Conductive eutectogels have emerged as candidates for constructing functional flexible electronics as they are free from the constraints posed by inherent defects associated with solvents and feeble network structures. Nevertheless, developing a facile, environmentally friendly, and rapid polymerization strategy for the construction of conductive eutectogels with integrated multifunctionality is still immensely challenging. Herein, a conductive eutectogel is fabricated through a one-step dialdehyde xylan (DAX)/liquid metal (LM)-initiated polymerization of a deep eutectic solvent. DAX acts as a stabilizer for the preparation of LM nanodroplets and plays a crucial role in facilitating ultrafast gelation (less than 2 min) by virtue of its reducing dialdehyde groups. Notably, this fabrication strategy obviates the use of toxic chemical initiators and cross-linkers. The resultant eutectogels exhibit extremely high stretchability (2860%), desirable self-healing ability, high conductivity (0.72 S m–1), biocompatibility, excellent environmental stability, and exceptional responsiveness to tensile strain (GF = 4.08) and temperature (TCR = 5.35% K–1). Benefiting from these integrated features, the conductive eutectogels serve as multifunctional flexible sensors for human motion recognition and temperature monitoring. Furthermore, the eutectogel serves as a pliable electrode in the assembly of a triboelectric nanogenerator (TENG), designed to harvest mechanical energy, convert it into stable electrical outputs, and enable self-powered sensing. This study offers an approach to fabricating multifunctional integrated conductive eutectogels, making it a step closer to the development of intelligent flexible electronics.
{"title":"Conductive Eutectogels Fabricated by Dialdehyde Xylan/Liquid Metal-Initiated Rapid Polymerization for Multi-Response Sensors and Self-Powered Applications","authors":"Jiyou Yang, Yin Yan, Lingzhi Huang, Mingguo Ma, Mingfei Li, Feng Peng, Weiwei Huan, Jing Bian","doi":"10.1021/acsnano.4c11127","DOIUrl":"https://doi.org/10.1021/acsnano.4c11127","url":null,"abstract":"Conductive eutectogels have emerged as candidates for constructing functional flexible electronics as they are free from the constraints posed by inherent defects associated with solvents and feeble network structures. Nevertheless, developing a facile, environmentally friendly, and rapid polymerization strategy for the construction of conductive eutectogels with integrated multifunctionality is still immensely challenging. Herein, a conductive eutectogel is fabricated through a one-step dialdehyde xylan (DAX)/liquid metal (LM)-initiated polymerization of a deep eutectic solvent. DAX acts as a stabilizer for the preparation of LM nanodroplets and plays a crucial role in facilitating ultrafast gelation (less than 2 min) by virtue of its reducing dialdehyde groups. Notably, this fabrication strategy obviates the use of toxic chemical initiators and cross-linkers. The resultant eutectogels exhibit extremely high stretchability (2860%), desirable self-healing ability, high conductivity (0.72 S m<sup>–1</sup>), biocompatibility, excellent environmental stability, and exceptional responsiveness to tensile strain (GF = 4.08) and temperature (TCR = 5.35% K<sup>–1</sup>). Benefiting from these integrated features, the conductive eutectogels serve as multifunctional flexible sensors for human motion recognition and temperature monitoring. Furthermore, the eutectogel serves as a pliable electrode in the assembly of a triboelectric nanogenerator (TENG), designed to harvest mechanical energy, convert it into stable electrical outputs, and enable self-powered sensing. This study offers an approach to fabricating multifunctional integrated conductive eutectogels, making it a step closer to the development of intelligent flexible electronics.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"204 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940633","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}
Cristina Gonzàlez Gutierrez, Adrien Aimard, Martine Biarnes-Pélicot, Brigitte Kerfelec, Pierre-Henri Puech, Philippe Robert, Francesco Piazza, Patrick Chames, Laurent Limozin
Immune cell engagers are molecular agents, usually antibody-based constructs, engineered to recruit immune cells against cancer cells and kill them. They are versatile and powerful tools for cancer immunotherapy. Despite the multiplication of engagers tested and accepted in the clinic, how molecular and cellular parameters influence their actions is poorly understood. In particular, disentangling the respective roles of host immune cells and engager biophysical characteristics is needed to improve their design and efficiency. Focusing here on harnessing antibody-dependent Natural Killer cell cytotoxicity, we measure the efficiency of 6 original bispecific antibodies (bsAb), associating an anti-HER2 nanobody and an anti-CD16 nanobody. In vitro cytotoxicity data using primary human NK cells on different target cell lines exposing different antigen densities were collected, exhibiting a wide range of bsAb dose response. In order to rationalize our observations, we introduce a simple multiscale model, postulating that the density of bsAb bridging the two cells is the main parameter triggering the cytotoxic response. We introduce two microscopic parameters: the surface cooperativity describing bsAb affinity at the bridging step and the threshold of bridge density determining the donor-dependent response. Both parameters permit ranking Abs and donors and predicting bsAb potency as a function of antibodies bulk affinities and receptor surface densities on cells. Our approach thus provides a general way to decouple donor response from immune engager characteristics, rationalizing the landscape of molecule design.
{"title":"Decoupling Individual Host Response and Immune Cell Engager Cytotoxic Potency","authors":"Cristina Gonzàlez Gutierrez, Adrien Aimard, Martine Biarnes-Pélicot, Brigitte Kerfelec, Pierre-Henri Puech, Philippe Robert, Francesco Piazza, Patrick Chames, Laurent Limozin","doi":"10.1021/acsnano.4c08541","DOIUrl":"https://doi.org/10.1021/acsnano.4c08541","url":null,"abstract":"Immune cell engagers are molecular agents, usually antibody-based constructs, engineered to recruit immune cells against cancer cells and kill them. They are versatile and powerful tools for cancer immunotherapy. Despite the multiplication of engagers tested and accepted in the clinic, how molecular and cellular parameters influence their actions is poorly understood. In particular, disentangling the respective roles of host immune cells and engager biophysical characteristics is needed to improve their design and efficiency. Focusing here on harnessing antibody-dependent Natural Killer cell cytotoxicity, we measure the efficiency of 6 original bispecific antibodies (bsAb), associating an anti-HER2 nanobody and an anti-CD16 nanobody. In vitro cytotoxicity data using primary human NK cells on different target cell lines exposing different antigen densities were collected, exhibiting a wide range of bsAb dose response. In order to rationalize our observations, we introduce a simple multiscale model, postulating that the density of bsAb bridging the two cells is the main parameter triggering the cytotoxic response. We introduce two microscopic parameters: the surface cooperativity describing bsAb affinity at the bridging step and the threshold of bridge density determining the donor-dependent response. Both parameters permit ranking Abs and donors and predicting bsAb potency as a function of antibodies bulk affinities and receptor surface densities on cells. Our approach thus provides a general way to decouple donor response from immune engager characteristics, rationalizing the landscape of molecule design.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"28 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940619","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}
Yangqian Zhang, Han Liu, Fangyan Liu, Shuoxiao Zhang, Mengyuan Zhou, Yaqi Liao, Ying Wei, Weixia Dong, Tianyi Li, Chen Liu, Qi Liu, Henghui Xu, Gang Sun, Zhenbo Wang, Yang Ren, Jiayi Yang
Solid polymer electrolytes (SPEs) are promising candidates for lithium metal batteries (LMBs) owing to their safety features and compatibility with lithium metal anodes. However, the inferior ionic conductivity and electrochemical stability of SPEs hinder their application in high-voltage solid-state LMBs (HVSSLMBs). Here, a strategy is proposed to develop a dual-anion-rich solvation structure by implementing ferroelectric barium titanate (BTO) nanoparticles (NPs) and dual lithium salts into poly(vinylidene fluoride) (PVDF)-based SPEs for HVSSLMBs. The BTO NPs regulate the spatial structure of PVDF segments, enhancing the local built-in electric field in the SPEs, which, in turn, facilitates the dissolution and dissociation of lithium salts. This contributes to the dual-anion-rich solvation structure with an enhanced steric effect, which significantly improves Li+ transport kinetics and electrochemical stability. The designed PVDF-based SPE achieves a high ionic conductivity of 4.1 × 10–4 S cm–1 and a transference number of 0.70 at 25 °C. The Li//Li symmetric cells deliver an excellent critical current density of 2.4 mA cm–2 and maintain a stable Li plating/stripping process for over 5000 h. After 1000 cycles at 2C, the LiFePO4//Li cells achieve a discharge capacity of 108.3 mAh g–1. Furthermore, the LiNi0.8Co0.1Mn0.1O2 (NCM811)//Li cells present high capacity retention after 300 cycles at 1C with a cutoff voltage of 4.4 V. The NCM811/Graphite pouch batteries exhibit excellent cycling and safety performance. This work illustrates that the synergistic integration of functional nanoparticles with multiple lithium salts holds significant potential for the development of high-voltage SPEs.
{"title":"Dual-Anion-Rich Polymer Electrolytes for High-Voltage Solid-State Lithium Metal Batteries","authors":"Yangqian Zhang, Han Liu, Fangyan Liu, Shuoxiao Zhang, Mengyuan Zhou, Yaqi Liao, Ying Wei, Weixia Dong, Tianyi Li, Chen Liu, Qi Liu, Henghui Xu, Gang Sun, Zhenbo Wang, Yang Ren, Jiayi Yang","doi":"10.1021/acsnano.4c09953","DOIUrl":"https://doi.org/10.1021/acsnano.4c09953","url":null,"abstract":"Solid polymer electrolytes (SPEs) are promising candidates for lithium metal batteries (LMBs) owing to their safety features and compatibility with lithium metal anodes. However, the inferior ionic conductivity and electrochemical stability of SPEs hinder their application in high-voltage solid-state LMBs (HVSSLMBs). Here, a strategy is proposed to develop a dual-anion-rich solvation structure by implementing ferroelectric barium titanate (BTO) nanoparticles (NPs) and dual lithium salts into poly(vinylidene fluoride) (PVDF)-based SPEs for HVSSLMBs. The BTO NPs regulate the spatial structure of PVDF segments, enhancing the local built-in electric field in the SPEs, which, in turn, facilitates the dissolution and dissociation of lithium salts. This contributes to the dual-anion-rich solvation structure with an enhanced steric effect, which significantly improves Li<sup>+</sup> transport kinetics and electrochemical stability. The designed PVDF-based SPE achieves a high ionic conductivity of 4.1 × 10<sup>–4</sup> S cm<sup>–1</sup> and a transference number of 0.70 at 25 °C. The Li//Li symmetric cells deliver an excellent critical current density of 2.4 mA cm<sup>–2</sup> and maintain a stable Li plating/stripping process for over 5000 h. After 1000 cycles at 2C, the LiFePO<sub>4</sub>//Li cells achieve a discharge capacity of 108.3 mAh g<sup>–1</sup>. Furthermore, the LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> (NCM811)//Li cells present high capacity retention after 300 cycles at 1C with a cutoff voltage of 4.4 V. The NCM811/Graphite pouch batteries exhibit excellent cycling and safety performance. This work illustrates that the synergistic integration of functional nanoparticles with multiple lithium salts holds significant potential for the development of high-voltage SPEs.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"36 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961353","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}
Sheng Ma, Sisi Li, Shengyao Jiang, Lirui Wang, Dian Zhan, Manyi Xiong, Yanping Jiang, Qixian Huang, Haozhan Kui, Xinhong Li
Undifferentiated spermatogonia (Undiff-SPG) plays a critical role in maintaining continual spermatogenesis. However, the toxic effects and molecular mechanisms of maternal exposure to nanoplastics on offspring Undiff-SPG remain elusive. Here, we utilized a multiomics combined cytomorphological approach to explore the reproductive toxicity and mechanisms of polystyrene nanoplastics (PS-NPs) on offspring Undiff-SPG in mice after maternal exposure. The results indicated that PS-NPs decreased testosterone levels and reduced sperm concentration and quality in offspring male mice through maternal exposure. Moreover, PS-NPs could enter offspring Undiff-SPG, increase ROS levels, and decrease the viability of Undiff-SPG. According to the transcriptomics and proteomics analyses, PS-NPs caused offspring male mice Undiff-SPG inflammation by increasing the expression of Tnfsf18/Nlrp6. Mechanistically, we found that inflammation induced overexpression of the transcription factor Prdm14 in Undiff-SPG, which suppressed the expression of Ccdc33 and Tcirg1. Additionally, PS-NPs disrupted offspring spermatogenesis by inhibiting the Osbp2/Zcwpw1/Dhps expression. Furthermore, PS-NPs reduced the Undiff-SPG autophagic flux by reducing the expression of Igbp1/Gabarapl2. In conclusion, maternal exposure to PS-NPs caused inflammation in offspring Undiff-SPG, which resulted in Prdm14 overexpression that could disrupt spermatogenesis and normal autophagy.
{"title":"Maternal Exposure to Polystyrene Nanoplastics Disrupts Spermatogenesis in Mouse Offspring by Inducing Prdm14 Overexpression in Undifferentiated Spermatogonia","authors":"Sheng Ma, Sisi Li, Shengyao Jiang, Lirui Wang, Dian Zhan, Manyi Xiong, Yanping Jiang, Qixian Huang, Haozhan Kui, Xinhong Li","doi":"10.1021/acsnano.4c10701","DOIUrl":"https://doi.org/10.1021/acsnano.4c10701","url":null,"abstract":"Undifferentiated spermatogonia (Undiff-SPG) plays a critical role in maintaining continual spermatogenesis. However, the toxic effects and molecular mechanisms of maternal exposure to nanoplastics on offspring Undiff-SPG remain elusive. Here, we utilized a multiomics combined cytomorphological approach to explore the reproductive toxicity and mechanisms of polystyrene nanoplastics (PS-NPs) on offspring Undiff-SPG in mice after maternal exposure. The results indicated that PS-NPs decreased testosterone levels and reduced sperm concentration and quality in offspring male mice through maternal exposure. Moreover, PS-NPs could enter offspring Undiff-SPG, increase ROS levels, and decrease the viability of Undiff-SPG. According to the transcriptomics and proteomics analyses, PS-NPs caused offspring male mice Undiff-SPG inflammation by increasing the expression of <i>Tnfsf18</i>/<i>Nlrp6</i>. Mechanistically, we found that inflammation induced overexpression of the transcription factor <i>Prdm14</i> in Undiff-SPG, which suppressed the expression of <i>Ccdc33</i> and <i>Tcirg1</i>. Additionally, PS-NPs disrupted offspring spermatogenesis by inhibiting the <i>Osbp2</i>/<i>Zcwpw1</i>/<i>Dhps</i> expression. Furthermore, PS-NPs reduced the Undiff-SPG autophagic flux by reducing the expression of <i>Igbp1</i>/<i>Gabarapl2</i>. In conclusion, maternal exposure to PS-NPs caused inflammation in offspring Undiff-SPG, which resulted in <i>Prdm14</i> overexpression that could disrupt spermatogenesis and normal autophagy.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"36 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940621","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}
Thermally activated delayed fluorescence (TADF) materials have received increasing attention from organic electronics to other related fields, such as bioapplications and photocatalysts. However, it remains a challenging task for TADF emitters to showcase the versatility concurrent with high performance in multiple applications. Herein, we first present such a proof-of-concept TADF material, namely, QCN-SAC, through strategically manipulating exciton dynamics. On the one hand, QCN-SAC displays obvious aggregate-induced deep-red/near-infrared emission with a high radiative rate beyond 107 s–1, thereby demonstrating nearly 100% exciton utilization under oxygen-free conditions. In a QCN-SAC-based nondoped organic light-emitting diode (OLED), a superb external quantum efficiency of 16.4% can be reached with a peak at 708 nm. On the other hand, QCN-SAC also exhibits a high intersystem crossing rate over 108 s–1 without leveraging the heavy-atom effect, which makes QCN-SAC-based nanoparticles perform well in boosting reactive oxygen species generation for imaging-guided photodynamic therapy (PDT). This work presents a fundamental principle for designing high-performance all-in-one TADF molecules for OLED and PDT applications. This discovery holds promise for advancing the development of versatile TADF materials with a range of uses in the near future.
{"title":"Versatile Thermally Activated Delayed Fluorescence Material Enabling High Efficiencies in both Photodynamic Therapy and Deep-Red/NIR Electroluminescence","authors":"Hui Wang, Yijian Gao, Jiaxiong Chen, Xiao-Chun Fan, Yi-Zhong Shi, Jia Yu, Kai Wang, Shengliang Li, Chun-Sing Lee, Xiaohong Zhang","doi":"10.1021/acsnano.4c14129","DOIUrl":"https://doi.org/10.1021/acsnano.4c14129","url":null,"abstract":"Thermally activated delayed fluorescence (TADF) materials have received increasing attention from organic electronics to other related fields, such as bioapplications and photocatalysts. However, it remains a challenging task for TADF emitters to showcase the versatility concurrent with high performance in multiple applications. Herein, we first present such a proof-of-concept TADF material, namely, QCN-SAC, through strategically manipulating exciton dynamics. On the one hand, QCN-SAC displays obvious aggregate-induced deep-red/near-infrared emission with a high radiative rate beyond 10<sup>7</sup> s<sup>–1</sup>, thereby demonstrating nearly 100% exciton utilization under oxygen-free conditions. In a QCN-SAC-based nondoped organic light-emitting diode (OLED), a superb external quantum efficiency of 16.4% can be reached with a peak at 708 nm. On the other hand, QCN-SAC also exhibits a high intersystem crossing rate over 10<sup>8</sup> s<sup>–1</sup> without leveraging the heavy-atom effect, which makes QCN-SAC-based nanoparticles perform well in boosting reactive oxygen species generation for imaging-guided photodynamic therapy (PDT). This work presents a fundamental principle for designing high-performance all-in-one TADF molecules for OLED and PDT applications. This discovery holds promise for advancing the development of versatile TADF materials with a range of uses in the near future.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"57 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940515","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}
Hao Fu, Ziyun Zhong, Zhong Liang, Yong Jiang, Di Qiu, Mengzhen Zhang, Mengdie Jin, Zhichao Zeng, Leilei Yin, Yaping Du
The regulation of the f–f transition is the basis of utilizing the abundant optical properties of lanthanide (Ln), of which the key is to modulate the local environment of Ln ions. Here, we constructed Eu(III)-based unit-cell-sized ultrathin nanowires (UCNWs) with red luminescence and polymer-like behavior, which appears as an ideal carrier for regulating f–f transition. The f–f transition of Eu(III) in UCNWs could be precisely regulated through various ligands. It is the unusual surface states that make the UCNWs exhibit greater electric dipole strength and better sensitivity to various ligands compared with the carefully constructed ultrathin nanosheets. In addition, the possibility of regulating f–f transition in UCNWs through energy transfer and a high entropy strategy was also revealed. Finally, a temperature-dependent universal fluorescent ink was prepared based on UCNWs, which provides ideas for intelligent flexible fluorescent materials.
{"title":"Local Environment-Modulated f–f Transition in Unit-Cell-Sized Lanthanide Ultrathin Nanostructures","authors":"Hao Fu, Ziyun Zhong, Zhong Liang, Yong Jiang, Di Qiu, Mengzhen Zhang, Mengdie Jin, Zhichao Zeng, Leilei Yin, Yaping Du","doi":"10.1021/acsnano.4c11368","DOIUrl":"https://doi.org/10.1021/acsnano.4c11368","url":null,"abstract":"The regulation of the f–f transition is the basis of utilizing the abundant optical properties of lanthanide (Ln), of which the key is to modulate the local environment of Ln ions. Here, we constructed Eu(III)-based unit-cell-sized ultrathin nanowires (UCNWs) with red luminescence and polymer-like behavior, which appears as an ideal carrier for regulating f–f transition. The f–f transition of Eu(III) in UCNWs could be precisely regulated through various ligands. It is the unusual surface states that make the UCNWs exhibit greater electric dipole strength and better sensitivity to various ligands compared with the carefully constructed ultrathin nanosheets. In addition, the possibility of regulating f–f transition in UCNWs through energy transfer and a high entropy strategy was also revealed. Finally, a temperature-dependent universal fluorescent ink was prepared based on UCNWs, which provides ideas for intelligent flexible fluorescent materials.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"62 5 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940632","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}
Monolayers of transition-metal dichalcogenides, such as MoS2, have attracted significant attention for their exceptional electronic and optical properties, positioning them as ideal candidates for advanced optoelectronic applications. Despite their strong excitonic effects, the atomic-scale thickness of these materials limits their light absorption efficiency, necessitating innovative strategies to enhance light–matter interactions. Plasmonic nanostructures offer a promising solution to overcome those challenges by amplifying the electromagnetic field and also introducing other mechanisms, such as hot electron injection. In this study, we investigate the vibrational and optical properties of MoS2 monolayer deposited on gold substrates and gratings, emphasizing the role of strain and plasmonic effects using conventional spectroscopic techniques. Our results reveal significant biaxial strain in the supported regions and a uniaxial strain gradient in the suspended ones, showing a strain-induced exciton and carrier funneling effect toward the center of the nanogaps. Moreover, we observed an additional polarization-dependent doping mechanism in the suspended regions. This effect was attributed to localized surface plasmons generated within the slits, as confirmed by numerical simulations, which may decay nonradiatively into hot electrons and be injected into the monolayer. Photoluminescence measurements further demonstrated a polarization-dependent trion-to-A exciton intensity ratio, supporting the hypothesis of additional plasmon-induced doping. These findings provide a comprehensive understanding of the strain-mediated funneling effects and plasmonic interactions in hybrid MoS2/Au nanostructures, offering valuable insights for developing high-efficiency photonic devices and quantum technologies, including polarization-sensitive detectors and excitonic circuits.
{"title":"Polarization-Dependent Plasmon-Induced Doping and Strain Effects in MoS2 Monolayers on Gold Nanostructures","authors":"Matheus Fernandes Sousa Lemes, Ana Clara Sampaio Pimenta, Gaston Lozano Calderón, Marcelo A. Pereira-da-Silva, Alessandra Ames, Marcio Daldin Teodoro, Guilherme Migliato Marega, Riccardo Chiesa, Zhenyu Wang, Andras Kis, Euclydes Marega Junior","doi":"10.1021/acsnano.4c13867","DOIUrl":"https://doi.org/10.1021/acsnano.4c13867","url":null,"abstract":"Monolayers of transition-metal dichalcogenides, such as MoS<sub>2</sub>, have attracted significant attention for their exceptional electronic and optical properties, positioning them as ideal candidates for advanced optoelectronic applications. Despite their strong excitonic effects, the atomic-scale thickness of these materials limits their light absorption efficiency, necessitating innovative strategies to enhance light–matter interactions. Plasmonic nanostructures offer a promising solution to overcome those challenges by amplifying the electromagnetic field and also introducing other mechanisms, such as hot electron injection. In this study, we investigate the vibrational and optical properties of MoS<sub>2</sub> monolayer deposited on gold substrates and gratings, emphasizing the role of strain and plasmonic effects using conventional spectroscopic techniques. Our results reveal significant biaxial strain in the supported regions and a uniaxial strain gradient in the suspended ones, showing a strain-induced exciton and carrier funneling effect toward the center of the nanogaps. Moreover, we observed an additional polarization-dependent doping mechanism in the suspended regions. This effect was attributed to localized surface plasmons generated within the slits, as confirmed by numerical simulations, which may decay nonradiatively into hot electrons and be injected into the monolayer. Photoluminescence measurements further demonstrated a polarization-dependent trion-to-A exciton intensity ratio, supporting the hypothesis of additional plasmon-induced doping. These findings provide a comprehensive understanding of the strain-mediated funneling effects and plasmonic interactions in hybrid MoS<sub>2</sub>/Au nanostructures, offering valuable insights for developing high-efficiency photonic devices and quantum technologies, including polarization-sensitive detectors and excitonic circuits.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"39 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940506","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}
Christopher W. Johnson, Lizhu Zhang, Keira E. Culley, Sol Mi Oh, Douglas L. Gin, Geoffrey M. Geise, Amish J. Patel, Karen I. Winey, Chinedum O. Osuji
Ordered nanoporous polymer membranes offer opportunities for systematically probing the mechanisms of ion transport under confinement and for realizing useful materials for electrochemical devices. Here, we examine the impact of morphology and ion hydration on the transport of hydroxide and bromide anions in nanostructured polymer membranes with 1 nm scale pores. We use aqueous lyotropic self-assembly of an amphiphilic monomer, with a polymerizable surfactant to create direct hexagonal (HI) and gyroid mesophases. UV-induced cross-linking leads to the formation of nanoporous polymers with water continuous channels. The membranes are mechanically robust and chemically durable, resisting degradation during extended exposure to 1 M NaOH solutions. We use a combination of electrochemical impedance spectroscopy, pulsed-field gradient NMR spectroscopy, and molecular simulations to elucidate anion and water transport. The as-prepared hexagonal systems display higher conductivity and lower activation energies for both anions relative to the gyroid system. When compared at equivalent hydration, however, gyroid and hexagonal membranes show similar activation energies, with nearly identical conductivities at ambient temperatures. Both ionic conductivity and water diffusivity increase with increasing hydration. The water uptake as a function of relative humidity for the hexagonal and gyroid mesophases ultimately dictates the water diffusion and magnitude of the ionic conductivity, with the hexagonal system showing overall higher capacity for hydration and thus faster ion transport. The durability of these materials under aggressive alkaline conditions and their relatively high hydroxide ion conductivity suggest that these nanostructured polymers could be of interest as membranes for alkaline fuel cells.
{"title":"The Effects of Morphology and Hydration on Anion Transport in Self-Assembled Nanoporous Membranes","authors":"Christopher W. Johnson, Lizhu Zhang, Keira E. Culley, Sol Mi Oh, Douglas L. Gin, Geoffrey M. Geise, Amish J. Patel, Karen I. Winey, Chinedum O. Osuji","doi":"10.1021/acsnano.4c14234","DOIUrl":"https://doi.org/10.1021/acsnano.4c14234","url":null,"abstract":"Ordered nanoporous polymer membranes offer opportunities for systematically probing the mechanisms of ion transport under confinement and for realizing useful materials for electrochemical devices. Here, we examine the impact of morphology and ion hydration on the transport of hydroxide and bromide anions in nanostructured polymer membranes with 1 nm scale pores. We use aqueous lyotropic self-assembly of an amphiphilic monomer, with a polymerizable surfactant to create direct hexagonal (H<sub>I</sub>) and gyroid mesophases. UV-induced cross-linking leads to the formation of nanoporous polymers with water continuous channels. The membranes are mechanically robust and chemically durable, resisting degradation during extended exposure to 1 M NaOH solutions. We use a combination of electrochemical impedance spectroscopy, pulsed-field gradient NMR spectroscopy, and molecular simulations to elucidate anion and water transport. The as-prepared hexagonal systems display higher conductivity and lower activation energies for both anions relative to the gyroid system. When compared at equivalent hydration, however, gyroid and hexagonal membranes show similar activation energies, with nearly identical conductivities at ambient temperatures. Both ionic conductivity and water diffusivity increase with increasing hydration. The water uptake as a function of relative humidity for the hexagonal and gyroid mesophases ultimately dictates the water diffusion and magnitude of the ionic conductivity, with the hexagonal system showing overall higher capacity for hydration and thus faster ion transport. The durability of these materials under aggressive alkaline conditions and their relatively high hydroxide ion conductivity suggest that these nanostructured polymers could be of interest as membranes for alkaline fuel cells.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"28 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940507","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}
Zan Cui, Chenyu Shi, Ran An, Yan Tang, Yinping Li, Xueting Cao, Xukai Jiang, Chang-Cheng Liu, Min Xiao, Li Xu
Cancer vaccines utilizing nanoparticle (NP) structures that integrate antigens and adjuvants to enhance delivery and stimulate immune responses are emerging as a promising avenue in cancer immunotherapy. However, the development of cancer vaccines has been significantly hindered by the low immunogenicity of tumor antigens. To address this challenge, substantial efforts have been made in developing innovative adjuvants to elicit effective immune responses. In this study, we develop a NP cancer vaccine assisted by a polysaccharide derivative adjuvant, designed through a computational strategy, to evoke effective antigen-specific antitumor immunity. Using TLR4 as the putative receptor, we conducted a comprehensive evaluation of a prescreening library consisting of 34 inulin derivatives through docking and molecular dynamics simulation. Consequently, a new derivative, benzoylated inulin (InBz), is selected as the most promising TLR4 agonist. The adjuvant effect of InBz is evaluated by fabricating InBz NPs encapsulating the model antigen ovalbumin (OVA). In vitro, InBz-OVA NPs effectively activate the TLR4 signaling pathways and facilitate dendritic cell maturation, thereby enhancing the antigen delivery and presentation. In vivo, InBz-OVA NPs outperform a commercial aluminum-based adjuvant, elicit robust antibody titers, induce antigen-specific cytotoxic T lymphocytes, and achieve significant tumor suppression in murine models. Besides, the adjuvant effects of other representative derivatives, namely, acetylated and chloroacetylated inulin, with moderate and low potential from the library, are also chemically synthesized and experimentally evaluated and found to be in agreement with computational predictions, confirming the credibility of the strategy. This study provides an effective platform for the pursuit of efficient polysaccharide-based vaccine adjuvants.
{"title":"In Silico-Guided Discovery of Polysaccharide Derivatives as Adjuvants in Nanoparticle Vaccines for Cancer Immunotherapy","authors":"Zan Cui, Chenyu Shi, Ran An, Yan Tang, Yinping Li, Xueting Cao, Xukai Jiang, Chang-Cheng Liu, Min Xiao, Li Xu","doi":"10.1021/acsnano.4c08898","DOIUrl":"https://doi.org/10.1021/acsnano.4c08898","url":null,"abstract":"Cancer vaccines utilizing nanoparticle (NP) structures that integrate antigens and adjuvants to enhance delivery and stimulate immune responses are emerging as a promising avenue in cancer immunotherapy. However, the development of cancer vaccines has been significantly hindered by the low immunogenicity of tumor antigens. To address this challenge, substantial efforts have been made in developing innovative adjuvants to elicit effective immune responses. In this study, we develop a NP cancer vaccine assisted by a polysaccharide derivative adjuvant, designed through a computational strategy, to evoke effective antigen-specific antitumor immunity. Using TLR4 as the putative receptor, we conducted a comprehensive evaluation of a prescreening library consisting of 34 inulin derivatives through docking and molecular dynamics simulation. Consequently, a new derivative, benzoylated inulin (InBz), is selected as the most promising TLR4 agonist. The adjuvant effect of InBz is evaluated by fabricating InBz NPs encapsulating the model antigen ovalbumin (OVA). In vitro, InBz-OVA NPs effectively activate the TLR4 signaling pathways and facilitate dendritic cell maturation, thereby enhancing the antigen delivery and presentation. In vivo, InBz-OVA NPs outperform a commercial aluminum-based adjuvant, elicit robust antibody titers, induce antigen-specific cytotoxic T lymphocytes, and achieve significant tumor suppression in murine models. Besides, the adjuvant effects of other representative derivatives, namely, acetylated and chloroacetylated inulin, with moderate and low potential from the library, are also chemically synthesized and experimentally evaluated and found to be in agreement with computational predictions, confirming the credibility of the strategy. This study provides an effective platform for the pursuit of efficient polysaccharide-based vaccine adjuvants.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"36 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940631","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}
Jisoo Seok, Jae Eun Seo, Dae Kyu Lee, Joon Young Kwak, Jiwon Chang
MoS2, one of the most researched two-dimensional semiconductor materials, has great potential as the channel material in dynamic random-access memory (DRAM) due to the low leakage current inherited from the atomically thin thickness, high band gap, and heavy effective mass. In this work, we fabricate one-transistor-one-capacitor (1T1C) DRAM using chemical vapor deposition (CVD)-grown monolayer (ML) MoS2 in large area and confirm the ultralow leakage current of approximately 10–18 A/μm, significantly lower than the previous report (10–15 A/μm) in two-transistor-zero-capacitor (2T0C) DRAM based on a few-layer MoS2 flake. Through rigorous analysis of leakage current considering thermionic emission, tunneling at the source/drain, Shockley–Read–Hall recombination, and trap-assisted tunneling (TAT) current, the TAT current is identified as the primary source of leakage current. These findings highlight the potential of CVD-grown ML MoS2 to extend the retention time in DRAM and provide a deep understanding of the leakage current sources in MoS2 1T1C DRAM for further optimization to minimize the leakage current.
{"title":"Attoampere Level Leakage Current in Chemical Vapor Deposition-Grown Monolayer MoS2 Dynamic Random-Access Memory in Trap-Assisted Tunneling Limit","authors":"Jisoo Seok, Jae Eun Seo, Dae Kyu Lee, Joon Young Kwak, Jiwon Chang","doi":"10.1021/acsnano.4c13376","DOIUrl":"https://doi.org/10.1021/acsnano.4c13376","url":null,"abstract":"MoS<sub>2</sub>, one of the most researched two-dimensional semiconductor materials, has great potential as the channel material in dynamic random-access memory (DRAM) due to the low leakage current inherited from the atomically thin thickness, high band gap, and heavy effective mass. In this work, we fabricate one-transistor-one-capacitor (1T1C) DRAM using chemical vapor deposition (CVD)-grown monolayer (ML) MoS<sub>2</sub> in large area and confirm the ultralow leakage current of approximately 10<sup>–18</sup> A/μm, significantly lower than the previous report (10<sup>–15</sup> A/μm) in two-transistor-zero-capacitor (2T0C) DRAM based on a few-layer MoS<sub>2</sub> flake. Through rigorous analysis of leakage current considering thermionic emission, tunneling at the source/drain, Shockley–Read–Hall recombination, and trap-assisted tunneling (TAT) current, the TAT current is identified as the primary source of leakage current. These findings highlight the potential of CVD-grown ML MoS<sub>2</sub> to extend the retention time in DRAM and provide a deep understanding of the leakage current sources in MoS<sub>2</sub> 1T1C DRAM for further optimization to minimize the leakage current.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"15 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936931","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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