Pub Date : 2025-04-22DOI: 10.1021/acsnano.4c1705310.1021/acsnano.4c17053
Ilaria Tomei, Simone Prili, Christian Petrucci, Fabrizio Arciprete and Claudio Goletti*,
{"title":"Comment on “In-Plane Optical Anisotropy and Linear Dichroism in Low-Symmetry Layered TlSe”","authors":"Ilaria Tomei, Simone Prili, Christian Petrucci, Fabrizio Arciprete and Claudio Goletti*, ","doi":"10.1021/acsnano.4c1705310.1021/acsnano.4c17053","DOIUrl":"https://doi.org/10.1021/acsnano.4c17053https://doi.org/10.1021/acsnano.4c17053","url":null,"abstract":"","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"19 15","pages":"14521–14522 14521–14522"},"PeriodicalIF":15.8,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853932","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}
Polypeptide-based liquid–liquid phase separation (LLPS) has received considerable attention as it governs the formation of membraneless organelles in cells. However, the detailed mechanistic understanding of how one of the most prevalent cationic amino acids in proteins, arginine, interacts with various biomolecules to induce phase separation and undergo morphogenesis remains to be resolved. Herein, we report the phase separation behavior and transformation of arginine-rich coacervates into vesicular structures upon introducing polyphosphates. Transformation into vesicles was shown to occur independent of the initial anionic counterparts and was driven by salt-bridge interactions between guanidinium groups of arginine residues and phosphates. We also investigate the role of intermolecular forces and ionic effects on the morphological transformation and further exploit their potential in the assembly of artificial tissue-like constructs. Overall, our findings underpin a unifying principle for vesicle transformation from arginine-rich coacervates and their potency for reconstituting hierarchical biological microcompartments.
{"title":"Salt-Bridge-Mediated Coacervate-to-Vesicle Transformation in Arginine-Rich Coacervates","authors":"Hanjin Seo, Hyun Su Lee, Hyomin Lee","doi":"10.1021/acsnano.5c02235","DOIUrl":"https://doi.org/10.1021/acsnano.5c02235","url":null,"abstract":"Polypeptide-based liquid–liquid phase separation (LLPS) has received considerable attention as it governs the formation of membraneless organelles in cells. However, the detailed mechanistic understanding of how one of the most prevalent cationic amino acids in proteins, arginine, interacts with various biomolecules to induce phase separation and undergo morphogenesis remains to be resolved. Herein, we report the phase separation behavior and transformation of arginine-rich coacervates into vesicular structures upon introducing polyphosphates. Transformation into vesicles was shown to occur independent of the initial anionic counterparts and was driven by salt-bridge interactions between guanidinium groups of arginine residues and phosphates. We also investigate the role of intermolecular forces and ionic effects on the morphological transformation and further exploit their potential in the assembly of artificial tissue-like constructs. Overall, our findings underpin a unifying principle for vesicle transformation from arginine-rich coacervates and their potency for reconstituting hierarchical biological microcompartments.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"41 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857325","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}
Fiki Owhoso, Hongju Jung, Hyungdon Joo, Bin Wang, Eranda Nikolla, Nicholas A. Kotov, David G. Kwabi
Self-assembled complex nanoparticles with spiky surfaces can accommodate significant amounts of excess charge, which can enable various energy storage and conversion technologies. Their combination of high charge storage capacity, high dispersibility, and synthetic simplicity renders them attractive for use in redox-flow batteries. Here we show that hedgehog-like FeSe2 particles (HPs) are effective charge carriers in aqueous redox-flow batteries for long-duration energy storage. The spikes reduce particle-to-particle attraction, engendering stable aqueous dispersions. Shear thinning behavior of the spiky particles observed in this work for the first time facilitates their utilization in redox-flow batteries. HP suspensions exhibited a half-wave potential (E1/2) of 0.45 V vs RHE (−0.47 vs Hg/HgO) at high HP loadings under strongly alkaline conditions (pH 14). A compositionally asymmetric flow cell comprising FeSe2 HPs in the negative electrolyte and ferro/ferricyanide in the positive electrolyte displayed an open circuit voltage of ∼1.0 V. Up to 1.4 mol e/L (∼36.4 Ah/L) of volumetric capacity in the negative electrolyte was attained. Both the spiky shapes of these particles and their high densities in dispersion were responsible for capacity increase relative to nonspiky particles. The slow formation of iron hydroxide-species was responsible for capacity fade at 0.6–5.8%/cycle. Such capacity fade may be mitigated in future work through conformal particle coatings and judicious adjustments to electrolyte composition.
{"title":"High Capacity Redox-Flow Batteries with High Density Suspensions of Spiky Nanostructured Particles","authors":"Fiki Owhoso, Hongju Jung, Hyungdon Joo, Bin Wang, Eranda Nikolla, Nicholas A. Kotov, David G. Kwabi","doi":"10.1021/acsnano.4c14174","DOIUrl":"https://doi.org/10.1021/acsnano.4c14174","url":null,"abstract":"Self-assembled complex nanoparticles with spiky surfaces can accommodate significant amounts of excess charge, which can enable various energy storage and conversion technologies. Their combination of high charge storage capacity, high dispersibility, and synthetic simplicity renders them attractive for use in redox-flow batteries. Here we show that hedgehog-like FeSe<sub>2</sub> particles (HPs) are effective charge carriers in aqueous redox-flow batteries for long-duration energy storage. The spikes reduce particle-to-particle attraction, engendering stable aqueous dispersions. Shear thinning behavior of the spiky particles observed in this work for the first time facilitates their utilization in redox-flow batteries. HP suspensions exhibited a half-wave potential (<i>E</i><sub>1/2</sub>) of 0.45 V vs RHE (−0.47 vs Hg/HgO) at high HP loadings under strongly alkaline conditions (pH 14). A compositionally asymmetric flow cell comprising FeSe<sub>2</sub> HPs in the negative electrolyte and ferro/ferricyanide in the positive electrolyte displayed an open circuit voltage of ∼1.0 V. Up to 1.4 mol <i>e</i>/L (∼36.4 Ah/L) of volumetric capacity in the negative electrolyte was attained. Both the spiky shapes of these particles and their high densities in dispersion were responsible for capacity increase relative to nonspiky particles. The slow formation of iron hydroxide-species was responsible for capacity fade at 0.6–5.8%/cycle. Such capacity fade may be mitigated in future work through conformal particle coatings and judicious adjustments to electrolyte composition.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"38 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857607","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}
Regulating the artificial solid electrolyte interphase (SEI) and interfacial solvation structure of the electrolyte is crucial for developing rechargeable magnesium batteries (RMBs) with long cycling life, high current density tolerance, and fast ion transport capability operated under extreme environments, such as low temperatures. Herein, an effective strategy using oligomeric poly(3,4-dihydro-2H-pyran) (polyDHP) is proposed to modulate the interfacial solvation structure of RMBs, with the construction of an artificial SEI with rapid Mg-ion conductivity. The steric hindrance of polyDHP and its electrostatic interaction with Mg2+ reduce the solvent molecules in the first solvation shell, allowing polyDHP molecules to participate in coordination, thus lowering the desolvation energy barrier of Mg2+ and facilitating their deposition and stripping. Furthermore, due to the glass transition behavior, oligomeric polyDHP exhibits a more ordered structure with more continuous internal ion transport channels at −20 °C, therefore enabling stable RMB operation at lower temperatures for the first time. The corresponding Mg symmetric cells display a much lower overpotential (400 mV) and excellent cycling stability at both room temperature (over 5000 h at 5 mA cm–2 and 10 mA h cm–2) and a low temperature of −20 °C (over 1300 h at 3 mA cm–2 and 3 mA h cm–2). This strategy supports the stable cycling of CuS∥Mg full cells for over 200 cycles at −20 °C. This work reveals the importance of regulating the interfacial solvation structure, promoting the realistic applications of RMBs under extreme conditions.
{"title":"Regulating the Interfacial Solvation Environment by a Pyran-Based Polymer for High-Areal-Capacity and Low-Temperature-Endurable Magnesium Metal Batteries","authors":"Tengfei Wang, Keyi Chen, Guyue Li, Zhang Chen, Yanfeng Gao, Chilin Li","doi":"10.1021/acsnano.5c02206","DOIUrl":"https://doi.org/10.1021/acsnano.5c02206","url":null,"abstract":"Regulating the artificial solid electrolyte interphase (SEI) and interfacial solvation structure of the electrolyte is crucial for developing rechargeable magnesium batteries (RMBs) with long cycling life, high current density tolerance, and fast ion transport capability operated under extreme environments, such as low temperatures. Herein, an effective strategy using oligomeric poly(3,4-dihydro-2<i>H</i>-pyran) (polyDHP) is proposed to modulate the interfacial solvation structure of RMBs, with the construction of an artificial SEI with rapid Mg-ion conductivity. The steric hindrance of polyDHP and its electrostatic interaction with Mg<sup>2+</sup> reduce the solvent molecules in the first solvation shell, allowing polyDHP molecules to participate in coordination, thus lowering the desolvation energy barrier of Mg<sup>2+</sup> and facilitating their deposition and stripping. Furthermore, due to the glass transition behavior, oligomeric polyDHP exhibits a more ordered structure with more continuous internal ion transport channels at −20 °C, therefore enabling stable RMB operation at lower temperatures for the first time. The corresponding Mg symmetric cells display a much lower overpotential (400 mV) and excellent cycling stability at both room temperature (over 5000 h at 5 mA cm<sup>–2</sup> and 10 mA h cm<sup>–2</sup>) and a low temperature of −20 °C (over 1300 h at 3 mA cm<sup>–2</sup> and 3 mA h cm<sup>–2</sup>). This strategy supports the stable cycling of CuS∥Mg full cells for over 200 cycles at −20 °C. This work reveals the importance of regulating the interfacial solvation structure, promoting the realistic applications of RMBs under extreme conditions.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"52 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857608","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}
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}
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.
{"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}
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