Two-dimensional (2D) MXenes. have emerged as promising candidates to serve as Schottky contact electrodes for the development of high-performance photodiodes owing to their extraordinary electronic properties. However, it remains a formidable challenge to fabricate large-area, uniform MXene layer for the practical device application. Here, we develop a facile route to produce large-area Ti3C2Tx layer by post-etching treatment of pulsed laser-deposited Ti3AlC2 film, enabling the in situ construction of a back-illuminated Ti3C2Tx/n-Si Schottky-barrier photodiode. Significantly, the device exhibits excellent performance with a distinctive self-filtered near-infrared (NIR) photoresponse behavior in the range of 700-1100 nm. By avoiding disturbances caused by ambient light, the NIR photodiode-based transmission-type photoplethysmographic (PPG) measurement system is capable of more reliable detection of PPG waveforms than the commercial PPG sensors for continuously monitoring the heart rate. This enables the accurate extraction of the blood pressures using a PPG-only method. Our findings not only pave the way for large-area fabrication of high-quality 2D MXene layer, but also provide a general design principle for developing high-performance MXene/Si photodiodes for health monitoring systems.
{"title":"In situ fabrication of self-filtered near-infrared Ti3C2Tx/n-Si Schottky-barrier photodiodes for continuous non-invasive photoplethysmographic system","authors":"Chen Wang, Yu Xia, Wenli Duan, Yongqiang Yu, Qingyan Yang, Jianyong Jie, Xiujuan Zhang, Jiansheng Jie","doi":"10.1039/d4nr03110e","DOIUrl":"https://doi.org/10.1039/d4nr03110e","url":null,"abstract":"Two-dimensional (2D) MXenes. have emerged as promising candidates to serve as Schottky contact electrodes for the development of high-performance photodiodes owing to their extraordinary electronic properties. However, it remains a formidable challenge to fabricate large-area, uniform MXene layer for the practical device application. Here, we develop a facile route to produce large-area Ti3C2Tx layer by post-etching treatment of pulsed laser-deposited Ti3AlC2 film, enabling the in situ construction of a back-illuminated Ti3C2Tx/n-Si Schottky-barrier photodiode. Significantly, the device exhibits excellent performance with a distinctive self-filtered near-infrared (NIR) photoresponse behavior in the range of 700-1100 nm. By avoiding disturbances caused by ambient light, the NIR photodiode-based transmission-type photoplethysmographic (PPG) measurement system is capable of more reliable detection of PPG waveforms than the commercial PPG sensors for continuously monitoring the heart rate. This enables the accurate extraction of the blood pressures using a PPG-only method. Our findings not only pave the way for large-area fabrication of high-quality 2D MXene layer, but also provide a general design principle for developing high-performance MXene/Si photodiodes for health monitoring systems.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"36 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637115","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}
Haolai Mao, Xuefeng Yang, Yonghong Shi, Tonghan Zhao, Yi Zhang, Xue Jin, Pengfei Duan, Jin Zhou
Optically active persistent luminescent materials are highly promising for anticounterfeiting applications due to their distinct luminescent features and the ability to display unique optical polarization properties. Despite significant progress in the development of circularly polarized persistent luminescence (CPPL) materials, the fabrication of upconverted circularly polarized persistent luminescence (UC-CPPL) materials remains a considerable challenge. In this study, we present an efficient strategy to construct UC-CPPL materials by embedding upconversion nanoparticles (UCNPs) and phosphors into chiral nematic liquid crystals (N*LC). The system operates through a radiative energy transfer mechanism between the UCNPs and phosphors. Upon excitation by low-energy near-infrared light (980 nm), the UCNPs emit high-energy ultraviolet light, which is effectively transferred to the phosphors, resulting in the emission of circularly polarized persistent visible light. By precisely tuning the photonic bandgap of the chiral N*LC, the UC-CPPL luminescence dissymmetry factor (gUC-CPPL) can be amplified to approximately 0.6. The concept of UC-CPPL was realized through the integration of three advanced optical properties: circularly polarized luminescence, long persistent luminescence, and upconversion luminescence. This integration enables more sophisticated and secure information encryption. The incorporation of upconversion materials facilitates the controlled concealment and selective release of encrypted information, while the multileveled encoding scheme further enhances the complexity and security of the encryption process, achieving true information hiding and encryption.
{"title":"Radiative energy transfer enabling upconverted circularly polarized persistent luminescence for multilevel information encryption","authors":"Haolai Mao, Xuefeng Yang, Yonghong Shi, Tonghan Zhao, Yi Zhang, Xue Jin, Pengfei Duan, Jin Zhou","doi":"10.1039/d4nr03819c","DOIUrl":"https://doi.org/10.1039/d4nr03819c","url":null,"abstract":"Optically active persistent luminescent materials are highly promising for anticounterfeiting applications due to their distinct luminescent features and the ability to display unique optical polarization properties. Despite significant progress in the development of circularly polarized persistent luminescence (CPPL) materials, the fabrication of upconverted circularly polarized persistent luminescence (UC-CPPL) materials remains a considerable challenge. In this study, we present an efficient strategy to construct UC-CPPL materials by embedding upconversion nanoparticles (UCNPs) and phosphors into chiral nematic liquid crystals (N*LC). The system operates through a radiative energy transfer mechanism between the UCNPs and phosphors. Upon excitation by low-energy near-infrared light (980 nm), the UCNPs emit high-energy ultraviolet light, which is effectively transferred to the phosphors, resulting in the emission of circularly polarized persistent visible light. By precisely tuning the photonic bandgap of the chiral N*LC, the UC-CPPL luminescence dissymmetry factor (gUC-CPPL) can be amplified to approximately 0.6. The concept of UC-CPPL was realized through the integration of three advanced optical properties: circularly polarized luminescence, long persistent luminescence, and upconversion luminescence. This integration enables more sophisticated and secure information encryption. The incorporation of upconversion materials facilitates the controlled concealment and selective release of encrypted information, while the multileveled encoding scheme further enhances the complexity and security of the encryption process, achieving true information hiding and encryption.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"11 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637112","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}
Shin-ichi Naya, Mio Nagamitsu, Hisashi Sugime, Tetsuro Soejima, Hiroaki Tada
Hydrogen production by proton exchange membrane water electrolysis requires the anode with low overpotential for oxygen evolution reaction (OER) and robustness in acidic solution. While exploring new electrode materials to improve the performance and durability, optimizing the morphology of typical materials using new methods is a big challenge in materials science. RuO2 is one of the most active and stable electrocatalysts, but further improvement in the performances and cost reduction must be achieved for practical use. Here we present a novel technology “metal oxide plating” that can provide maximum performances with minimum amount. A uniform single-crystal RuO2 film with thickness of ~2.5 nm by a solvothermal-post heating method at theamount (x) of only 18 μg cm−2 (ST-RuO2(18)//TiO2 NWA). OER stably proceeds on ST-RuO2(18)//TiO2 NWA with ~100% efficiency to provide mass-specific activity (MSA) of 341 A g−1catal at 1.50 V (vs. RHE) exceeding the values for most of the state-of-the-art RuO2 electrodes.
{"title":"Metal oxide plating for maximizing the performance in ruthenium(IV) oxide-catalyzed electrochemical oxygen evolution reaction","authors":"Shin-ichi Naya, Mio Nagamitsu, Hisashi Sugime, Tetsuro Soejima, Hiroaki Tada","doi":"10.1039/d4nr03678f","DOIUrl":"https://doi.org/10.1039/d4nr03678f","url":null,"abstract":"Hydrogen production by proton exchange membrane water electrolysis requires the anode with low overpotential for oxygen evolution reaction (OER) and robustness in acidic solution. While exploring new electrode materials to improve the performance and durability, optimizing the morphology of typical materials using new methods is a big challenge in materials science. RuO2 is one of the most active and stable electrocatalysts, but further improvement in the performances and cost reduction must be achieved for practical use. Here we present a novel technology “metal oxide plating” that can provide maximum performances with minimum amount. A uniform single-crystal RuO2 film with thickness of ~2.5 nm by a solvothermal-post heating method at theamount (x) of only 18 μg cm−2 (ST-RuO2(18)//TiO2 NWA). OER stably proceeds on ST-RuO2(18)//TiO2 NWA with ~100% efficiency to provide mass-specific activity (MSA) of 341 A g−1catal at 1.50 V (vs. RHE) exceeding the values for most of the state-of-the-art RuO2 electrodes.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"190 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637116","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}
Antonia Kagkoura, Shuangying Wei, Lunjie Zeng, Eva Olsson, Filipa Manuela Oliveira, Jan Luxa, Zdenek Sofer
The ongoing energy crisis has made it imperative to develop low-cost, easily fabricated, yet efficient materials. It is highly desirable for these nanomaterials to function effectively in multiple applications. Among transition metal dichalcogenides, tungsten diselenide (WSe2) shows great promise but remains understudied. In this work, we doped WSe2 with Mn using a simple hydrothermal method. The resulting material exhibited excellent electrocatalytic activity for the hydrogen evolution reaction, achieving a low overpotential of –0.28 V vs RHE at -10 mA/cm2, enhanced conductivity, and high stability and durability. Moreover, as an anode material in in lithium-ion batteries, the Mn-doped WSe2 outperformed pristine WSe2, reaching discharge and charge capacities of 1223 and 922 mAh g−1, respectively. Additionally, the Mn-doped material maintained a significantly higher discharge capacity of 201 mAh g−1 compared to intact WSe2, which had 68 mAh g−1 after 150 cycles. This work offers novel insights into designing efficient bifunctional nanomaterials using transition metal dichalcogenides.
当前的能源危机使得开发低成本、易制造、高效率的材料成为当务之急。这些纳米材料最好能在多种应用中有效发挥作用。在过渡金属二钙化物中，二硒化钨（WSe2）前景广阔，但仍未得到充分研究。在这项工作中，我们采用简单的水热法在 WSe2 中掺入了锰。由此获得的材料在氢气进化反应中表现出优异的电催化活性，在 -10 mA/cm2 的条件下，过电位低至 -0.28 V vs RHE，导电性增强，并且具有高稳定性和耐久性。此外，作为锂离子电池的阳极材料，掺锰 WSe2 的性能优于原始 WSe2，放电容量和充电容量分别达到 1223 mAh g-1 和 922 mAh g-1。此外，与完整的 WSe2 相比，掺锰材料的放电容量明显更高，达到 201 mAh g-1，而完整的 WSe2 在 150 次循环后的放电容量仅为 68 mAh g-1。这项研究为利用过渡金属二钴化物设计高效的双功能纳米材料提供了新的见解。
{"title":"Mn-doped WSe2 as an efficient electrocatalyst for hydrogen production and as anode material for lithium-ion batteries","authors":"Antonia Kagkoura, Shuangying Wei, Lunjie Zeng, Eva Olsson, Filipa Manuela Oliveira, Jan Luxa, Zdenek Sofer","doi":"10.1039/d4nr04348k","DOIUrl":"https://doi.org/10.1039/d4nr04348k","url":null,"abstract":"The ongoing energy crisis has made it imperative to develop low-cost, easily fabricated, yet efficient materials. It is highly desirable for these nanomaterials to function effectively in multiple applications. Among transition metal dichalcogenides, tungsten diselenide (WSe2) shows great promise but remains understudied. In this work, we doped WSe2 with Mn using a simple hydrothermal method. The resulting material exhibited excellent electrocatalytic activity for the hydrogen evolution reaction, achieving a low overpotential of –0.28 V vs RHE at -10 mA/cm2, enhanced conductivity, and high stability and durability. Moreover, as an anode material in in lithium-ion batteries, the Mn-doped WSe2 outperformed pristine WSe2, reaching discharge and charge capacities of 1223 and 922 mAh g−1, respectively. Additionally, the Mn-doped material maintained a significantly higher discharge capacity of 201 mAh g−1 compared to intact WSe2, which had 68 mAh g−1 after 150 cycles. This work offers novel insights into designing efficient bifunctional nanomaterials using transition metal dichalcogenides.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"109 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637114","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}
With exceptional biocompatibility and biodegradability, plant-derived materials have garnered significant interest for a myriad of biomedical applications. This minireview presents a concise overview of prevalent plant-derived materials, encompassing polysaccharide-based polymers, protein-based polymers, extracellular vesicles, mucilage, decellularized scaffolds, and the whole plant-based biomass. Through different processing techniques, these plant-derived materials can be tailored into a variety of forms, such as nanoparticles, nanofibers, and hydrogels, to address the nuanced requirements of biomedical applications. With the emphasis on wound healing, tissue engineering, and drug delivery, this review underscores the unique advantages of plant-derived materials, such as lower risk of endotoxin and virus contamination, reduced ethical concerns, scalability, and eco-friendly attributes. However, challenges such as the need for the development of standardized isolation methods of these materials, and further transition from preclinical to clinical applications still remain to be solved.
{"title":"Plant-Derived Materials for Biomedical Applications","authors":"Lele Li, Danni Zhong, Shoujie Wang, Min Zhou","doi":"10.1039/d4nr03057e","DOIUrl":"https://doi.org/10.1039/d4nr03057e","url":null,"abstract":"With exceptional biocompatibility and biodegradability, plant-derived materials have garnered significant interest for a myriad of biomedical applications. This minireview presents a concise overview of prevalent plant-derived materials, encompassing polysaccharide-based polymers, protein-based polymers, extracellular vesicles, mucilage, decellularized scaffolds, and the whole plant-based biomass. Through different processing techniques, these plant-derived materials can be tailored into a variety of forms, such as nanoparticles, nanofibers, and hydrogels, to address the nuanced requirements of biomedical applications. With the emphasis on wound healing, tissue engineering, and drug delivery, this review underscores the unique advantages of plant-derived materials, such as lower risk of endotoxin and virus contamination, reduced ethical concerns, scalability, and eco-friendly attributes. However, challenges such as the need for the development of standardized isolation methods of these materials, and further transition from preclinical to clinical applications still remain to be solved.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"13 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610456","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}
Mingshuo Tang, Zhiwei He, Yunlong Wang, Zhihao Wang
Doping fluorescent substances in polymer matrices has shown promising applications as radiation dose sensors. In this work, quinoline dye based polyvinyl chloride fibrous films with fiber diameters of 123 nm, 540 nm and 864 nm were obtained by electrostatic spinning. The introduction of the fiber film structure makes the fluorescent film dosimeter flexible and lightweight compared to normal solid fluorescent films and further extends the linear range of X-ray detection to 0-350 Gy. Furthermore, the dosimeter shows energy and dose rate independence, and the sensitivity of the dosimeter can be improved by the application of fiber films with thinner diameters. This flexible fiber membrane provides a candidate material for wearable visual dosimeters.
{"title":"Flexible and Energy Independent Fluorescence Radiation Fiber Film Dosimeter by Electrostatic Spinning","authors":"Mingshuo Tang, Zhiwei He, Yunlong Wang, Zhihao Wang","doi":"10.1039/d4nr03392b","DOIUrl":"https://doi.org/10.1039/d4nr03392b","url":null,"abstract":"Doping fluorescent substances in polymer matrices has shown promising applications as radiation dose sensors. In this work, quinoline dye based polyvinyl chloride fibrous films with fiber diameters of 123 nm, 540 nm and 864 nm were obtained by electrostatic spinning. The introduction of the fiber film structure makes the fluorescent film dosimeter flexible and lightweight compared to normal solid fluorescent films and further extends the linear range of X-ray detection to 0-350 Gy. Furthermore, the dosimeter shows energy and dose rate independence, and the sensitivity of the dosimeter can be improved by the application of fiber films with thinner diameters. This flexible fiber membrane provides a candidate material for wearable visual dosimeters.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"18 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610510","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}
The adsorption behaviors of H2 and CO molecules in crown-motif [PtAu8(PPh3)8]-H[PMo12O40] (PtAu8-PMo12) solid were investigated by in-situ quick-scan X-ray absorption fine structure (QXAFS) measurements with time resolution of 0.1 s. The electronic state of Pt in the PtAu8-PMo12 was drastically changed by the adsorptions of H2 and CO molecules because of the formation of Pt-H2/Pt-CO interactions. The H2 adsorbed more rapidly (< 0.5 s) on Pt than CO did (~2.5 s) and showed reversible adsorption/desorption behavior on Pt atoms in the PtAu8-PMo12. The rapid adsorption of H2 is due to the fast diffusion of H2, which has smaller kinetic diameter than CO, in the narrow channels between the closed voids in PtAu8-PMo12. Meanwhile, CO irreversibly adsorbed on Pt, resulting in structural isomerization to the stable “chalice-motif” PtAu8, determined by XAFS analysis and density functional theory calculations. The structural isomerization is involved by pushing ligands aside to make space for CO adsorption since the void size near Pt in the crown-motif PtAu8-PMo12 is narrower than kinetic diameter of CO.
通过时间分辨率为 0.1 秒的原位快速扫描 X 射线吸收精细结构（QXAFS）测量，研究了 H2 和 CO 分子在冠型 [PtAu8(PPh3)8]-H[PMo12O40]（PtAu8-PMo12）固体中的吸附行为。由于 Pt-H2/Pt-CO 相互作用的形成，PtAu8-PMo12 中铂的电子状态因 H2 和 CO 分子的吸附而发生了急剧变化。与 CO（约 2.5 秒）相比，H2 在铂上的吸附速度更快（< 0.5 秒），并且在 PtAu8-PMo12 中的铂原子上表现出可逆的吸附/解吸行为。H2 的快速吸附是由于 H2 在 PtAu8-PMo12 闭合空隙之间的狭窄通道中的快速扩散，而 H2 的动力学直径比 CO 小。同时，通过 XAFS 分析和密度泛函理论计算，CO 不可逆地吸附在铂上，导致结构异构化为稳定的 "茶色基团 "PtAu8。由于冠型 PtAu8-PMo12 中铂附近的空隙尺寸比 CO 的动力学直径窄，因此结构异构化是通过将配体推向一边来为 CO 的吸附腾出空间。
{"title":"In-situ QXAFS study on CO and H2 adsorption on Pt in solid [PtAu8(PPh3)8]-H[PMo12O40]","authors":"Tomoki Matsuyama, Taishi Suzuki, Yuto Oba, Soichi Kikkawa, Sayaka Uchida, Junya Ohyama, Kotaro Higashi, Takuma Kaneko, Kazuo Kato, Kiyofumi Nitta, Tomoya Uruga, Keisuke Hatada, Kazuki Yoshikawa, Amelie Heilmaier, Kosuke Suzuki, Kentaro Yonesato, Kazuya Yamaguchi, Naoki Nakatani, Hideyuki Kawasoko, Seiji Yamazoe","doi":"10.1039/d4nr03785e","DOIUrl":"https://doi.org/10.1039/d4nr03785e","url":null,"abstract":"The adsorption behaviors of H2 and CO molecules in crown-motif [PtAu8(PPh3)8]-H[PMo12O40] (PtAu8-PMo12) solid were investigated by in-situ quick-scan X-ray absorption fine structure (QXAFS) measurements with time resolution of 0.1 s. The electronic state of Pt in the PtAu8-PMo12 was drastically changed by the adsorptions of H2 and CO molecules because of the formation of Pt-H2/Pt-CO interactions. The H2 adsorbed more rapidly (< 0.5 s) on Pt than CO did (~2.5 s) and showed reversible adsorption/desorption behavior on Pt atoms in the PtAu8-PMo12. The rapid adsorption of H2 is due to the fast diffusion of H2, which has smaller kinetic diameter than CO, in the narrow channels between the closed voids in PtAu8-PMo12. Meanwhile, CO irreversibly adsorbed on Pt, resulting in structural isomerization to the stable “chalice-motif” PtAu8, determined by XAFS analysis and density functional theory calculations. The structural isomerization is involved by pushing ligands aside to make space for CO adsorption since the void size near Pt in the crown-motif PtAu8-PMo12 is narrower than kinetic diameter of CO.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"127 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610512","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}
Karina Kwapiszewska, Robert Holyst, Sakshi Sareen, Alicja kijewska
Prolonged starvation leads to acute stress, inducing a state of cellular dormancy with reduced energy consumption. Our research reveals that nutrient deprivation halts the movement of large ribosomal subunits, trapping them in a gel-like structure within the cytoplasm of surviving cells. This effect is due to water efflux from cells, causing a decrease in cell volume to half the original volume. This simple physical strategy saves, in a dormant state 107 ATP per second, which is needed for normal protein production. We monitored the diffusion of GFP (radius 2.3 nm) and 40S and 60S ribosomes (radii 3.75 and 15 nm, respectively) in the cytoplasm and nucleus during starvation of Hela cells. GFP and 40S ribosomes slowed their diffusion in the cytoplasm two and five times, respectively. 60S ribosomes exhibited only rotational diffusion. In non-starving cells, biomolecules get stuck in the gel structure of cytoplasm with sizes >100 nm. We show that the gel pore size decreased from 100 nm to 30 nm upon starvation. The diffusive transport in the cell nucleus didn't change during starvation. GFP and ribosomes had the same diffusion coefficients in non-starving and starving cells in the nucleus. This highlights the importance of nuclear transport in cancer cells during extreme stress conditions.
{"title":"Starvation induces diffusion hindrance at the nanoscale in mammalian cells","authors":"Karina Kwapiszewska, Robert Holyst, Sakshi Sareen, Alicja kijewska","doi":"10.1039/d4nr03620d","DOIUrl":"https://doi.org/10.1039/d4nr03620d","url":null,"abstract":"Prolonged starvation leads to acute stress, inducing a state of cellular dormancy with reduced energy consumption. Our research reveals that nutrient deprivation halts the movement of large ribosomal subunits, trapping them in a gel-like structure within the cytoplasm of surviving cells. This effect is due to water efflux from cells, causing a decrease in cell volume to half the original volume. This simple physical strategy saves, in a dormant state 10<small><sup>7</sup></small> ATP per second, which is needed for normal protein production. We monitored the diffusion of GFP (radius 2.3 nm) and 40S and 60S ribosomes (radii 3.75 and 15 nm, respectively) in the cytoplasm and nucleus during starvation of Hela cells. GFP and 40S ribosomes slowed their diffusion in the cytoplasm two and five times, respectively. 60S ribosomes exhibited only rotational diffusion. In non-starving cells, biomolecules get stuck in the gel structure of cytoplasm with sizes >100 nm. We show that the gel pore size decreased from 100 nm to 30 nm upon starvation. The diffusive transport in the cell nucleus didn't change during starvation. GFP and ribosomes had the same diffusion coefficients in non-starving and starving cells in the nucleus. This highlights the importance of nuclear transport in cancer cells during extreme stress conditions.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"16 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610455","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}
The reported copper nanoclusters (Cu NCs) of either CuII or CuI or mixed valence (MV) CuII/CuI or CuI/Cu0 characters are seen to be stabilized with a discrete set of ligand donors; hence, the analogues Cu NCs with a common architecture supported by same or nearly same donor set that exhibits different MV states of Cu, such as CuII/CuI and CuI/Cu0, are unknown. Such a series of highest nuclearity copper clusters supported by aromatic thiol-S donor ligands, like [(L4)12CuI15CuII(4-S)](PF6)3 (1), [(MeL4)12CuI15Cu0(4-S)]ClO4•8C7H8 (2) and [(L4)12CuI15Cu02)(DMF)](PF6)3•C2H5OH•2C7H8 (3), where, XL4 = 2-(3-X-thiophen)-2-yl-methylene)amino)-4-(trifluoromethyl)benzenethiol (X = H/Me), have been synthesized and their electronic structural properties have been examined and reported herein. The Cu16 NCs, 1 and 2, feature a central sulfido-S (Ss) bridged tetracopper, SsCu4 core inside a sphere shaped Cu12S12 truncated octahedron. As 1 and 2 has a non metal (chalogen or halogen) central atom ( here Ss) instead of a metallic Cu core inside the Cu12S12 shell, these are of inverse coordination complex (ICC) category, rather than superatomic with a core-shell (core is metal and shell is metal-ligand framework) structure. The NC 1, in presence of polar solvents converts to a two electron superatomic Cu17 NC, 3. The NC 3 features a trigonal pyramidal shaped Cu4 core inside the modified Cu12S12 i.e. Cu13S12 shell. The transformation of 1 to 3 may be visualized as the replacement of the central sulfido-S by an extra Cu atom (generated from decomposed molecules of 1) and shifting of a Cu atom of SsCu4 unit to the Cu12S12 shell, resulting Cu13S12 shell. The present work offers the first example of (i) an ICC that has Cu0 character (i.e. 2), (ii) a superatomic Cu NC (i.e. 3) stabilized by aromatic thiol-S donor ligand and (iii) the spontaneous ICC (i.e. 1) superatomic NC (i.e. 3) conversion that does not require any reducing agent rather occurs in presence of dioxygen oxidant. The probable mechanisms for the reversible 13 conversions have been discussed. The presence of Ss in 1 and 2 unveils the first evidence of the benzene thiol C-S bond clavage, to the best of our knowledge. The spectroelectrochemical studies shed light onto the choice of CuII/CuI and CuI/Cu0 character of 1 and 2 respectively which are supported by the high resolution XPS and Cu LMM Auger spectroscopy.
{"title":"Analogues Copper Nanoclusters (Cu16/17) with Two Electron Superatomic and Mixed Valence Copper(II)/Copper(I) and Copper(I)/Copper(0) Characters†","authors":"Shibaditya Kumar, Saikat Mishra, Aniruddha Das, Kuldeep Mahiya, Sourav Laha, Milan Maji, Apurba Kumar Patra","doi":"10.1039/d4nr03578j","DOIUrl":"https://doi.org/10.1039/d4nr03578j","url":null,"abstract":"The reported copper nanoclusters (Cu NCs) of either CuII or CuI or mixed valence (MV) CuII/CuI or CuI/Cu0 characters are seen to be stabilized with a discrete set of ligand donors; hence, the analogues Cu NCs with a common architecture supported by same or nearly same donor set that exhibits different MV states of Cu, such as CuII/CuI and CuI/Cu0, are unknown. Such a series of highest nuclearity copper clusters supported by aromatic thiol-S donor ligands, like [(L4)12CuI15CuII(4-S)](PF6)3 (1), [(MeL4)12CuI15Cu0(4-S)]ClO4•8C7H8 (2) and [(L4)12CuI15Cu02)(DMF)](PF6)3•C2H5OH•2C7H8 (3), where, XL4 = 2-(3-X-thiophen)-2-yl-methylene)amino)-4-(trifluoromethyl)benzenethiol (X = H/Me), have been synthesized and their electronic structural properties have been examined and reported herein. The Cu16 NCs, 1 and 2, feature a central sulfido-S (Ss) bridged tetracopper, SsCu4 core inside a sphere shaped Cu12S12 truncated octahedron. As 1 and 2 has a non metal (chalogen or halogen) central atom ( here Ss) instead of a metallic Cu core inside the Cu12S12 shell, these are of inverse coordination complex (ICC) category, rather than superatomic with a core-shell (core is metal and shell is metal-ligand framework) structure. The NC 1, in presence of polar solvents converts to a two electron superatomic Cu17 NC, 3. The NC 3 features a trigonal pyramidal shaped Cu4 core inside the modified Cu12S12 i.e. Cu13S12 shell. The transformation of 1 to 3 may be visualized as the replacement of the central sulfido-S by an extra Cu atom (generated from decomposed molecules of 1) and shifting of a Cu atom of SsCu4 unit to the Cu12S12 shell, resulting Cu13S12 shell. The present work offers the first example of (i) an ICC that has Cu0 character (i.e. 2), (ii) a superatomic Cu NC (i.e. 3) stabilized by aromatic thiol-S donor ligand and (iii) the spontaneous ICC (i.e. 1) superatomic NC (i.e. 3) conversion that does not require any reducing agent rather occurs in presence of dioxygen oxidant. The probable mechanisms for the reversible 13 conversions have been discussed. The presence of Ss in 1 and 2 unveils the first evidence of the benzene thiol C-S bond clavage, to the best of our knowledge. The spectroelectrochemical studies shed light onto the choice of CuII/CuI and CuI/Cu0 character of 1 and 2 respectively which are supported by the high resolution XPS and Cu LMM Auger spectroscopy.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"30 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610501","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}
Molybdenum disulfide (MoS2) is a highly effective visible light photocatalyst when used as well-exfoliated 2D nanosheets. The ability to make effective use these properties is significantly compromised by the challenge of preventing nanosheet aggregation or restacking in fluid suspensions. We report a strategy for immobilizing chemically exfoliated MoS2 as single and few-layer nanosheets in porous crosslinked polymers prepared as microbeads. The polymeric support prevents aggregation of the nanosheets while permitting access to the nanomaterial by model organic compounds present in a surrounding fluid. Exposure to visible light results in high degradation yields (>99%) of these organic species in aqueous media, and the MoS2 nanosheets maintained their photocatalytic efficacy through multiple cycles of use. The recoverability of the porous beads and the persistent photocatalytic activity of the polymer-supported MoS2 offer the potential of realizing an effective, environmentally sustainable platform for photocatalytic degradation of dissolved solutes.
{"title":"MoS2 nanosheets immobilized in porous microbeads as recoverable photocatalysts","authors":"Daehwan Park, Jin Woong Kim, Chinedum O. Osuji","doi":"10.1039/d4nr03492a","DOIUrl":"https://doi.org/10.1039/d4nr03492a","url":null,"abstract":"Molybdenum disulfide (MoS2) is a highly effective visible light photocatalyst when used as well-exfoliated 2D nanosheets. The ability to make effective use these properties is significantly compromised by the challenge of preventing nanosheet aggregation or restacking in fluid suspensions. We report a strategy for immobilizing chemically exfoliated MoS2 as single and few-layer nanosheets in porous crosslinked polymers prepared as microbeads. The polymeric support prevents aggregation of the nanosheets while permitting access to the nanomaterial by model organic compounds present in a surrounding fluid. Exposure to visible light results in high degradation yields (>99%) of these organic species in aqueous media, and the MoS2 nanosheets maintained their photocatalytic efficacy through multiple cycles of use. The recoverability of the porous beads and the persistent photocatalytic activity of the polymer-supported MoS2 offer the potential of realizing an effective, environmentally sustainable platform for photocatalytic degradation of dissolved solutes.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"37 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610511","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：