Ilaria Tomei, Simone Prili, Christian Petrucci, Fabrizio Arciprete, Claudio Goletti
In an article by Yang et al. (1) published in <i>ACS Nano</i>, the authors report (see Figure 3, panel d) and comment on the optical anisotropy spectrum of a chalcogenide alloy, namely, TlSe. The spectrum has been measured by a modulation optical technique there mentioned as “Azimuth-dependent reflectance difference microscopy” (ADRDM), that acquires the difference between two spectra having different and independent linearly polarized beams, modulated by a liquid crystal variable retarder. This technique is a version of reflectance anisotropy spectroscopy (RAS), (2) widely used to characterize clean surfaces in ultra high vacuum (3) and in liquid, (4) to investigate organic layers, (5) low dimensional systems, (6) and recently strain-engineered GaAsBi alloys. (7) The anisotropy spectrum reported in the article (Figure 3, panel d) is not due to the dichroism of the alloy, as instead commented by the authors: it is an artifact of the birefringence of the sample and not the result of the optical absorption of chalcogenide electronic states. Although in the paper the description of the experimental apparatus is not detailed, from the Supporting Information, it appears that reflected light after impinging on the sample surface passes again through the polarizer (see Figure S15 of ref (1)). This is more evident in another schematic diagram of the ADRDM setup, reported in the Supporting Information of a previous paper from the same group (8) (see Figure S11 of ref (8)). This configuration (with two polarizers) is the most common version of a RAS spectrometer, the so-called Aspnes version. (9) A second, rarely used version of a RAS setup (in our knowledge only two groups use also this kind of RAS spectrometer (10)) is used instead with only one polarizer (Safarov version). (10) It has been demonstrated conclusively that both versions of RAS produce the same spectra when the anisotropy in the intensity of the reflected beams is measured. (11) However, when the investigated system is birefringent (and TlSe is definitively birefringent (12)), the presence of the second polarizer (also called analyzer) produces a modulation of the light intensity that is due to the rotation of the reflected electric field and not to the absorption of the electronic states of the sample. This has been clearly demonstrated for a transparent and birefringent substrate, potassium acid phatalate (KAP): measuring an optical anisotropy spectrum in the same spectral range with (before) and without (later) an analyzer, the characteristic artifacts due to birefringence disappear completely. (13) We have then performed a new experiment on a birefringent chalcogenide sample, namely, an ordered cubic Ge<sub>2</sub>Sb<sub>2</sub>Te<sub>5</sub> alloy with (111) out of plane orientation. The 21 nm film was grown by molecular beam epitaxy (MBE) via coevaporation of ultrapure Ge, Sb, and Te on mica at a substrate temperature of 220 °C. The spectrum measured when the electric field of linearl
{"title":"Comment on “In-Plane Optical Anisotropy and Linear Dichroism in Low-Symmetry Layered TlSe”","authors":"Ilaria Tomei, Simone Prili, Christian Petrucci, Fabrizio Arciprete, Claudio Goletti","doi":"10.1021/acsnano.4c17053","DOIUrl":"https://doi.org/10.1021/acsnano.4c17053","url":null,"abstract":"In an article by Yang et al. (1) published in <i>ACS Nano</i>, the authors report (see Figure 3, panel d) and comment on the optical anisotropy spectrum of a chalcogenide alloy, namely, TlSe. The spectrum has been measured by a modulation optical technique there mentioned as “Azimuth-dependent reflectance difference microscopy” (ADRDM), that acquires the difference between two spectra having different and independent linearly polarized beams, modulated by a liquid crystal variable retarder. This technique is a version of reflectance anisotropy spectroscopy (RAS), (2) widely used to characterize clean surfaces in ultra high vacuum (3) and in liquid, (4) to investigate organic layers, (5) low dimensional systems, (6) and recently strain-engineered GaAsBi alloys. (7) The anisotropy spectrum reported in the article (Figure 3, panel d) is not due to the dichroism of the alloy, as instead commented by the authors: it is an artifact of the birefringence of the sample and not the result of the optical absorption of chalcogenide electronic states. Although in the paper the description of the experimental apparatus is not detailed, from the Supporting Information, it appears that reflected light after impinging on the sample surface passes again through the polarizer (see Figure S15 of ref (1)). This is more evident in another schematic diagram of the ADRDM setup, reported in the Supporting Information of a previous paper from the same group (8) (see Figure S11 of ref (8)). This configuration (with two polarizers) is the most common version of a RAS spectrometer, the so-called Aspnes version. (9) A second, rarely used version of a RAS setup (in our knowledge only two groups use also this kind of RAS spectrometer (10)) is used instead with only one polarizer (Safarov version). (10) It has been demonstrated conclusively that both versions of RAS produce the same spectra when the anisotropy in the intensity of the reflected beams is measured. (11) However, when the investigated system is birefringent (and TlSe is definitively birefringent (12)), the presence of the second polarizer (also called analyzer) produces a modulation of the light intensity that is due to the rotation of the reflected electric field and not to the absorption of the electronic states of the sample. This has been clearly demonstrated for a transparent and birefringent substrate, potassium acid phatalate (KAP): measuring an optical anisotropy spectrum in the same spectral range with (before) and without (later) an analyzer, the characteristic artifacts due to birefringence disappear completely. (13) We have then performed a new experiment on a birefringent chalcogenide sample, namely, an ordered cubic Ge<sub>2</sub>Sb<sub>2</sub>Te<sub>5</sub> alloy with (111) out of plane orientation. The 21 nm film was grown by molecular beam epitaxy (MBE) via coevaporation of ultrapure Ge, Sb, and Te on mica at a substrate temperature of 220 °C. The spectrum measured when the electric field of linearl","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"1 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857216","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}
Solar-driven interfacial evaporation (SDIE) has emerged as an efficient approach for sustainable freshwater generation, with current research predominantly focusing on photothermal materials and evaporator configurations. However, there is less attention from a practical engineering perspective for SDIE applications in extreme environments or industrial requirements, such as strong acids, alkalis, and high-salinity wastewater. Herein, we propose a one-dimensional (1D) MAX phase-based photothermal evaporator that combines exceptional solar-thermal conversion efficiency with high chemical stability, enabling efficient solar energy conversion to produce freshwater in various extreme environments. The engineered Ti2AlSnC nanofiber membrane evaporator demonstrates a continuous 30-day operation in concentrated acids (pH < 1) while maintaining a stable evaporation rate of 2.8 kg m–2 h–1. Furthermore, the integrated Joule heating module enables all-day operation under low-light conditions with a minimal energy input (≤3 V). The development of such a material establishes a promising strategy for more practical and durable water treatment solutions to harsh environments.
{"title":"Nanofiber Membranes Comprising Mn+1AXn Phases as the Basis of Durable Photothermal Evaporators in Extreme Environments","authors":"Yuting Li, Xiang Liu, Mingxue Xiang, Qinhuan Wang, Yu Zhang, Yu Wang","doi":"10.1021/acsnano.5c03189","DOIUrl":"https://doi.org/10.1021/acsnano.5c03189","url":null,"abstract":"Solar-driven interfacial evaporation (SDIE) has emerged as an efficient approach for sustainable freshwater generation, with current research predominantly focusing on photothermal materials and evaporator configurations. However, there is less attention from a practical engineering perspective for SDIE applications in extreme environments or industrial requirements, such as strong acids, alkalis, and high-salinity wastewater. Herein, we propose a one-dimensional (1D) MAX phase-based photothermal evaporator that combines exceptional solar-thermal conversion efficiency with high chemical stability, enabling efficient solar energy conversion to produce freshwater in various extreme environments. The engineered Ti<sub>2</sub>AlSnC nanofiber membrane evaporator demonstrates a continuous 30-day operation in concentrated acids (pH < 1) while maintaining a stable evaporation rate of 2.8 kg m<sup>–2</sup> h<sup>–1</sup>. Furthermore, the integrated Joule heating module enables all-day operation under low-light conditions with a minimal energy input (≤3 V). The development of such a material establishes a promising strategy for more practical and durable water treatment solutions to harsh environments.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"24 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862632","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}
Yuqi Guo, Yingqian Chen, Gwendolyn J. H. Lim, Siyu Zhu, Yulia Lekina, Yi Cai, Vivek Verma, Kwok Kiong Chan, J. J. Nicholas Lim, Ernest Jun Jie Tang, Pinit Kidkhunthod, Ming Wah Wong, Yizhong Huang, Ze Xiang Shen, Madhavi Srinivasan
Aqueous sulfur batteries are promising for high-performance and low-cost energy storage. However, their energy density is limited by low battery voltages due to the negative potential [E0 = −0.51 V vs standard hydrogen electrode (SHE)] of low valent sulfur redox (S0/S2–) and low discharge capacity (∼300 mA h g–1) of high valent sulfur redox (S2O32–/S4O62– or S4+/S0). Herein, we develop a reversible alkaline sulfur cathode via introducing Cu2+ and Zn2+ ion mediators, exhibiting a redox potential above 0 V vs SHE, which is higher than low valent sulfur redox and high specific capacity of 1340 mA h g–1. Furthermore, the proposed rechargeable alkaline sulfur batteries achieve a high operating battery voltage of approximately 1.1 V and rapid reaction kinetics, sustained even at high current densities of up to 10 A g–1. In-depth characterization and DFT calculations reveal that the alkaline sulfur electrochemistry follows a six-electron conversion reaction S ↔ CuS ↔ ZnS + Cu2O ↔ Cu, delivering an energy density of 1168 W h kg–1 and a power density of 8110 W kg–1. This work offers insights into aqueous sulfur electrochemistry and shows an alternative to achieving high energy density aqueous batteries.
水硫电池有望实现高性能、低成本的能量存储。然而，由于低价硫氧化还原（S0/S2-）的负电位[与标准氢电极（SHE）相比，E0 = -0.51 V]和高价硫氧化还原（S2O32-/S4O62-或 S4+/S0）的低放电容量（∼300 mA h g-1），它们的能量密度受到低电池电压的限制。在此，我们通过引入 Cu2+ 和 Zn2+ 离子介质，开发出一种可逆的碱性硫阴极，其氧化还原电位高于 0 V vs SHE，高于低价硫氧化还原电位，比容量高达 1340 mA h g-1。此外，所提出的可充电碱性硫电池的工作电压高达约 1.1 V，反应动力学迅速，即使在高达 10 A g-1 的高电流密度下也能保持稳定。深入表征和 DFT 计算显示，碱性硫电化学遵循六电子转换反应 S ↔ CuS ↔ ZnS + Cu2O ↔ Cu，能量密度为 1168 W h kg-1，功率密度为 8110 W kg-1。这项研究为水性硫电化学提供了新的见解，并为实现高能量密度水性电池提供了新的选择。
{"title":"Reversible Alkaline Sulfur Cathode Based on Six-Electron Electrochemistry for Advanced Aqueous Sulfur Batteries","authors":"Yuqi Guo, Yingqian Chen, Gwendolyn J. H. Lim, Siyu Zhu, Yulia Lekina, Yi Cai, Vivek Verma, Kwok Kiong Chan, J. J. Nicholas Lim, Ernest Jun Jie Tang, Pinit Kidkhunthod, Ming Wah Wong, Yizhong Huang, Ze Xiang Shen, Madhavi Srinivasan","doi":"10.1021/acsnano.4c16835","DOIUrl":"https://doi.org/10.1021/acsnano.4c16835","url":null,"abstract":"Aqueous sulfur batteries are promising for high-performance and low-cost energy storage. However, their energy density is limited by low battery voltages due to the negative potential [<i>E</i><sup>0</sup> = −0.51 V vs standard hydrogen electrode (SHE)] of low valent sulfur redox (S<sup>0</sup>/S<sup>2–</sup>) and low discharge capacity (∼300 mA h g<sup>–1</sup>) of high valent sulfur redox (S<sub>2</sub>O<sub>3</sub><sup>2–</sup>/S<sub>4</sub>O<sub>6</sub><sup>2–</sup> or S<sup>4+</sup>/S<sup>0</sup>). Herein, we develop a reversible alkaline sulfur cathode via introducing Cu<sup>2+</sup> and Zn<sup>2+</sup> ion mediators, exhibiting a redox potential above 0 V vs SHE, which is higher than low valent sulfur redox and high specific capacity of 1340 mA h g<sup>–1</sup>. Furthermore, the proposed rechargeable alkaline sulfur batteries achieve a high operating battery voltage of approximately 1.1 V and rapid reaction kinetics, sustained even at high current densities of up to 10 A g<sup>–1</sup>. In-depth characterization and DFT calculations reveal that the alkaline sulfur electrochemistry follows a six-electron conversion reaction S ↔ CuS ↔ ZnS + Cu<sub>2</sub>O ↔ Cu, delivering an energy density of 1168 W h kg<sup>–1</sup> and a power density of 8110 W kg<sup>–1</sup>. This work offers insights into aqueous sulfur electrochemistry and shows an alternative to achieving high energy density aqueous batteries.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"66 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853723","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}
Heterogeneous yolk@shell (YS) metal oxides (MOs) with tailorable chemical compositions and spatial locations have great potential in sensors and heterogeneous catalysis. However, achieving the one-step synthesis of heterogeneous YS MOs, with a spinel oxide shell and rock salt-structured oxide yolk, remains a challenging task. Herein, we present an inhomogeneous metal–organic framework (MOF)-derived “ship-in-bottle” strategy for preparing YS NiO@NiFe2O4 heterostructure nanospheres. The methodology relies on a kinetically controlled reaction via the Kirkendall effect, during which the synchronous etching of Ni-MOF and framework cation substitution take place simultaneously, forming an inhomogeneous double-shelled MOF precursor with an inner shell of Ni-MOF and an outer shell of Fe/Ni-MOF. Subsequently, adopting a thermal contraction strategy for further MOF precursor derivatization contributes to the interface separation between the inner and outer shells and then induces voids to in situ form YS heterostructure nanospheres. Accordingly, the resultant heterogeneous YS NiO@NiFe2O4 is applied in gas sensors, exhibiting regional reaction and shell catalytic filter effects, which stably and selectively detect traces of p-xylene (6.9 ppb) in a highly discriminative manner (Sp-xylene/Stoluene = 4.0) under high humidity (90% RH). This work paves a path for the elaborate design of different functional YS nanomaterials for use in sensors and catalysis.
{"title":"Metal–Organic Framework–Derived “Ship-in-Bottle” Method: Heterogeneous Yolk@Shell Metal Oxides for Heterogeneous Sensing","authors":"Qi Yu, Zihe Liu, Tianshuang Wang, Xueying Kou, Liupeng Zhao, Peng Sun, Geyu Lu","doi":"10.1021/acsnano.5c00604","DOIUrl":"https://doi.org/10.1021/acsnano.5c00604","url":null,"abstract":"Heterogeneous yolk@shell (YS) metal oxides (MOs) with tailorable chemical compositions and spatial locations have great potential in sensors and heterogeneous catalysis. However, achieving the one-step synthesis of heterogeneous YS MOs, with a spinel oxide shell and rock salt-structured oxide yolk, remains a challenging task. Herein, we present an inhomogeneous metal–organic framework (MOF)-derived “ship-in-bottle” strategy for preparing YS NiO@NiFe<sub>2</sub>O<sub>4</sub> heterostructure nanospheres. The methodology relies on a kinetically controlled reaction via the Kirkendall effect, during which the synchronous etching of Ni-MOF and framework cation substitution take place simultaneously, forming an inhomogeneous double-shelled MOF precursor with an inner shell of Ni-MOF and an outer shell of Fe/Ni-MOF. Subsequently, adopting a thermal contraction strategy for further MOF precursor derivatization contributes to the interface separation between the inner and outer shells and then induces voids to in situ form YS heterostructure nanospheres. Accordingly, the resultant heterogeneous YS NiO@NiFe<sub>2</sub>O<sub>4</sub> is applied in gas sensors, exhibiting regional reaction and shell catalytic filter effects, which stably and selectively detect traces of <i>p</i>-xylene (6.9 ppb) in a highly discriminative manner (<i>S</i><sub><i>p-</i>xylene</sub>/<i>S</i><sub>toluene</sub> = 4.0) under high humidity (90% RH). This work paves a path for the elaborate design of different functional YS nanomaterials for use in sensors and catalysis.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"12 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857610","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}
Qinying Nan, Chunchun Yin, Runyu Tian, Jing Zhang, Jinfeng Wang, Chenghu Yan, Jinming Zhang, Jin Wu, Jun Zhang
Environmental humidity regulation is crucial for diverse applications ranging from healthcare, food preservation, drug storage, to electronics protection. Herein, we employed natural cellulose as the raw material to fabricate superhygroscopic aerogels with hierarchical string-bag structure for effective humidity control. The aggregation state of cellulose chains was regulated to fabricate micronano materials, including the cellulose nanofiber network (CNFN), dendritic microfibers (CDF), and pleated microfibers (CPF), via changing the precipitation process of cellulose/ionic liquid solutions. They immobilized hygroscopic salts (LiCl, CaCl2, and MgSO4) to form uniform aerogels featuring micrometer macropores and nanometer string-bags. The molecular-level distribution of metal salts along the macropore wall and nanofibers, combined with the high hydrophilicity of cellulose, enabled rapid moisture absorption from the environment and transportation within the hierarchical string-bag structure. Moreover, the micronano hierarchical structure was conducive to the water storage. CNFN/LiCl aerogel demonstrated exceptional moisture absorption performance, achieving a water uptake of 1.36 and 3.14 g/g at 30% and 70% RH, respectively. Such superhygroscopic materials could rapidly and effectively control the environmental humidity, indicating a huge potential in food preservation, healthcare, and environmental regulation.
{"title":"Superhygroscopic Aerogels with Hierarchical String-Bag Structure for Effective Humidity Control","authors":"Qinying Nan, Chunchun Yin, Runyu Tian, Jing Zhang, Jinfeng Wang, Chenghu Yan, Jinming Zhang, Jin Wu, Jun Zhang","doi":"10.1021/acsnano.5c00979","DOIUrl":"https://doi.org/10.1021/acsnano.5c00979","url":null,"abstract":"Environmental humidity regulation is crucial for diverse applications ranging from healthcare, food preservation, drug storage, to electronics protection. Herein, we employed natural cellulose as the raw material to fabricate superhygroscopic aerogels with hierarchical string-bag structure for effective humidity control. The aggregation state of cellulose chains was regulated to fabricate micronano materials, including the cellulose nanofiber network (CNFN), dendritic microfibers (CDF), and pleated microfibers (CPF), via changing the precipitation process of cellulose/ionic liquid solutions. They immobilized hygroscopic salts (LiCl, CaCl<sub>2</sub>, and MgSO<sub>4</sub>) to form uniform aerogels featuring micrometer macropores and nanometer string-bags. The molecular-level distribution of metal salts along the macropore wall and nanofibers, combined with the high hydrophilicity of cellulose, enabled rapid moisture absorption from the environment and transportation within the hierarchical string-bag structure. Moreover, the micronano hierarchical structure was conducive to the water storage. CNFN/LiCl aerogel demonstrated exceptional moisture absorption performance, achieving a water uptake of 1.36 and 3.14 g/g at 30% and 70% RH, respectively. Such superhygroscopic materials could rapidly and effectively control the environmental humidity, indicating a huge potential in food preservation, healthcare, and environmental regulation.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"43 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857612","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}
The huge volume changes of silicon (Si) anodes during cycling lead to continuous solid electrolyte interphase thickening, mechanical failure, and loss of electrical contact, which have become key bottlenecks limiting their practical applications. This work presents a trimodal in situ growth strategy for constructing hierarchical carbon nanoarchitecture networks on Si substrates (Si@Gr@CNT). The designed “Edge-Surface-Inter” (E-S-I) architecture exhibits three synergistic features: an edge-protruding structure forming vertical conductive channels for rapid Li+ transport, a surface-entangled structure providing mechanical enhancement, and an interbridging structure constructing continuous three-dimensional electron transport networks. The Si@Gr@CNT electrode demonstrates a 63.2% improvement in half-cell rate performance compared with traditional Si@Gr. The E-S-I architecture contributes to suppressing excessive LiF formation through improved local current distribution, devoted to the stable and thinner solid electrolyte interphase layer. The three-dimensional conductive network possesses a significant stress regulation effect, which provides stress release space in the vertical direction and lateral stress buffering through surface flexible entanglement. For practical applications, the full cell assembled with the LiFePO4 cathode and the Si@Gr@CNT/graphite composite anode delivers high energy density and enhanced durability. This study establishes a strategy for hierarchical carbon nanoarchitectures and provides design insights into high-performance Si-based electrodes.
{"title":"Edge-Surface-Inter Carbon Nanoarchitecture on Silicon","authors":"Yin Yang, Jian Wang, Dong Sun, Yulong Li, Ting Xiao, Chen Zhang, Changbo Lu, Jinsen Gao, Chunming Xu, Yongfeng Li, Xinlong Ma","doi":"10.1021/acsnano.5c00371","DOIUrl":"https://doi.org/10.1021/acsnano.5c00371","url":null,"abstract":"The huge volume changes of silicon (Si) anodes during cycling lead to continuous solid electrolyte interphase thickening, mechanical failure, and loss of electrical contact, which have become key bottlenecks limiting their practical applications. This work presents a trimodal in situ growth strategy for constructing hierarchical carbon nanoarchitecture networks on Si substrates (Si@Gr@CNT). The designed “Edge-Surface-Inter” (E-S-I) architecture exhibits three synergistic features: an edge-protruding structure forming vertical conductive channels for rapid Li<sup>+</sup> transport, a surface-entangled structure providing mechanical enhancement, and an interbridging structure constructing continuous three-dimensional electron transport networks. The Si@Gr@CNT electrode demonstrates a 63.2% improvement in half-cell rate performance compared with traditional Si@Gr. The E-S-I architecture contributes to suppressing excessive LiF formation through improved local current distribution, devoted to the stable and thinner solid electrolyte interphase layer. The three-dimensional conductive network possesses a significant stress regulation effect, which provides stress release space in the vertical direction and lateral stress buffering through surface flexible entanglement. For practical applications, the full cell assembled with the LiFePO<sub>4</sub> cathode and the Si@Gr@CNT/graphite composite anode delivers high energy density and enhanced durability. This study establishes a strategy for hierarchical carbon nanoarchitectures and provides design insights into high-performance Si-based electrodes.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"17 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857576","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}
The von Hippel–Lindau (VHL) tumor suppressor gene product, pVHL, is frequently deficient in a variety of human cancers. In addressing the treatment of pVHL-deficient tumors, hypoxia-inducible factor 2α (HIF-2α) has risen as a promising therapeutic target, culminating in the development of specific inhibitors like PT2385 and its analogues. Nonetheless, the absence of targeted delivery capabilities in these inhibitors heightens the risk of on-target toxicities. To mitigate these limitations, we have engineered a nanoparticle, termed PMMF (PT/MMSN@DSPE-PEG-FA), capable of delivering both a HIF-2α antagonist (PT2385) and manganese directly to tumor sites. PMMF has shown effective targeting of pVHL-deficient clear-cell renal cell carcinoma and melanoma, leading to significant therapeutic benefits and alleviating hypoxic and immunosuppressive traits of the tumor microenvironment. Functionally, PMMF boosts the cyclic GMP–AMP synthase–stimulator of interferon genes signaling pathway, which, in turn, stimulates a robust innate immune response. This response activates natural killer (NK) cells and CD8+ T lymphocytes while curbing the infiltration of regulatory T cells. Notably, the therapeutic efficacy of PMMF is markedly reduced when NK cells are blocked but not affected by neutrophil blockade, highlighting the critical role of NK cells in PMMF-induced antitumor immunity. Additionally, the safety profile of PMMF showed minimal systemic post-treatment cytotoxicity. In summary, our findings position PMMF as a promising platform for treating tumors with pVHL deficiency and underscore the therapeutic potential of metalloimmunotherapy.
{"title":"Manganese-Doped Nanoparticles with Hypoxia-Inducible Factor 2α Inhibitor That Elicit Innate Immune Responses against von Hippel–Lindau Protein-Deficient Tumors","authors":"Yan Fang, Feiyang Shen, Rui Huang, Yao Lin, Yijia Wu, Qian Li, Zhu Xie, Xiaoyu Yang, Zhe Zhang, Xiaoliang Jin, Xianqun Fan, Jianfeng Shen","doi":"10.1021/acsnano.4c14277","DOIUrl":"https://doi.org/10.1021/acsnano.4c14277","url":null,"abstract":"The von Hippel–Lindau (VHL) tumor suppressor gene product, pVHL, is frequently deficient in a variety of human cancers. In addressing the treatment of pVHL-deficient tumors, hypoxia-inducible factor 2α (HIF-2α) has risen as a promising therapeutic target, culminating in the development of specific inhibitors like PT2385 and its analogues. Nonetheless, the absence of targeted delivery capabilities in these inhibitors heightens the risk of on-target toxicities. To mitigate these limitations, we have engineered a nanoparticle, termed PMMF (PT/MMSN@DSPE-PEG-FA), capable of delivering both a HIF-2α antagonist (PT2385) and manganese directly to tumor sites. PMMF has shown effective targeting of pVHL-deficient clear-cell renal cell carcinoma and melanoma, leading to significant therapeutic benefits and alleviating hypoxic and immunosuppressive traits of the tumor microenvironment. Functionally, PMMF boosts the cyclic GMP–AMP synthase–stimulator of interferon genes signaling pathway, which, in turn, stimulates a robust innate immune response. This response activates natural killer (NK) cells and CD8<sup>+</sup> T lymphocytes while curbing the infiltration of regulatory T cells. Notably, the therapeutic efficacy of PMMF is markedly reduced when NK cells are blocked but not affected by neutrophil blockade, highlighting the critical role of NK cells in PMMF-induced antitumor immunity. Additionally, the safety profile of PMMF showed minimal systemic post-treatment cytotoxicity. In summary, our findings position PMMF as a promising platform for treating tumors with pVHL deficiency and underscore the therapeutic potential of metalloimmunotherapy.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"35 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853868","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}
Rare-earth adatoms on surfaces have been studied for potential atomic-scale magnetic storage, quantum sensing, and quantum computing applications. Despite accumulating experimental efforts, a comprehensive description of the electronic configurations of the adatoms remains elusive. Here, we investigate two charge states and several electronic configurations, including 5d and 6s valence shells, for a Sm adatom on a MgO substrate using multiconfigurational ab initio methods, for the possibility of using the Sm nuclear spin levels as qubits. For the configurations in a neutral charge state, we find that the electronic ground state is a singlet, and thus the hyperfine interaction associated with the 147Sm nucleus is absent, which may greatly enhance nuclear spin coherence time. The degeneracy of the nuclear levels is lifted by the nuclear quadrupole interaction. We show that the splitting of the nuclear levels can be controlled by a static electric field, and that Rabi oscillations between the nuclear levels can be induced by a time-dependent electric field. For the configurations in a singly charged state, electronic Kramers doublets are formed. The electronic configurations including an unpaired 6s orbital exhibit a strong hyperfine Stark effect due to a large Fermi contact contribution to the hyperfine interaction. In these configurations, electric-field-induced Rabi oscillations between the electronic-nuclear levels can occur at frequencies up to 3 orders of magnitude higher than those for the neutral charge state. The proposed system may be experimentally observed within scanning tunneling microscopy.
{"title":"Electrical Control of the Nuclear Spin States of Rare-Earth Adatoms","authors":"Homa Karimi, Aleksander L. Wysocki, Kyungwha Park","doi":"10.1021/acsnano.4c16416","DOIUrl":"https://doi.org/10.1021/acsnano.4c16416","url":null,"abstract":"Rare-earth adatoms on surfaces have been studied for potential atomic-scale magnetic storage, quantum sensing, and quantum computing applications. Despite accumulating experimental efforts, a comprehensive description of the electronic configurations of the adatoms remains elusive. Here, we investigate two charge states and several electronic configurations, including 5d and 6s valence shells, for a Sm adatom on a MgO substrate using multiconfigurational <i>ab initio</i> methods, for the possibility of using the Sm nuclear spin levels as qubits. For the configurations in a neutral charge state, we find that the electronic ground state is a singlet, and thus the hyperfine interaction associated with the <sup>147</sup>Sm nucleus is absent, which may greatly enhance nuclear spin coherence time. The degeneracy of the nuclear levels is lifted by the nuclear quadrupole interaction. We show that the splitting of the nuclear levels can be controlled by a static electric field, and that Rabi oscillations between the nuclear levels can be induced by a time-dependent electric field. For the configurations in a singly charged state, electronic Kramers doublets are formed. The electronic configurations including an unpaired 6s orbital exhibit a strong hyperfine Stark effect due to a large Fermi contact contribution to the hyperfine interaction. In these configurations, electric-field-induced Rabi oscillations between the electronic-nuclear levels can occur at frequencies up to 3 orders of magnitude higher than those for the neutral charge state. The proposed system may be experimentally observed within scanning tunneling microscopy.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"17 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857609","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}
Junyeop Kim, Sumin Kim, Yerim Hwang, Saemin An, Jeonghyun Park, Yoo-Bin Kwon, Byounggook Cho, Daeyeol Kwon, Yunkyung Kim, Soi Kang, Young-Kwan Kim, Jongpil Kim
MXenes, a two-dimensional transition metal carbide and nitride, have shown significant potential in various biological applications. In particular, the distinct properties of MXenes─including their functionalizable surface, biocompatibility, and conductive characteristics, make them highly promising materials for advancing biomedical technologies. Here, we report that MXene, under specific electromagnetic field (EMF) conditions, effectively promotes the direct lineage reprogramming of induced dopaminergic (iDA) neurons both in vitro and in vivo. Remarkably, we found that electromagnetized MXene leads to specific activation of histone acetylation during the induced dopaminergic neuronal reprogramming process and efficiently alleviates symptoms in a mouse model of Parkinson’s disease (PD). Moreover, MXene-mediated electromagnetic stimulation effectively promotes the direct reprogramming of human iDA neurons from skin fibroblasts. Therefore, our study highlights MXene’s application in cell reprogramming, offering promising advancements in regenerative medicine through improved efficiency and reliability.
{"title":"Electromagnetized MXenes Enhance the Efficient Direct Reprogramming of Dopamine Neurons for Parkinson’s Disease Therapy","authors":"Junyeop Kim, Sumin Kim, Yerim Hwang, Saemin An, Jeonghyun Park, Yoo-Bin Kwon, Byounggook Cho, Daeyeol Kwon, Yunkyung Kim, Soi Kang, Young-Kwan Kim, Jongpil Kim","doi":"10.1021/acsnano.5c01457","DOIUrl":"https://doi.org/10.1021/acsnano.5c01457","url":null,"abstract":"MXenes, a two-dimensional transition metal carbide and nitride, have shown significant potential in various biological applications. In particular, the distinct properties of MXenes─including their functionalizable surface, biocompatibility, and conductive characteristics, make them highly promising materials for advancing biomedical technologies. Here, we report that MXene, under specific electromagnetic field (EMF) conditions, effectively promotes the direct lineage reprogramming of induced dopaminergic (iDA) neurons both <i>in vitro</i> and <i>in vivo</i>. Remarkably, we found that electromagnetized MXene leads to specific activation of histone acetylation during the induced dopaminergic neuronal reprogramming process and efficiently alleviates symptoms in a mouse model of Parkinson’s disease (PD). Moreover, MXene-mediated electromagnetic stimulation effectively promotes the direct reprogramming of human iDA neurons from skin fibroblasts. Therefore, our study highlights MXene’s application in cell reprogramming, offering promising advancements in regenerative medicine through improved efficiency and reliability.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"126 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853870","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}
Lead-halide perovskite light-emitting diodes (PeLEDs) are intrinsically capable of delivering high efficiency at high current densities compared to conventional solution-processed light-emitting diodes. While such performance and relevant high radiance have been well demonstrated in green and near-infrared ones, blue PeLEDs have lagged far behind due to extremely severe luminance-efficiency roll-off, especially in the pure-blue region (<480 nm, a CIEy coordinate below 0.15). Here, by tackling the critical limitations of phosphonic acid functional carbazoles (PACs) as hole injection layers and simultaneously leveraging their advantages on hole injection, we achieved ultrabright pure blue PeLEDs with minimized efficiency roll-off at high brightness with a CIEy coordinate below 0.15. We show that devices based on prevailing small-molecule PACs generally exhibit significant leakage currents. This is due to a synergistic effect of uneven surface coverage from reverse micelle formation and the nanoisland structure of thin-film lead-halide perovskite emitters. By using polymeric PACs instead, we demonstrate bright blue PeLEDs showing a peak luminance of ∼29 800 cd m–2 (478 nm, at a CIEy coordinate below 0.15). We also achieve a high brightness reaching ∼140 000 cd m–2 under pulsed driven. Our study not only provides a useful guidance for developing bright blue PeLEDs but also resolves a long-standing puzzle regarding the interfacial properties of PACs and their impact on hole transport, and it helps with the further design of these materials for lead-halide perovskite applications.
{"title":"Ultrabright Blue Lead-Halide Perovskite Light-Emitting Diodes Based on Phosphonic Acid Functionalized Hole Injection Layer","authors":"Xiyu Luo, Cong Tao, Yanru Lu, Zhijun Ren, Zengguang Zhang, Jiawei Chen, Qi Wang, Danlei Zhu, Haifeng Zhao, Zhongbin Wu, Xiaowang Liu, Yatao Zou, Dongdong Zhang, Shangshang Chen, Weidong Xu, Lian Duan","doi":"10.1021/acsnano.5c01879","DOIUrl":"https://doi.org/10.1021/acsnano.5c01879","url":null,"abstract":"Lead-halide perovskite light-emitting diodes (PeLEDs) are intrinsically capable of delivering high efficiency at high current densities compared to conventional solution-processed light-emitting diodes. While such performance and relevant high radiance have been well demonstrated in green and near-infrared ones, blue PeLEDs have lagged far behind due to extremely severe luminance-efficiency roll-off, especially in the pure-blue region (<480 nm, a CIEy coordinate below 0.15). Here, by tackling the critical limitations of phosphonic acid functional carbazoles (PACs) as hole injection layers and simultaneously leveraging their advantages on hole injection, we achieved ultrabright pure blue PeLEDs with minimized efficiency roll-off at high brightness with a CIEy coordinate below 0.15. We show that devices based on prevailing small-molecule PACs generally exhibit significant leakage currents. This is due to a synergistic effect of uneven surface coverage from reverse micelle formation and the nanoisland structure of thin-film lead-halide perovskite emitters. By using polymeric PACs instead, we demonstrate bright blue PeLEDs showing a peak luminance of ∼29 800 cd m<sup>–2</sup> (478 nm, at a CIEy coordinate below 0.15). We also achieve a high brightness reaching ∼140 000 cd m<sup>–2</sup> under pulsed driven. Our study not only provides a useful guidance for developing bright blue PeLEDs but also resolves a long-standing puzzle regarding the interfacial properties of PACs and their impact on hole transport, and it helps with the further design of these materials for lead-halide perovskite applications.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"28 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853737","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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