Pub Date : 2025-01-17DOI: 10.1021/acs.chemmater.4c03098
Mads B. Amdisen, Torben R. Jensen
Solid-state calcium batteries can potentially contribute to future renewable energy storage systems, however the discovery of electrolytes with sufficiently high Ca2+ conductivity at ambient conditions is a challenge. Here we present mechanochemical synthesis and properties of five different urea calcium tetrahydridoborate compositions as well as three crystal structures, Ca(BH4)2·xCO(NH2)2, x = 2, 4, and 6. The orthorhombic structure of Ca(BH4)2·2CO(NH2)2 consists of dinuclear molecular units, [Ca2(BH4)4(OC(NH2)2)4], with the two Ca2+ ions bridged by three urea molecules. The low symmetry monoclinic structures of Ca(BH4)2·4CO(NH2)2 and Ca(BH4)2·6CO(NH2)2 consist of [Ca(BH4)2(OC(NH2)2)4] and [Ca(OC(NH2)2)6]2+ octahedra with BH4– counterions in the later, and all three structures are held together by dihydrogen bonds. The calcium ionic conductivity reaches a maximum of σ(Ca2+) = 2.46 × 10–7 S cm–1 for the composition Ca(BH4)2–3.30CO(NH2)2 at RT, and of σ(Ca2+) = 1.23 × 10–4 S cm–1 for Ca(BH4)2–6.52CO(NH2)2 at 70 °C. Activation energies in the range 0.5 < Ea < 2.4 eV depending on the urea content and heating or cooling during measurement of ionic conductivity and an ionic transport number of Tion = 0.997 are also reported. The investigation of this series of compounds and their composites provides approaches for optimizing multiple physical phenomena that facilitate increased cationic conductivity.
{"title":"Urea Calcium Borohydrides as Ca2+ Solid-State Electrolytes","authors":"Mads B. Amdisen, Torben R. Jensen","doi":"10.1021/acs.chemmater.4c03098","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03098","url":null,"abstract":"Solid-state calcium batteries can potentially contribute to future renewable energy storage systems, however the discovery of electrolytes with sufficiently high Ca<sup>2+</sup> conductivity at ambient conditions is a challenge. Here we present mechanochemical synthesis and properties of five different urea calcium tetrahydridoborate compositions as well as three crystal structures, Ca(BH<sub>4</sub>)<sub>2</sub>·<i>x</i>CO(NH<sub>2</sub>)<sub>2</sub>, <i>x</i> = 2, 4, and 6. The orthorhombic structure of Ca(BH<sub>4</sub>)<sub>2</sub>·2CO(NH<sub>2</sub>)<sub>2</sub> consists of dinuclear molecular units, [Ca<sub>2</sub>(BH<sub>4</sub>)<sub>4</sub>(OC(NH<sub>2</sub>)<sub>2</sub>)<sub>4</sub>], with the two Ca<sup>2+</sup> ions bridged by three urea molecules. The low symmetry monoclinic structures of Ca(BH<sub>4</sub>)<sub>2</sub>·4CO(NH<sub>2</sub>)<sub>2</sub> and Ca(BH<sub>4</sub>)<sub>2</sub>·6CO(NH<sub>2</sub>)<sub>2</sub> consist of [Ca(BH<sub>4</sub>)<sub>2</sub>(OC(NH<sub>2</sub>)<sub>2</sub>)<sub>4</sub>] and [Ca(OC(NH<sub>2</sub>)<sub>2</sub>)<sub>6</sub>]<sup>2+</sup> octahedra with BH<sub>4</sub><sup>–</sup> counterions in the later, and all three structures are held together by dihydrogen bonds. The calcium ionic conductivity reaches a maximum of σ(Ca<sup>2+</sup>) = 2.46 × 10<sup>–7</sup> S cm<sup>–1</sup> for the composition Ca(BH<sub>4</sub>)<sub>2</sub>–3.30CO(NH<sub>2</sub>)<sub>2</sub> at RT, and of σ(Ca<sup>2+</sup>) = 1.23 × 10<sup>–4</sup> S cm<sup>–1</sup> for Ca(BH<sub>4</sub>)<sub>2</sub>–6.52CO(NH<sub>2</sub>)<sub>2</sub> at 70 °C. Activation energies in the range 0.5 < <i>E</i><sub>a</sub> < 2.4 eV depending on the urea content and heating or cooling during measurement of ionic conductivity and an ionic transport number of <i>T</i><sub>ion</sub> = 0.997 are also reported. The investigation of this series of compounds and their composites provides approaches for optimizing multiple physical phenomena that facilitate increased cationic conductivity.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"44 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987857","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}
Rui Ge, Xiudi Xiao, Lirong Chen, Chengyu Jiang, Youliang Nie, Yan Qing Zhu, Liuwen Zhong, Gang Xu
Self-powered electrochromic devices (SECDs) that employ metal electrodes have attracted considerable attention owing to their low voltage, low energy consumption, and ability to function independently from external power supplies; however, further research is still needed to enhance aspects such as portability, freeze resistance, and rapid responsiveness, etc. Herein, low temperature resistance and high ionic conductivity of the gel electrolyte were achieved through the mixed solvent immersion method. The highest ionic conductivity of 24.5 mS cm⁻¹ was achieved at 2 M concentration of aluminum perchlorate (Al(ClO4)3) at room temperature, and an ionic conductivity of 10.1 mS cm⁻¹ was achieved at -40°C. The device assembled by this electrolyte exhibits a coloring response time as low as 2.39 seconds at room temperature and 9.62 seconds at -40°C, with a modulation of 77.0%. Additionally, due to the inherent oxidizing properties of Al(ClO4)3, the SECDs using gel electrolytes of different components exhibited an adjustable self-bleaching response time from 29.92 min to 2.93 min after circuit disconnection. Based on excellent stability and reliability of the gel electrolyte, the SECDs can be precisely customized to function without packaging, thereby significantly advancing their applicability in low temperature environments and enabling tailored application scenarios.
{"title":"Anti-freezing polyacrylamide hydrogel electrolyte for rapid response self-powered electrochromic devices","authors":"Rui Ge, Xiudi Xiao, Lirong Chen, Chengyu Jiang, Youliang Nie, Yan Qing Zhu, Liuwen Zhong, Gang Xu","doi":"10.1039/d4ta08037h","DOIUrl":"https://doi.org/10.1039/d4ta08037h","url":null,"abstract":"Self-powered electrochromic devices (SECDs) that employ metal electrodes have attracted considerable attention owing to their low voltage, low energy consumption, and ability to function independently from external power supplies; however, further research is still needed to enhance aspects such as portability, freeze resistance, and rapid responsiveness, etc. Herein, low temperature resistance and high ionic conductivity of the gel electrolyte were achieved through the mixed solvent immersion method. The highest ionic conductivity of 24.5 mS cm⁻¹ was achieved at 2 M concentration of aluminum perchlorate (Al(ClO<small><sub>4</sub></small>)<small><sub>3</sub></small>) at room temperature, and an ionic conductivity of 10.1 mS cm⁻¹ was achieved at -40°C. The device assembled by this electrolyte exhibits a coloring response time as low as 2.39 seconds at room temperature and 9.62 seconds at -40°C, with a modulation of 77.0%. Additionally, due to the inherent oxidizing properties of Al(ClO<small><sub>4</sub></small>)<small><sub>3</sub></small>, the SECDs using gel electrolytes of different components exhibited an adjustable self-bleaching response time from 29.92 min to 2.93 min after circuit disconnection. Based on excellent stability and reliability of the gel electrolyte, the SECDs can be precisely customized to function without packaging, thereby significantly advancing their applicability in low temperature environments and enabling tailored application scenarios.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"56 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987866","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}
Pub Date : 2025-01-17DOI: 10.1016/j.jallcom.2025.178711
Sangmin Park, Yoonhyung Keum, Jaeyun Jeong, Seunghun Cha, Ju-Young Cho, Hyunchul Kim, Jiseong Lee, Taek-Soo Kim, Dae-Kyeom Kim, Myungsuk Song
Magnesium (Mg) is widely applied in various fields because of its excellent properties, such as its light weight, high oxidation efficiency and good pharmacological properties. Recently, based on the highly selective reactivities between Mg and certain rare earth elements (REEs), liquid metal extraction, which is a representative eco-friendly process for recovering REEs from permanent magnets, has been regarded as an innovative application of Mg. As an industrial paradigm is shifted to management systems that considers the sustainability of resources, the generation of stockpiled wastes from the die casting process to fabricate Mg alloys is urgently needed for application in reindustrialization. In this work, waste AZ91 alloy (Mg-aluminum (Al)-zinc (Zn)) is an extraction agent based on its ability to manipulate the reactivity of the system. Moreover, the extraction behavior of waste AZ91 is investigated via liquid metal extraction to address supply risks. The main challenge faced by REE recovery is the presence of intermetallic compounds between Al in waste AZ91 and REE in permanent magnets. Based on the different affinities between elements, the phase of Al-iron (Fe)-REE is controlled by adding the absorbing agent zirconium (Zr). Finally, the recovery efficiency of each REE is 91.2%. This value is close to that of pure Mg, and it is approximately 16% greater than that of waste Mg. It is suggested that technology for enhancing the sustainability of resources to address supply risk for circular economy is feasible. Waste resources can be used to optimize additional parameters affecting the absorbing agent.
{"title":"Manipulation of reactivity based on metallic adsorption in magnesium alloy scraps for rare-earth recycling by liquid metal extraction","authors":"Sangmin Park, Yoonhyung Keum, Jaeyun Jeong, Seunghun Cha, Ju-Young Cho, Hyunchul Kim, Jiseong Lee, Taek-Soo Kim, Dae-Kyeom Kim, Myungsuk Song","doi":"10.1016/j.jallcom.2025.178711","DOIUrl":"https://doi.org/10.1016/j.jallcom.2025.178711","url":null,"abstract":"Magnesium (Mg) is widely applied in various fields because of its excellent properties, such as its light weight, high oxidation efficiency and good pharmacological properties. Recently, based on the highly selective reactivities between Mg and certain rare earth elements (REEs), liquid metal extraction, which is a representative eco-friendly process for recovering REEs from permanent magnets, has been regarded as an innovative application of Mg. As an industrial paradigm is shifted to management systems that considers the sustainability of resources, the generation of stockpiled wastes from the die casting process to fabricate Mg alloys is urgently needed for application in reindustrialization. In this work, waste AZ91 alloy (Mg-aluminum (Al)-zinc (Zn)) is an extraction agent based on its ability to manipulate the reactivity of the system. Moreover, the extraction behavior of waste AZ91 is investigated via liquid metal extraction to address supply risks. The main challenge faced by REE recovery is the presence of intermetallic compounds between Al in waste AZ91 and REE in permanent magnets. Based on the different affinities between elements, the phase of Al-iron (Fe)-REE is controlled by adding the absorbing agent zirconium (Zr). Finally, the recovery efficiency of each REE is 91.2%. This value is close to that of pure Mg, and it is approximately 16% greater than that of waste Mg. It is suggested that technology for enhancing the sustainability of resources to address supply risk for circular economy is feasible. Waste resources can be used to optimize additional parameters affecting the absorbing agent.","PeriodicalId":344,"journal":{"name":"Journal of Alloys and Compounds","volume":"24 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988017","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}
Pub Date : 2025-01-17DOI: 10.1016/j.jallcom.2025.178681
B.D. Aparicio-Huacarpuma, C. A Vilca-Huayhua, A. Pandolfo Silveira, Sônia Nair Báo, S.W. da Silva, J.A.H. Coaquira
Polycrystalline CuO films with different thickness were successfully produced by the DC magnetron sputtering technique and subsequent thermal annealing at 500∘C in air atmosphere. The formation of the monoclinic phase was confirmed via XRD data analysis in consistency with Raman spectroscopy. Furthermore, larger residual strain was determined for the thinner film, which was assigned to the occurrence of strong tensile strain related to structural disorder likely coming from the film/substrate interface region. That resulting strain goes to relaxations as the film thickness increases. The positions of the Raman modes determined for the thinner film show a blueshift to values expected for bulk CuO as the thickness increases. Cross-sectional SEM micrographs indicate that the film thickness ranges from 256 to 1230 nm. UV-Vis spectroscopy revealed that the optical band gap and Urbach energy decreases with increasing thickness which was attributed to the relaxation of the tensile strain as the film thickness increases. Additionally, methane gas sensitivity tests at 473K revealed higher response for the thinner film, which was associated with its smaller grain size (larger surface area), which seems to be the determining parameter in order to improve the sensing response. Our obtained results suggest that CuO films are promising for gas sensing applications.
{"title":"Influence of the thickness effect on the structural, morphological, vibrational, optical, electrical and gas sensor properties of polycrystalline CuO films","authors":"B.D. Aparicio-Huacarpuma, C. A Vilca-Huayhua, A. Pandolfo Silveira, Sônia Nair Báo, S.W. da Silva, J.A.H. Coaquira","doi":"10.1016/j.jallcom.2025.178681","DOIUrl":"https://doi.org/10.1016/j.jallcom.2025.178681","url":null,"abstract":"Polycrystalline CuO films with different thickness were successfully produced by the DC magnetron sputtering technique and subsequent thermal annealing at 500<sup>∘</sup>C in air atmosphere. The formation of the monoclinic phase was confirmed via XRD data analysis in consistency with Raman spectroscopy. Furthermore, larger residual strain was determined for the thinner film, which was assigned to the occurrence of strong tensile strain related to structural disorder likely coming from the film/substrate interface region. That resulting strain goes to relaxations as the film thickness increases. The positions of the Raman modes determined for the thinner film show a blueshift to values expected for bulk CuO as the thickness increases. Cross-sectional SEM micrographs indicate that the film thickness ranges from 256 to 1230 nm. UV-Vis spectroscopy revealed that the optical band gap and Urbach energy decreases with increasing thickness which was attributed to the relaxation of the tensile strain as the film thickness increases. Additionally, methane gas sensitivity tests at 473K revealed higher response for the thinner film, which was associated with its smaller grain size (larger surface area), which seems to be the determining parameter in order to improve the sensing response. Our obtained results suggest that CuO films are promising for gas sensing applications.","PeriodicalId":344,"journal":{"name":"Journal of Alloys and Compounds","volume":"13 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988020","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}
Pub Date : 2025-01-17DOI: 10.1016/j.jallcom.2025.178707
Gehad Mohammed Subaiea, Hala H. Abd El-Gawad, Bushra Shaheen, Zeinhom M. El-Bahy, Muhammad Shahid, Muhammad Farooq Warsi
Semiconductor metal oxides are identified as excellent materials for photodegradation of pollutants due to their distinctive properties such as flexibility, adjustable electronic structure, efficient degradable ability, and high stability. Herein, we reported the tuning of optical band gap of Ni(OH)2 via a novel approach. The Ni(OH)2 confines the light absorption in Ultra Violet region. It is worth noting that gamma irradiation served as a medium to decrease the optical band gap of materials and boost their light harvesting capability. Gamma irradiation produced defects in crystal lattice improving the chemical bonding and electronic structure of transition metal oxides. This can be attributed to increase the stability of photo anodes. PL study manifested that irradiated samples decreased the carries combination and notably increase the photocatalytic efficiency. Gamma irradiation modified the structural and optical properties of Ni(OH)2 nanoparticles. Experimental results revealed that irradiated Ni(OH)2 with 60 KGy demonstrated the best photodegradation performance against both pollutants. It was noticed that gamma irradiated samples revealed enhanced photocatalytic activity as compared to pristine sample. It is concluded that gamma irradiated photocatalysts are potential candidates for efficient degradation of environmental pollutants.
{"title":"Improved Photocatalytic Efficiency of Ni(OH)2 via Gamma Irradiation: A New Approach to Optimize the Optical Parameters","authors":"Gehad Mohammed Subaiea, Hala H. Abd El-Gawad, Bushra Shaheen, Zeinhom M. El-Bahy, Muhammad Shahid, Muhammad Farooq Warsi","doi":"10.1016/j.jallcom.2025.178707","DOIUrl":"https://doi.org/10.1016/j.jallcom.2025.178707","url":null,"abstract":"Semiconductor metal oxides are identified as excellent materials for photodegradation of pollutants due to their distinctive properties such as flexibility, adjustable electronic structure, efficient degradable ability, and high stability. Herein, we reported the tuning of optical band gap of Ni(OH)<sub>2</sub> via a novel approach. The Ni(OH)<sub>2</sub> confines the light absorption in Ultra Violet region. It is worth noting that gamma irradiation served as a medium to decrease the optical band gap of materials and boost their light harvesting capability. Gamma irradiation produced defects in crystal lattice improving the chemical bonding and electronic structure of transition metal oxides. This can be attributed to increase the stability of photo anodes. PL study manifested that irradiated samples decreased the carries combination and notably increase the photocatalytic efficiency. Gamma irradiation modified the structural and optical properties of Ni(OH)<sub>2</sub> nanoparticles. Experimental results revealed that irradiated Ni(OH)<sub>2</sub> with 60 KGy demonstrated the best photodegradation performance against both pollutants. It was noticed that gamma irradiated samples revealed enhanced photocatalytic activity as compared to pristine sample. It is concluded that gamma irradiated photocatalysts are potential candidates for efficient degradation of environmental pollutants.","PeriodicalId":344,"journal":{"name":"Journal of Alloys and Compounds","volume":"38 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988021","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}
Jin Gao, Liu-Jun Yang, Guan Wang, Chen-Fan Xie, Han Yin, Hua Li, Jian-Mei Lu
Although the design of photocatalysts incorporating donor–acceptor units has garnered significant attention for its potential to enhance the efficiency of the photocatalysis process, the primary bottleneck lies in the challenge of generating long-lived charge separation states during exciton separation. Therefore, a novel Janus-nanomicelles photocatalyst is developed using carbazole (Cz) as the donor unit, perylene-3,4,9,10-tetracarboxydiimide (PDI) with long-excited state as the acceptor unit and polyethylene glycol (PEG) as the hydrophilic segment through ROMP polymerization. After optimizing the ratio, Cz19-PDI18-PEG10 rapidly adsorbs bisphenol A (BPA) within 10 s through π–π interaction, hydrogen-bonding interaction, and hydrophobic interaction between BPA and hydrophobic blocks when exposed to aqueous humor and efficiently photodegrades BPA (50 ppm) within 120 min for water purification purposes due to its long-lived charge separation state and achieving the highest reported efficiency so far. Mechanistic studies have shown that this excellent performance of Cz19-PDI18-PEG10 can be attributed to synergistic interactions between highly efficient adsorption capacity and long-lived charge separation states during photocatalysis. This novel Janus-nanomicelles design strategy holds promise as an effective candidate for water purification.
{"title":"Efficient Photocatalytic Water Purification Through Novel Janus-Nanomicelles with Long-Lived Charge Separation Properties","authors":"Jin Gao, Liu-Jun Yang, Guan Wang, Chen-Fan Xie, Han Yin, Hua Li, Jian-Mei Lu","doi":"10.1002/smll.202410805","DOIUrl":"https://doi.org/10.1002/smll.202410805","url":null,"abstract":"Although the design of photocatalysts incorporating donor–acceptor units has garnered significant attention for its potential to enhance the efficiency of the photocatalysis process, the primary bottleneck lies in the challenge of generating long-lived charge separation states during exciton separation. Therefore, a novel Janus-nanomicelles photocatalyst is developed using carbazole (Cz) as the donor unit, perylene-3,4,9,10-tetracarboxydiimide (PDI) with long-excited state as the acceptor unit and polyethylene glycol (PEG) as the hydrophilic segment through ROMP polymerization. After optimizing the ratio, Cz<sub>19</sub>-PDI<sub>18</sub>-PEG<sub>10</sub> rapidly adsorbs bisphenol A (BPA) within 10 s through <i>π</i>–<i>π</i> interaction, hydrogen-bonding interaction, and hydrophobic interaction between BPA and hydrophobic blocks when exposed to aqueous humor and efficiently photodegrades BPA (50 ppm) within 120 min for water purification purposes due to its long-lived charge separation state and achieving the highest reported efficiency so far. Mechanistic studies have shown that this excellent performance of Cz<sub>19</sub>-PDI<sub>18</sub>-PEG<sub>10</sub> can be attributed to synergistic interactions between highly efficient adsorption capacity and long-lived charge separation states during photocatalysis. This novel Janus-nanomicelles design strategy holds promise as an effective candidate for water purification.","PeriodicalId":228,"journal":{"name":"Small","volume":"30 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988112","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}
Jinzha Zhang, Mingkang Shi, Jiawen Sun, Lingxia Xu, Yuping Xu, Wentao Jiang, Wenbo Zhao, Min Zhou, Chun Mao, Shirong Zhang
The designability and high reactivity of nanotechnology provide strategies for antitumor therapy by regulating the redox state in tumor cells. Here, we synthesize a kind of vanadium dioxide nanoparticle encapsulated in bovine serum albumin and containing disulfide bonds (VSB NPs) for photothermal-enhanced ferroptosis and pyroptosis effects. Mechanism studies show that disulfide bonds can effectively consume overexpressed glutathione (GSH) in the tumor microenvironment, leading to a decrease in glutathione peroxidase 4 (GPX4) activity. Simultaneously, tetravalent vanadium can induce a catalytic reaction of overexpressed H2O2, producing plenty of toxic hydroxyl radicals (·OH) and singlet oxygen (1O2), leading to tumor cell ferroptosis. In addition, the consumption of disulfide bonds can also lead to the degradation of nanoparticles into high-valent vanadates, activating thermal protein domain-associated protein 3 (NLRP3) inflammasomes and causing tumor cell pyroptosis. It is worth mentioning that VSB NPs can not only ablate tumor cells under near-infrared light irradiation but also further disrupt the redox homeostasis of the tumor microenvironment, thereby enhancing the ferroptosis and pyroptosis of tumor cells induced by biodegradable vanadium-based nanomaterials. This strategy, based on the biological effects of vanadium to regulate the redox state in tumor cells, provides possibilities for cancer treatment.
{"title":"Biodegradable Vanadium-Based Nanomaterials for Photothermal-Enhanced Tumor Ferroptosis and Pyroptosis","authors":"Jinzha Zhang, Mingkang Shi, Jiawen Sun, Lingxia Xu, Yuping Xu, Wentao Jiang, Wenbo Zhao, Min Zhou, Chun Mao, Shirong Zhang","doi":"10.1021/acsami.4c16568","DOIUrl":"https://doi.org/10.1021/acsami.4c16568","url":null,"abstract":"The designability and high reactivity of nanotechnology provide strategies for antitumor therapy by regulating the redox state in tumor cells. Here, we synthesize a kind of vanadium dioxide nanoparticle encapsulated in bovine serum albumin and containing disulfide bonds (VSB NPs) for photothermal-enhanced ferroptosis and pyroptosis effects. Mechanism studies show that disulfide bonds can effectively consume overexpressed glutathione (GSH) in the tumor microenvironment, leading to a decrease in glutathione peroxidase 4 (GPX4) activity. Simultaneously, tetravalent vanadium can induce a catalytic reaction of overexpressed H<sub>2</sub>O<sub>2</sub>, producing plenty of toxic hydroxyl radicals (·OH) and singlet oxygen (<sup>1</sup>O<sub>2</sub>), leading to tumor cell ferroptosis. In addition, the consumption of disulfide bonds can also lead to the degradation of nanoparticles into high-valent vanadates, activating thermal protein domain-associated protein 3 (NLRP3) inflammasomes and causing tumor cell pyroptosis. It is worth mentioning that VSB NPs can not only ablate tumor cells under near-infrared light irradiation but also further disrupt the redox homeostasis of the tumor microenvironment, thereby enhancing the ferroptosis and pyroptosis of tumor cells induced by biodegradable vanadium-based nanomaterials. This strategy, based on the biological effects of vanadium to regulate the redox state in tumor cells, provides possibilities for cancer treatment.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"41 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988326","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 multiple perceptual behaviors of creatures to the highly complex world greatly benefit their survival in the cruel environment. Inspired by this, multimodal sensing materials have been expected as one of the most crucial elements to bridge artificial intelligence with reality in rapidly evolving technological competition. The well-organized integration of multiple independent stimulus responses in a single material rather than simple integration is expected to benefit the accuracy and multifunctional applications of sensing devices greatly. However, the desired multi-function coupling through elaborate nanostructure and supramolecular design still remains challenges and attracts great attention. Under the framework of nanostructure design for multimodal response, the coupling of mechanoluminescent ability and advanced stimulus-response has been reported being able to realize comprehensive perception and multifunctional applications for more complex scenarios. Herein, this mini review briefly outlines an overview about latest advances of multimodal mechanoluminescent sensors, concentrates on the nanostructure design strategy for multiple function coupling, including triboelectric compositing, supramolecular interfacial connection, and band structure modulation, etc., emphatically discusses the advantages of mechanoluminescence coupling with self-powered sensing, piezoresistive response, temperature/chemical detection, and corresponding advanced tools for heterogeneous output decoupling. Finally, the conclusions and outlooks of multimodal mechanoluminescent sensors are presented.
{"title":"Recent advances in multimodal mechanoluminescent sensors enabled by nanostructure design","authors":"Zihao Wang, Jiaman Hu, Minglin Yang, Jize Liu, Xinxing Zhang","doi":"10.1039/d4nr04875j","DOIUrl":"https://doi.org/10.1039/d4nr04875j","url":null,"abstract":"The multiple perceptual behaviors of creatures to the highly complex world greatly benefit their survival in the cruel environment. Inspired by this, multimodal sensing materials have been expected as one of the most crucial elements to bridge artificial intelligence with reality in rapidly evolving technological competition. The well-organized integration of multiple independent stimulus responses in a single material rather than simple integration is expected to benefit the accuracy and multifunctional applications of sensing devices greatly. However, the desired multi-function coupling through elaborate nanostructure and supramolecular design still remains challenges and attracts great attention. Under the framework of nanostructure design for multimodal response, the coupling of mechanoluminescent ability and advanced stimulus-response has been reported being able to realize comprehensive perception and multifunctional applications for more complex scenarios. Herein, this mini review briefly outlines an overview about latest advances of multimodal mechanoluminescent sensors, concentrates on the nanostructure design strategy for multiple function coupling, including triboelectric compositing, supramolecular interfacial connection, and band structure modulation, etc., emphatically discusses the advantages of mechanoluminescence coupling with self-powered sensing, piezoresistive response, temperature/chemical detection, and corresponding advanced tools for heterogeneous output decoupling. Finally, the conclusions and outlooks of multimodal mechanoluminescent sensors are presented.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"37 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986220","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Donguk Kim, Dayeon Lee, Wonjung Kim, Ho Jung Lee, Changwook Kim, Kwang-Hee Lee, Moonil Jung, Jee-Eun Yang, Younjin Jang, Sungjun Kim, Sangwook Kim, Dae Hwan Kim
In this study, we analyze the characteristics of fast transient drain current (ID) in IGZO-based field-effect transistors (FETs) with different composition ratios (device O: ratio of 1:1:1 for In, Ga, Zn, device G: ratio of 0.307:0.39:0.303) for reliable operations. Overshoot currents, which can cause device degradation, are caused by fast transients and are attributed to the trapping of electrons in the energy band. As the lateral electric field (Elat) of the IGZO channel is increased, the overshoot drain current difference (ΔIOS) is increased for both devices. It is also found that the increase in ΔIOS with decreasing L is less pronounced in device G compared with that for device O. While device G yields larger ΔIOS values than device O in long channels (L = 5, 10 μm), it yields smaller ΔIOS in short channels (L = 0.5, 1 μm). This phenomenon is explained using three physical parameters (nOS, Ever, and NOT), based on Technology Computer-Aided Design (TCAD) simulation modeling. Device G has stronger immunity against ΔIOS in a short-channel region; this can be attributed to the lower concentration of oxygen vacancies in device G that suppresses dopant diffusion effects within IGZO layer. These results experimentally demonstrate that the short-channel effects on fast-transient ID can be improved by controlling the Ga composition ratio of IGZO.
{"title":"Modeling of Composition and Channel Length-Dependent Transient Characteristics in Short-Channel IGZO Field-Effect Transistors","authors":"Donguk Kim, Dayeon Lee, Wonjung Kim, Ho Jung Lee, Changwook Kim, Kwang-Hee Lee, Moonil Jung, Jee-Eun Yang, Younjin Jang, Sungjun Kim, Sangwook Kim, Dae Hwan Kim","doi":"10.1021/acsami.4c17007","DOIUrl":"https://doi.org/10.1021/acsami.4c17007","url":null,"abstract":"In this study, we analyze the characteristics of fast transient drain current (<i>I</i><sub>D</sub>) in IGZO-based field-effect transistors (FETs) with different composition ratios (device O: ratio of 1:1:1 for In, Ga, Zn, device G: ratio of 0.307:0.39:0.303) for reliable operations. Overshoot currents, which can cause device degradation, are caused by fast transients and are attributed to the trapping of electrons in the energy band. As the lateral electric field (<i>E</i><sub>lat</sub>) of the IGZO channel is increased, the overshoot drain current difference (Δ<i>I</i><sub>OS</sub>) is increased for both devices. It is also found that the increase in Δ<i>I</i><sub>OS</sub> with decreasing <i>L</i> is less pronounced in device G compared with that for device O. While device G yields larger Δ<i>I</i><sub>OS</sub> values than device O in long channels (<i>L</i> = 5, 10 μm), it yields smaller Δ<i>I</i><sub>OS</sub> in short channels (<i>L</i> = 0.5, 1 μm). This phenomenon is explained using three physical parameters (<i>n</i><sub>OS</sub>, <i>E</i><sub>ver</sub>, and <i>N</i><sub>OT</sub>), based on Technology Computer-Aided Design (TCAD) simulation modeling. Device G has stronger immunity against Δ<i>I</i><sub>OS</sub> in a short-channel region; this can be attributed to the lower concentration of oxygen vacancies in device G that suppresses dopant diffusion effects within IGZO layer. These results experimentally demonstrate that the short-channel effects on fast-transient <i>I</i><sub>D</sub> can be improved by controlling the Ga composition ratio of IGZO.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"74 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986292","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}
Binge Deng, Linley Li Lin, Yan Wang, Xiangdong Bu, Jin Li, Jingsong Lu, Yaohui Wang, Yao Chen, Jian Ye
The use of dual-tracer contrast agents in clinical applications, such as sentinel lymph node (SLN) identification, offers significant advantages including enhanced accuracy, sensitivity, as well as comprehensive and multimodal visualization. In the current clinical practice, SLNs are typically marked prior to surgical resection by multiple and sequential injections of two tracers, the radioactive tracer and methylene blue (MB) dye. This imposes physical and psychological burden on patients and medical staff. Surface-enhanced Raman scattering (SERS) nanotags have emerged as promising SLN tracers due to their high sensitivity and specificity. In this study, we propose a novel single-injection composite tracer consisting of SERS nanotags and MB dye solution, to achieve the accurate intraoperative visualization and localization of SLNs. Laser excitation at the second near-infrared window (1064 nm) minimizes the MB fluorescence background interference, allowing the integration of SERS nanotags with MB solution to form the composite tracer, bridging two distinctive but complementary optical modalities. The feasibility of the composite tracer is demonstrated for SLN navigation on rabbit models. For the first time, we successfully visualize and localize multiple SLNs in the axilla of rhesus monkeys. Our study demonstrates the potential of combining MB with SERS nanotags for SLN navigation as the composite tracer, making a significant advancement toward the SLN biopsy in clinical applications.
{"title":"Single-Injection Composite Tracer Achieves Intraoperative Dual-Tracing and Precise Localization of Sentinel Lymph Nodes","authors":"Binge Deng, Linley Li Lin, Yan Wang, Xiangdong Bu, Jin Li, Jingsong Lu, Yaohui Wang, Yao Chen, Jian Ye","doi":"10.1021/acsami.4c20139","DOIUrl":"https://doi.org/10.1021/acsami.4c20139","url":null,"abstract":"The use of dual-tracer contrast agents in clinical applications, such as sentinel lymph node (SLN) identification, offers significant advantages including enhanced accuracy, sensitivity, as well as comprehensive and multimodal visualization. In the current clinical practice, SLNs are typically marked prior to surgical resection by multiple and sequential injections of two tracers, the radioactive tracer and methylene blue (MB) dye. This imposes physical and psychological burden on patients and medical staff. Surface-enhanced Raman scattering (SERS) nanotags have emerged as promising SLN tracers due to their high sensitivity and specificity. In this study, we propose a novel single-injection composite tracer consisting of SERS nanotags and MB dye solution, to achieve the accurate intraoperative visualization and localization of SLNs. Laser excitation at the second near-infrared window (1064 nm) minimizes the MB fluorescence background interference, allowing the integration of SERS nanotags with MB solution to form the composite tracer, bridging two distinctive but complementary optical modalities. The feasibility of the composite tracer is demonstrated for SLN navigation on rabbit models. For the first time, we successfully visualize and localize multiple SLNs in the axilla of rhesus monkeys. Our study demonstrates the potential of combining MB with SERS nanotags for SLN navigation as the composite tracer, making a significant advancement toward the SLN biopsy in clinical applications.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"3 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986301","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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