photoimmunotherapy. In this study, photosensitizer hematoporphyrin-modified G5 PAMAM (G5-HP) nanomaterials are synthesized, which exhibit excellent photothermal conversion capability and photodynamic effects under 660 nm irradiation, effectively inducing tumor cell ablation and immunogenic cell death (ICD). Besides, ICD induced by G5-HP can generate tumor-associated antigens, thereby enhancing dendritic cell (DC) maturation and subsequent T cell activation. In addition, G5-HP polymers can bind to Toll-like receptor (TLR) agonists CpG-ODN through electrostatic interaction, forming stable G5-HP/CpG nanoparticles. The incorporation of CpG-ODN as an immunoadjuvant further amplified DC maturation, synergizing with phototherapy to strengthen antitumor immunity. Notably, in vivo studies confirmed that G5-HP/CpG nanoparticles significantly suppressed colorectal tumor growth under laser irradiation, while maintaining excellent biocompatibility. Taken together, the synthesized G5-HP polymers perform excellent PTT and PDT efficacy, and the formed G5-HP/CpG nanoparticles effectively integrate phototherapy with DC-mediated immunotherapy. This study offers a promising strategy for colorectal cancer treatment, leveraging the synergistic effects of phototherapy and immunotherapy to achieve superior antitumor outcomes.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"45 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853148","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tsubasa Ueda, Akihiko Nemoto, Akira Ishigami, Yutaka Kobayashi, Hiroshi Ito
The study demonstrates the effectiveness of ultrahigh-pressure homogenizer (UHPH) cellulose nanofibers (CNFs) in improving the mechanical properties of poly(vinyl alcohol) (PVA) microneedle arrays (MNA). CNFs were incorporated into PVA nanocomposite films at concentrations of 0, 5, and 8 wt % using solvent casting and a nickel mold coated with a fluoropolymer was used to thermally imprint the films with MNA micropatterns at optimal mold temperatures and pressing pressure. The integration of CNFs substantially enhanced the morphological properties, surface modulus, and the accuracy of pattern replication in the nanocomposite. The augmented mechanical strength observed in the micropatterns, attributed to CNFs and subjected to UHPH treatment, can be ascribed to the physical entanglement and hydrogen bonding facilitating formation within the MNA micropattern.
{"title":"Enhancing Mechanical Durability of Water-Soluble Microneedles with Cellulose Nanofibers via Thermal Imprinting","authors":"Tsubasa Ueda, Akihiko Nemoto, Akira Ishigami, Yutaka Kobayashi, Hiroshi Ito","doi":"10.1021/acsami.5c02368","DOIUrl":"https://doi.org/10.1021/acsami.5c02368","url":null,"abstract":"The study demonstrates the effectiveness of ultrahigh-pressure homogenizer (UHPH) cellulose nanofibers (CNFs) in improving the mechanical properties of poly(vinyl alcohol) (PVA) microneedle arrays (MNA). CNFs were incorporated into PVA nanocomposite films at concentrations of 0, 5, and 8 wt % using solvent casting and a nickel mold coated with a fluoropolymer was used to thermally imprint the films with MNA micropatterns at optimal mold temperatures and pressing pressure. The integration of CNFs substantially enhanced the morphological properties, surface modulus, and the accuracy of pattern replication in the nanocomposite. The augmented mechanical strength observed in the micropatterns, attributed to CNFs and subjected to UHPH treatment, can be ascribed to the physical entanglement and hydrogen bonding facilitating formation within the MNA micropattern.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"30 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853147","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Supercapacitors are electrical energy storage devices renowned for their high power density and long cycle life. However, their low energy density has limited their broader application, particularly in electric vehicles. Carbon nanomaterials, including carbon nanotubes and graphene, are among the most promising electrode materials for enhancing energy density due to their unique structures, excellent electrical, mechanical, and thermal properties, large specific surface area, and chemical inertness in both acidic and alkaline environments. Significant progress has been made in the development of high-performance carbon-based supercapacitors. In this Review, we begin by exploring the origin and mechanisms of charge storage in supercapacitors. We then summarize the current advancements in enhancing the capacitive performance. The theory and primary strategies for designing high-performance supercapacitors are discussed to provide guidance on electrode material selection and design. Finally, future research directions and perspectives are presented with the aim of advancing the development of efficient carbon-based supercapacitors.
{"title":"Toward Rational Design of Carbon-Based Electrodes for High-Performance Supercapacitors","authors":"Chao Li, Qiuyan Yue, Yong Gao, Zhenglong Li, Jing Zhang, Mingchang Zhang, Shengnan He, Zhijun Wu, Yaxiong Yang, Jiantuo Gan, Chenchen Li, Xu Xue, Fulai Qi, Liaona She, Chao Zheng, Jian Miao, Detao Zhang, Zhenhai Xia, Hongge Pan","doi":"10.1021/acsami.4c21036","DOIUrl":"https://doi.org/10.1021/acsami.4c21036","url":null,"abstract":"Supercapacitors are electrical energy storage devices renowned for their high power density and long cycle life. However, their low energy density has limited their broader application, particularly in electric vehicles. Carbon nanomaterials, including carbon nanotubes and graphene, are among the most promising electrode materials for enhancing energy density due to their unique structures, excellent electrical, mechanical, and thermal properties, large specific surface area, and chemical inertness in both acidic and alkaline environments. Significant progress has been made in the development of high-performance carbon-based supercapacitors. In this Review, we begin by exploring the origin and mechanisms of charge storage in supercapacitors. We then summarize the current advancements in enhancing the capacitive performance. The theory and primary strategies for designing high-performance supercapacitors are discussed to provide guidance on electrode material selection and design. Finally, future research directions and perspectives are presented with the aim of advancing the development of efficient carbon-based supercapacitors.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"41 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853228","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polythiophene and its derivatives have emerged as promising candidates for next-generation electronic applications due to their tunable conductivity and ease of synthesis via electropolymerization. Although fused-ring thiophene monomers have attracted considerable interest for the fabrication of polythiophene films with enhanced electronic properties, systematic investigations comparing their conductivities and elucidating the structural influence of fused-ring motifs remain limited. In this study, we explore the electropolymerization behavior of various fused-ring thiophene monomers and systematically evaluate their conductivities through in situ electrochemical conductance measurements. Complemented by theoretical calculations of monomer aromaticity using nucleus-independent chemical shift (NICS) and multicenter bond index (MCBI) analyses, our findings reveal that the inhomogeneous aromaticity of fused thiophene rings plays a pivotal role in determining the conductivity of the resulting polythiophene films.
{"title":"Conductivity of Electropolymerized Thiophene Films: Effect of Fused-Ring Thiophenes as the Monomer","authors":"Ganlin Liu, Xiangyu Zhang, Bohan Wang, Xinyu Wang, Haichao Liu, Cheng Zhou, Bing Yang, Liang Yao, Yuguang Ma","doi":"10.1021/acsami.5c01664","DOIUrl":"https://doi.org/10.1021/acsami.5c01664","url":null,"abstract":"Polythiophene and its derivatives have emerged as promising candidates for next-generation electronic applications due to their tunable conductivity and ease of synthesis via electropolymerization. Although fused-ring thiophene monomers have attracted considerable interest for the fabrication of polythiophene films with enhanced electronic properties, systematic investigations comparing their conductivities and elucidating the structural influence of fused-ring motifs remain limited. In this study, we explore the electropolymerization behavior of various fused-ring thiophene monomers and systematically evaluate their conductivities through in situ electrochemical conductance measurements. Complemented by theoretical calculations of monomer aromaticity using nucleus-independent chemical shift (NICS) and multicenter bond index (MCBI) analyses, our findings reveal that the inhomogeneous aromaticity of fused thiophene rings plays a pivotal role in determining the conductivity of the resulting polythiophene films.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"124 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858292","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The structural modification of metal–organic frameworks (MOFs) is of vital importance in many fields, especially in sensing with enhanced performance, while the efficient synthesis of functionalized MOF nanoparticles toward small molecule detection remains challenging. Here, a general cellulose nanofibril (CNF)-induced in situ one-step strategy was proposed for the synthesis of dual-ligand-functionalized europium-based MOF (EuMOF@CNF) nanoparticles under an effective regulation of the crystallization kinetics in hydrothermal synthesis. Based on the unique dual-ligand structure, the obtained EuMOF featured a tunable antenna effect and laid a good foundation for fluorescence-sensing materials. Benefiting from the superior self-assembly properties of CNFs and the tunable antenna effect of EuMOF@CNF, flexible sensing films were constructed, showing excellent mechanical properties (72 MPa for stress and 3.8% for strain) and tunable luminescence properties and achieving instant (1 s) and sensitive fluorescence sensing of sarin analogue vapor with a significantly low limit of detection (LOD, 2.8 ppb) and robust selectivity against a wide range of common interferents (>14 types), especially independent of common acids. We believe that this pioneering design of EuMOF with tunable antenna effects would positively advance the development of high-performance MOF-based fluorescent materials and devices.
{"title":"One-Step Coordinating POPD in H3BTB-Sensitized EuMOF-Enabled Tunable Antenna Effects for Fluorescence Turn-On Sensing of Sarin Analogue Vapor","authors":"Jialong Pang, Yali Liu, Chuanfang Zhao, Jiawen Li, Mengting Ran, Baiyi Zu, Xincun Dou","doi":"10.1021/acsami.5c04451","DOIUrl":"https://doi.org/10.1021/acsami.5c04451","url":null,"abstract":"The structural modification of metal–organic frameworks (MOFs) is of vital importance in many fields, especially in sensing with enhanced performance, while the efficient synthesis of functionalized MOF nanoparticles toward small molecule detection remains challenging. Here, a general cellulose nanofibril (CNF)-induced in situ one-step strategy was proposed for the synthesis of dual-ligand-functionalized europium-based MOF (EuMOF@CNF) nanoparticles under an effective regulation of the crystallization kinetics in hydrothermal synthesis. Based on the unique dual-ligand structure, the obtained EuMOF featured a tunable antenna effect and laid a good foundation for fluorescence-sensing materials. Benefiting from the superior self-assembly properties of CNFs and the tunable antenna effect of EuMOF@CNF, flexible sensing films were constructed, showing excellent mechanical properties (72 MPa for stress and 3.8% for strain) and tunable luminescence properties and achieving instant (1 s) and sensitive fluorescence sensing of sarin analogue vapor with a significantly low limit of detection (LOD, 2.8 ppb) and robust selectivity against a wide range of common interferents (>14 types), especially independent of common acids. We believe that this pioneering design of EuMOF with tunable antenna effects would positively advance the development of high-performance MOF-based fluorescent materials and devices.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"1 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858293","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Binchen Gong, Jinquan Lei, Yue Wang, Lingfeng Chao, Qing Song, Deli Li, Mingwei An, Yang Liu, Yang Wang, Yonghua Chen
Transparent optoelectronics are crucial in modern applications, advancing display technologies in smartphones and smart windows, and supporting high-speed communication systems and advanced sensors. CH3NH3PbCl3 (MAPbCl3) has garnered significant attention due to its ideal optical bandgap and outstanding optoelectronic performance. However, the fabrication of high-quality MAPbCl3 thin films faces significant challenges, primarily due to the uncontrolled nucleation process, which results in nonuniform crystallization, poor surface coverage with numerous voids, and high roughness. In this work, we utilized methylammonium acetate (MAAc) as a solvent to form the MAPbCl3 precursor. This approach not only enables the air-processed fabrication of MAPbCl3 but also produces uniform colloidal particles, which are beneficial for the formation of compact thin films. We investigated the influence of common hole transport layers (NiOx, PTAA, PEDOT:PSS) on the crystallization of MAPbCl3 films. By synergistically controlling both the precursor and the growth substrate, we significantly improved the quality of the MAPbCl3 film. The resulting photodiode, based on the high-quality MAPbCl3 film, demonstrated potential for transparent photovoltaics and exhibited excellent performance as a photodetector. Specifically, it achieved a responsivity R of 162.5 mA/W and a detectivity (D*) of 8.9 × 1012 Jones at 390 nm, with high response speed (1.37 μs rise time and 1.68 μs fall time) even under self-powered operation (0 V). Furthermore, the device was successfully integrated into an optical communication system. These results highlight the great potential of high-quality MAPbCl3 devices in transparent optoelectronic applications.
{"title":"Synergistic Control of Organic Lead Chloride Perovskite Crystallization through the Precursor and Growth Substrate for High-Performance and Stable Transparent Optoelectronics","authors":"Binchen Gong, Jinquan Lei, Yue Wang, Lingfeng Chao, Qing Song, Deli Li, Mingwei An, Yang Liu, Yang Wang, Yonghua Chen","doi":"10.1021/acsami.5c03992","DOIUrl":"https://doi.org/10.1021/acsami.5c03992","url":null,"abstract":"Transparent optoelectronics are crucial in modern applications, advancing display technologies in smartphones and smart windows, and supporting high-speed communication systems and advanced sensors. CH<sub>3</sub>NH<sub>3</sub>PbCl<sub>3</sub> (MAPbCl<sub>3</sub>) has garnered significant attention due to its ideal optical bandgap and outstanding optoelectronic performance. However, the fabrication of high-quality MAPbCl<sub>3</sub> thin films faces significant challenges, primarily due to the uncontrolled nucleation process, which results in nonuniform crystallization, poor surface coverage with numerous voids, and high roughness. In this work, we utilized methylammonium acetate (MAAc) as a solvent to form the MAPbCl<sub>3</sub> precursor. This approach not only enables the air-processed fabrication of MAPbCl<sub>3</sub> but also produces uniform colloidal particles, which are beneficial for the formation of compact thin films. We investigated the influence of common hole transport layers (NiO<sub><i>x</i></sub>, PTAA, PEDOT:PSS) on the crystallization of MAPbCl<sub>3</sub> films. By synergistically controlling both the precursor and the growth substrate, we significantly improved the quality of the MAPbCl<sub>3</sub> film. The resulting photodiode, based on the high-quality MAPbCl<sub>3</sub> film, demonstrated potential for transparent photovoltaics and exhibited excellent performance as a photodetector. Specifically, it achieved a responsivity <i>R</i> of 162.5 mA/W and a detectivity (<i>D*</i>) of 8.9 × 10<sup>12</sup> Jones at 390 nm, with high response speed (1.37 μs rise time and 1.68 μs fall time) even under self-powered operation (0 V). Furthermore, the device was successfully integrated into an optical communication system. These results highlight the great potential of high-quality MAPbCl<sub>3</sub> devices in transparent optoelectronic applications.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"33 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853227","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aptamer-functionalized nanopipettes are an emerging class of biosensors for the label-free detection of specific molecules. While various strategies exist for immobilizing single-stranded DNA aptamers onto the inner walls of glass nanopipettes, the impact of the fabrication method on sensor sensitivity, signal change, reproducibility, and reliability remains unexplored. In this study, we compared three fabrication methods and found that sensors fabricated using gold nanoparticles (AuNPs) synthesized within the nanopipettes produced the most reproducible results while also allowing control over the modification process. In contrast, two other aptamer immobilization methods, which relied on multistep polymer coatings with aminated or thiolated aptamer coupling, were hindered by water sensitivity and uneven polymer deposition, resulting in inconsistent sensor responses. Using the AuNP-coated nanopipettes, we successfully fabricated numerous sensors of varying sizes, demonstrating that smaller nanopipettes produce greater signal changes. Sensors constructed using glass nanopipettes with diameters ranging from 22 to 30 nm exhibited large signal changes (>40%) when AuNP synthesis produced particles near the tip opening without causing blockage. However, we also observed sensors with signal changes that were significantly lower (using the same-sized glass nanopipettes), which we attributed to either minimal Au present at the tip or conversely when Au significantly blocked the probe. These results highlight the critical role of fabrication methods in maximizing the signal change, enhancing the reproducibility, and identifying how and why sensors fail. This work aims to facilitate the broader adoption of aptamer-functionalized nanopipettes in analytical sensing applications.
{"title":"Fabricating Reproducible, Reversible, and High Signal Change Aptasensors with Gold-Modified Nanopipettes","authors":"Ana B. Ramirez, Robert A. Lazenby","doi":"10.1021/acsami.4c22935","DOIUrl":"https://doi.org/10.1021/acsami.4c22935","url":null,"abstract":"Aptamer-functionalized nanopipettes are an emerging class of biosensors for the label-free detection of specific molecules. While various strategies exist for immobilizing single-stranded DNA aptamers onto the inner walls of glass nanopipettes, the impact of the fabrication method on sensor sensitivity, signal change, reproducibility, and reliability remains unexplored. In this study, we compared three fabrication methods and found that sensors fabricated using gold nanoparticles (AuNPs) synthesized within the nanopipettes produced the most reproducible results while also allowing control over the modification process. In contrast, two other aptamer immobilization methods, which relied on multistep polymer coatings with aminated or thiolated aptamer coupling, were hindered by water sensitivity and uneven polymer deposition, resulting in inconsistent sensor responses. Using the AuNP-coated nanopipettes, we successfully fabricated numerous sensors of varying sizes, demonstrating that smaller nanopipettes produce greater signal changes. Sensors constructed using glass nanopipettes with diameters ranging from 22 to 30 nm exhibited large signal changes (>40%) when AuNP synthesis produced particles near the tip opening without causing blockage. However, we also observed sensors with signal changes that were significantly lower (using the same-sized glass nanopipettes), which we attributed to either minimal Au present at the tip or conversely when Au significantly blocked the probe. These results highlight the critical role of fabrication methods in maximizing the signal change, enhancing the reproducibility, and identifying how and why sensors fail. This work aims to facilitate the broader adoption of aptamer-functionalized nanopipettes in analytical sensing applications.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"23 5 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853142","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fatemeh Motaghedi, Lina Rose, Yunyun Wu, R. Stephen Carmichael, Mohammed Jalal Ahamed, Simon Rondeau-Gagné, Tricia Breen Carmichael
Wearable pressure sensors have the potential to revolutionize healthcare and promote wellness through the detection and monitoring of vital signs and human motion. Although textiles are an ideal platform for wearable sensors due to their ubiquity in daily life, textile-based pressure sensors typically suffer from low sensitivity. Capacitive pressure sensors require a porous, deformable dielectric layer to achieve high sensitivity, and off-the-shelf textiles have not met this challenge. In this paper, we present all-textile capacitive pressure sensors based on off-the-shelf cut-pile fabrics, in which we use selective solution metallization to integrate the electrode and cut-pile dielectric layer into a single piece of fabric. The resulting sensors exhibit sensitivities (0.029 kPa–1) and response times (3 ms) suitable for monitoring motions of the human body. We demonstrate their utility to detect subtle human facial motions, as well as grip strength. Through a comparative analysis of different cut-pile fabrics, we show that the compressibility of the cut-pile layer and thus the sensitivity of the sensor depend on the specific attributes of the cut piles. This work provides not only a new approach to wearable textile-based sensor fabrication but also insight into the textile structure/performance relationships necessary to advance the field of e-textiles.
{"title":"All-Textile Wearable Capacitive Pressure Sensors Based on Cut-Pile Fabrics with Integrated Electrodes","authors":"Fatemeh Motaghedi, Lina Rose, Yunyun Wu, R. Stephen Carmichael, Mohammed Jalal Ahamed, Simon Rondeau-Gagné, Tricia Breen Carmichael","doi":"10.1021/acsami.5c01461","DOIUrl":"https://doi.org/10.1021/acsami.5c01461","url":null,"abstract":"Wearable pressure sensors have the potential to revolutionize healthcare and promote wellness through the detection and monitoring of vital signs and human motion. Although textiles are an ideal platform for wearable sensors due to their ubiquity in daily life, textile-based pressure sensors typically suffer from low sensitivity. Capacitive pressure sensors require a porous, deformable dielectric layer to achieve high sensitivity, and off-the-shelf textiles have not met this challenge. In this paper, we present all-textile capacitive pressure sensors based on off-the-shelf cut-pile fabrics, in which we use selective solution metallization to integrate the electrode and cut-pile dielectric layer into a single piece of fabric. The resulting sensors exhibit sensitivities (0.029 kPa<sup>–1</sup>) and response times (3 ms) suitable for monitoring motions of the human body. We demonstrate their utility to detect subtle human facial motions, as well as grip strength. Through a comparative analysis of different cut-pile fabrics, we show that the compressibility of the cut-pile layer and thus the sensitivity of the sensor depend on the specific attributes of the cut piles. This work provides not only a new approach to wearable textile-based sensor fabrication but also insight into the textile structure/performance relationships necessary to advance the field of e-textiles.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"10 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853146","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Improving the room temperature ionic conductivity of solid-state polymer electrolytes for lithium batteries is a big challenge. Exploring new composite polymer electrolytes is one of the important solutions. Herein, a new inorganic two-dimensional layered metal boride nanomaterial (MBene) was first applied to the polymer electrolyte. The hyperbranched cross-linking composite polymer electrolyte is prepared by free radical polymerization of double bond modified MBene and hyperbranched ether with double bonds in the presence of PVDF-HFP and lithium salt. c provided by the two-dimensional layered material and the characteristics of adsorbing lithium salt anion. As a result, the room temperature ionic conductivity of DBMBene-DBHPG-PH CPEs reaches 9.35 × 10–4 S cm–1. Combination of ATR-FTIR spectra, XANES spectra, and DFT calculation reveals the influence of MBene on ion transport. Dendrite-free growth with high reversibility can be maintained for more than 2000 h by lithium plating/stripping in lithium symmetric batteries. The solid electrolyte can be adapted to LFP and LMFP, NCM523 high-voltage cathode materials. It is worth mentioning that the assembled pouch cell also can run stably for 150 cycles at 0.1 C, showing higher cycle capacity. This work not only demonstrates a novel MBene-based composite polymer electrolyte and provides an effective strategy to prevent the aggregation of inorganic fillers in polymer electrolyte but also exhibits excellent application prospects of two-dimensional layered MBene material in solid polymer electrolyte for high-energy density solid-state lithium batteries.
{"title":"Enhancing the Ion Transport Capacity of Composite Polymer Electrolyte via Covalent-Linked Two-Dimensional Layered MBene Nanomaterial for High-Performance Solid-State Lithium Metal Batteries","authors":"Lin Chen, Luqi Zhou, Zhenfeng Li, Qinghui Zeng, Yu Liu, Yuchen Jiang, Jiazhu Guan, Honghao Wang, Yong Cao, Rongzheng Li, Yajuan Zhou, Wenping Liu, Shangtao Chen, Wei Cui, Liaoyun Zhang","doi":"10.1021/acsami.4c22346","DOIUrl":"https://doi.org/10.1021/acsami.4c22346","url":null,"abstract":"Improving the room temperature ionic conductivity of solid-state polymer electrolytes for lithium batteries is a big challenge. Exploring new composite polymer electrolytes is one of the important solutions. Herein, a new inorganic two-dimensional layered metal boride nanomaterial (MBene) was first applied to the polymer electrolyte. The hyperbranched cross-linking composite polymer electrolyte is prepared by free radical polymerization of double bond modified MBene and hyperbranched ether with double bonds in the presence of PVDF-HFP and lithium salt. c provided by the two-dimensional layered material and the characteristics of adsorbing lithium salt anion. As a result, the room temperature ionic conductivity of DBMBene-DBHPG-PH CPEs reaches 9.35 × 10<sup>–4</sup> S cm<sup>–1</sup>. Combination of ATR-FTIR spectra, XANES spectra, and DFT calculation reveals the influence of MBene on ion transport. Dendrite-free growth with high reversibility can be maintained for more than 2000 h by lithium plating/stripping in lithium symmetric batteries. The solid electrolyte can be adapted to LFP and LMFP, NCM523 high-voltage cathode materials. It is worth mentioning that the assembled pouch cell also can run stably for 150 cycles at 0.1 C, showing higher cycle capacity. This work not only demonstrates a novel MBene-based composite polymer electrolyte and provides an effective strategy to prevent the aggregation of inorganic fillers in polymer electrolyte but also exhibits excellent application prospects of two-dimensional layered MBene material in solid polymer electrolyte for high-energy density solid-state lithium batteries.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"62 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858289","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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