Pub Date : 2024-10-01Epub Date: 2024-05-27DOI: 10.1002/smll.202401204
Siyu Fang, Chengyu Han, Shaojie Zhang, Yu Cao, Kang Ma, Yiming Zhang, Xinpeng Han, Juan Wang, Jie Sun
The demand for state-of-the-art high-energy-density lithium-ion batteries is increasing. However, the low specific capacity of electrode materials in conventional full-cell systems cannot meet the requirements. Ni-rich layered oxide cathodes such as Li(Ni0.8Co0.1Mn0.1)O2 (NCM811) have a high theoretical specific capacity of 200 mAh g-1, but it is always accompanied by side reactions on the electrode/electrolyte interface. Phosphorus anode possesses a high theoretical specific capacity of 2596 mAh g-1, but it has a huge volume expansion (≈300%). Herein, a highly compatible and secure electrolyte is reported via introducing an additive with a narrow electrochemical window, Lithium difluoro(oxalato)borate (LiDFOB), into 1 m LiPF6 EC/DMC with tris (2,2,2-trifluoroethyl) phosphate (TFEP) as a cosolvent. LiDFOB participates in the formation of organic/inorganic hybrid electrode/electrolyte interface layers at both the cathode and anode sides. The side reactions on the surface of the NCM811 cathode and the volume expansion of the phosphorus anode are effectively alleviated. The NCM811//RP full cell in this electrolyte shows high capacity retention of 82% after 150 cycles at a 0.5C rate. Meanwhile, the electrolyte shows non-flammability. This work highlights the importance of manipulating the electrode/electrolyte interface layers for the design of lithium-ion batteries with high energy density.
对最先进的高能量密度锂离子电池的需求与日俱增。然而,传统全电池系统中电极材料的比容量较低,无法满足要求。富镍层状氧化物阴极(如 Li(Ni0.8Co0.1Mn0.1)O2 (NCM811))的理论比容量高达 200 mAh g-1,但在电极/电解质界面上总是伴随着副反应。磷阳极的理论比容量高达 2596 mAh g-1,但体积膨胀很大(≈300%)。本文报告了一种高度兼容和安全的电解质,即在以磷酸三(2,2,2-三氟乙基)酯(TFEP)为共溶剂的 1 m LiPF6 EC/DMC 中引入一种电化学窗口较窄的添加剂--二氟(草酸)硼酸锂(LiDFOB)。LiDFOB 参与了阴极和阳极侧有机/无机混合电极/电解质界面层的形成。NCM811 阴极表面的副反应和磷阳极的体积膨胀得到了有效缓解。使用这种电解液的 NCM811//RP 全电池在 0.5C 速率下循环 150 次后,容量保持率高达 82%。同时,该电解液还具有不燃性。这项工作凸显了操纵电极/电解质界面层对于设计高能量密度锂离子电池的重要性。
{"title":"High Safety Electrolyte Design for Enabling High Energy-Density System of LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub>//Phosphorus by Simultaneously Adjusting Dual Electrode/Electrolyte Interfaces.","authors":"Siyu Fang, Chengyu Han, Shaojie Zhang, Yu Cao, Kang Ma, Yiming Zhang, Xinpeng Han, Juan Wang, Jie Sun","doi":"10.1002/smll.202401204","DOIUrl":"10.1002/smll.202401204","url":null,"abstract":"<p><p>The demand for state-of-the-art high-energy-density lithium-ion batteries is increasing. However, the low specific capacity of electrode materials in conventional full-cell systems cannot meet the requirements. Ni-rich layered oxide cathodes such as Li(Ni<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>)O<sub>2</sub> (NCM811) have a high theoretical specific capacity of 200 mAh g<sup>-1</sup>, but it is always accompanied by side reactions on the electrode/electrolyte interface. Phosphorus anode possesses a high theoretical specific capacity of 2596 mAh g<sup>-1</sup>, but it has a huge volume expansion (≈300%). Herein, a highly compatible and secure electrolyte is reported via introducing an additive with a narrow electrochemical window, Lithium difluoro(oxalato)borate (LiDFOB), into 1 m LiPF<sub>6</sub> EC/DMC with tris (2,2,2-trifluoroethyl) phosphate (TFEP) as a cosolvent. LiDFOB participates in the formation of organic/inorganic hybrid electrode/electrolyte interface layers at both the cathode and anode sides. The side reactions on the surface of the NCM811 cathode and the volume expansion of the phosphorus anode are effectively alleviated. The NCM811//RP full cell in this electrolyte shows high capacity retention of 82% after 150 cycles at a 0.5C rate. Meanwhile, the electrolyte shows non-flammability. This work highlights the importance of manipulating the electrode/electrolyte interface layers for the design of lithium-ion batteries with high energy density.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141154105","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01Epub Date: 2024-05-27DOI: 10.1002/smll.202402284
Doudou Ning, Zhaoqing Lu, Li Hua, Xinyi Zhang, Nan Li, Kaiyue Huang, Songfeng E
2D lamellar nanofiltration membrane is considered to be a promising approach for desalinating seawater/brackish water and recycling sewage. However, its practical feasibility is severely constrained by the lack of durability and stability. Herein, a ternary nanofiltration membrane via a mixed-dimensional assembly of 2D boron nitride nanosheets (BNNS) is fabricated, 1D aramid nanofibers (ANF), and 2D covalent organic frameworks (COF). The abundant 2D and 1D nanofluid channels endow the BNNS/ANF/COF membrane with a high flux of 194 L·m‒2·h‒1. By the synergies of the size sieving and Donnan effect, the BNNS/ANF/COF membrane demonstrates high rejection (among 98%) for those dyes whose size exceeds 1.0 nm. Moreover, the BNNS/ANF/COF membrane also exhibits remarkable durability and mechanical stability, which are attributed to the strong adhesion and interactions between BNNS, ANF, and COF, as well as the superior mechanical robustness of ANF. This work provides a novel strategy to develop robust and durable 2D lamellar nanofiltration membranes with high permeance and selectivity simultaneously.
{"title":"Designing Nanofluidic Channels of Boron Nitride Nanosheets/Aramid Nanofibers/Covalent Organic Frameworks Nanofiltration Membrane for Ultrafast Mass Transport.","authors":"Doudou Ning, Zhaoqing Lu, Li Hua, Xinyi Zhang, Nan Li, Kaiyue Huang, Songfeng E","doi":"10.1002/smll.202402284","DOIUrl":"10.1002/smll.202402284","url":null,"abstract":"<p><p>2D lamellar nanofiltration membrane is considered to be a promising approach for desalinating seawater/brackish water and recycling sewage. However, its practical feasibility is severely constrained by the lack of durability and stability. Herein, a ternary nanofiltration membrane via a mixed-dimensional assembly of 2D boron nitride nanosheets (BNNS) is fabricated, 1D aramid nanofibers (ANF), and 2D covalent organic frameworks (COF). The abundant 2D and 1D nanofluid channels endow the BNNS/ANF/COF membrane with a high flux of 194 L·m<sup>‒2</sup>·h<sup>‒1</sup>. By the synergies of the size sieving and Donnan effect, the BNNS/ANF/COF membrane demonstrates high rejection (among 98%) for those dyes whose size exceeds 1.0 nm. Moreover, the BNNS/ANF/COF membrane also exhibits remarkable durability and mechanical stability, which are attributed to the strong adhesion and interactions between BNNS, ANF, and COF, as well as the superior mechanical robustness of ANF. This work provides a novel strategy to develop robust and durable 2D lamellar nanofiltration membranes with high permeance and selectivity simultaneously.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141154059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polarization-sensitive photodetection grounded on low-symmetry 2D materials has immense potential in improving detection accuracy, realizing intelligent detection, and enabling multidimensional visual perception, which has promising application prospects in bio-identification, optical communications, near-infrared imaging, radar, military, and security. However, the majority of the reported polarized photodetection are limited by UV-vis response range and low anisotropic photoresponsivity factor, limiting the achievement of high-performance anisotropic photodetection. Herein, 2D t-InTe crystal is introduced into anisotropic systems and developed to realize broadband-response and high-anisotropy-ratio polarized photodetection. Stemming from its narrow band gap and intrinsic low-symmetry lattice characteristic, 2D t-InTe-based photodetector exhibits a UV-vis-NIR broadband photoresponse and significant photoresponsivity anisotropy behavior, with an exceptional in-plane anisotropic factor of 1.81@808 nm laser, surpassing the performance of most reported 2D counterparts. This work expounds the anisotropic structure-activity relationship of 2D t-InTe crystal, and identifies 2D t-InTe as a prospective candidate for high-performance polarization-sensitive optoelectronics, laying the foundation for future multifunctional device applications.
{"title":"Low-Symmetry 2D t-InTe for Polarization-Sensitive UV-Vis-NIR Photodetection.","authors":"Nan Zhou, Ziwei Dang, Haoran Li, Zongdong Sun, Shijie Deng, Junhao Li, Xiaobo Li, Xiaoxia Bai, Yong Xie, Liang Li, Tianyou Zhai","doi":"10.1002/smll.202400311","DOIUrl":"10.1002/smll.202400311","url":null,"abstract":"<p><p>Polarization-sensitive photodetection grounded on low-symmetry 2D materials has immense potential in improving detection accuracy, realizing intelligent detection, and enabling multidimensional visual perception, which has promising application prospects in bio-identification, optical communications, near-infrared imaging, radar, military, and security. However, the majority of the reported polarized photodetection are limited by UV-vis response range and low anisotropic photoresponsivity factor, limiting the achievement of high-performance anisotropic photodetection. Herein, 2D t-InTe crystal is introduced into anisotropic systems and developed to realize broadband-response and high-anisotropy-ratio polarized photodetection. Stemming from its narrow band gap and intrinsic low-symmetry lattice characteristic, 2D t-InTe-based photodetector exhibits a UV-vis-NIR broadband photoresponse and significant photoresponsivity anisotropy behavior, with an exceptional in-plane anisotropic factor of 1.81@808 nm laser, surpassing the performance of most reported 2D counterparts. This work expounds the anisotropic structure-activity relationship of 2D t-InTe crystal, and identifies 2D t-InTe as a prospective candidate for high-performance polarization-sensitive optoelectronics, laying the foundation for future multifunctional device applications.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141157177","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01Epub Date: 2024-05-30DOI: 10.1002/smll.202400326
Jinwei Bai, Xuan Zhang, Zhiwen Zhao, Shihao Sun, Wenyuan Cheng, Hongxiang Yu, Xinyue Chang, Baodui Wang
The latest research identifies that cysteine (Cys) is one of the key factors in tumor proliferation, metastasis, and recurrence. The direct depletion of intracellular Cys shows a profound antitumor effect. However, using nanozymes to efficiently deplete Cys for tumor therapy has not yet attracted widespread attention. Here, a (3-carboxypropyl) triphenylphosphonium bromide-derived hyaluronic acid-modified copper oxide nanorods (denoted as MitCuOHA) are designed with cysteine oxidase-like, glutathione oxidase-like and peroxidase-like activities to realize Cys depletion and further induce cellular ferroptosis and cuproptosis for synergistic tumor therapy. MitCuOHA nanozymes can efficiently catalyze the depletion of Cys and glutathione (GSH), accompanied by the generation of H2O2 and the subsequent conversion into highly active hydroxyl radicals, thereby successfully inducing ferroptosis in cancer cells. Meanwhile, copper ions released by MitCuOHA under tumor microenvironment stimulation directly bind to lipoylated proteins of the tricarboxylic acid cycle, leading to the abnormal aggregation of lipoylated proteins and subsequent loss of iron-sulfur cluster proteins, which ultimately triggers proteotoxic stress and cell cuproptosis. Both in vitro and in vivo results show the drastically enhanced anticancer efficacy of Cys oxidation catalyzed by the MitCuOHA nanozymes, demonstrating the high feasibility of such catalytic Cys depletion-induced synergistic ferroptosis and cuproptosis therapeutic concept.
{"title":"CuO Nanozymes Catalyze Cysteine and Glutathione Depletion Induced Ferroptosis and Cuproptosis for Synergistic Tumor Therapy.","authors":"Jinwei Bai, Xuan Zhang, Zhiwen Zhao, Shihao Sun, Wenyuan Cheng, Hongxiang Yu, Xinyue Chang, Baodui Wang","doi":"10.1002/smll.202400326","DOIUrl":"10.1002/smll.202400326","url":null,"abstract":"<p><p>The latest research identifies that cysteine (Cys) is one of the key factors in tumor proliferation, metastasis, and recurrence. The direct depletion of intracellular Cys shows a profound antitumor effect. However, using nanozymes to efficiently deplete Cys for tumor therapy has not yet attracted widespread attention. Here, a (3-carboxypropyl) triphenylphosphonium bromide-derived hyaluronic acid-modified copper oxide nanorods (denoted as MitCuOHA) are designed with cysteine oxidase-like, glutathione oxidase-like and peroxidase-like activities to realize Cys depletion and further induce cellular ferroptosis and cuproptosis for synergistic tumor therapy. MitCuOHA nanozymes can efficiently catalyze the depletion of Cys and glutathione (GSH), accompanied by the generation of H<sub>2</sub>O<sub>2</sub> and the subsequent conversion into highly active hydroxyl radicals, thereby successfully inducing ferroptosis in cancer cells. Meanwhile, copper ions released by MitCuOHA under tumor microenvironment stimulation directly bind to lipoylated proteins of the tricarboxylic acid cycle, leading to the abnormal aggregation of lipoylated proteins and subsequent loss of iron-sulfur cluster proteins, which ultimately triggers proteotoxic stress and cell cuproptosis. Both in vitro and in vivo results show the drastically enhanced anticancer efficacy of Cys oxidation catalyzed by the MitCuOHA nanozymes, demonstrating the high feasibility of such catalytic Cys depletion-induced synergistic ferroptosis and cuproptosis therapeutic concept.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141174123","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
2D semiconductor heterostructures exhibit broad application prospects. However, regular nanochannels of heterostructures rarely caught the researcher's attention. Herein, a metal-organic framework (i.e., Cu3(HHTP)2) and transition metal dichalcogenides (i.e., MoS2)-based multilayer van der Waals heterostructure (i.e., Cu3(HHTP)2/MoS2) realized band alignment-dominated light-driven ion transport and further light-enhanced ionic energy generation. High-density channels of the heterostructure provide high-speed pathways for ion transmembrane transport. Upon light illumination, a net ionic flow occurs at a symmetric concentration, suggesting a directional cationic transport from Cu3(HHTP)2 to MoS2. This is because Cu3(HHTP)2/MoS2 heterostructures containing type-II band alignment can generate photovoltaic motive force through light-induced efficient charge separation to drive ion transport. After introducing into the ionic power generation system, the maximum power density under illumination can achieve notable improvement under different concentration differences. In addition to the photovoltaic motive force, type-II band alignment and material defect capture-induced surface charge increase also raise ion selectivity and flux, greatly facilitating ionic energy generation. This work demonstrates that 2D semiconductor heterostructures with rational band alignment can not only be a potential platform for optimizing light-enhanced ionic energy harvesting but also provide a new thought for biomimetic iontronic devices.
{"title":"Enhanced Ionic Power Generation via Light-Driven Active Ion Transport Across 2D Semiconductor Heterostructures.","authors":"Yuhui Zhang, Lili Wang, Qing Bian, Chengcheng Zhong, Yupeng Chen, Lei Jiang","doi":"10.1002/smll.202311379","DOIUrl":"10.1002/smll.202311379","url":null,"abstract":"<p><p>2D semiconductor heterostructures exhibit broad application prospects. However, regular nanochannels of heterostructures rarely caught the researcher's attention. Herein, a metal-organic framework (i.e., Cu<sub>3</sub>(HHTP)<sub>2</sub>) and transition metal dichalcogenides (i.e., MoS<sub>2</sub>)-based multilayer van der Waals heterostructure (i.e., Cu<sub>3</sub>(HHTP)<sub>2</sub>/MoS<sub>2</sub>) realized band alignment-dominated light-driven ion transport and further light-enhanced ionic energy generation. High-density channels of the heterostructure provide high-speed pathways for ion transmembrane transport. Upon light illumination, a net ionic flow occurs at a symmetric concentration, suggesting a directional cationic transport from Cu<sub>3</sub>(HHTP)<sub>2</sub> to MoS<sub>2</sub>. This is because Cu<sub>3</sub>(HHTP)<sub>2</sub>/MoS<sub>2</sub> heterostructures containing type-II band alignment can generate photovoltaic motive force through light-induced efficient charge separation to drive ion transport. After introducing into the ionic power generation system, the maximum power density under illumination can achieve notable improvement under different concentration differences. In addition to the photovoltaic motive force, type-II band alignment and material defect capture-induced surface charge increase also raise ion selectivity and flux, greatly facilitating ionic energy generation. This work demonstrates that 2D semiconductor heterostructures with rational band alignment can not only be a potential platform for optimizing light-enhanced ionic energy harvesting but also provide a new thought for biomimetic iontronic devices.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141198647","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Porous polymer membranes as separator plays important roles in separating cathode and anode, storing electrolytes, and transporting ions in energy storage devices. Here, an effective strategy is reported to prepare an electrolyte superwetting membrane, which shows good Li+ transport rate and uniformity, as well as electrode-friendly properties to afford the reduction and oxidation of electrodes. It thereby improves the cycle stability and safety of Li metal batteries. With the arrayed capillaries technique, a thin layer of polyvinylidene fluoride (PVDF) and polyacrylonitrile (PAN) composite is uniformly coated on the surface and pores of polypropylene (PP) membrane with a total thickness of 30 µm. After treating it with n-butyllithium and LiNO3 in turn, a chemically inert membrane with efficient and uniform ion transport is prepared, and the cycle stability of Li||Li symmetric cells is up to 1500 h, 4 times higher than that of PP membrane. Moreover, the Li||LiFePO4 with as-prepared membranes achieve a higher capacity retention rate of 92% after 190 cycles at a current density of 3.6 mA cm-2 and a capacity of 3.6 mAh cm-2, and the Li||NCM721 batteries achieve a capacity retention rate of 71% after 600 cycles at a current density of 1.8 mA cm-2.
多孔聚合物膜作为隔膜在储能设备中的阴阳极分离、电解质存储和离子传输方面发挥着重要作用。本文报告了一种制备电解质超湿润膜的有效策略,该膜具有良好的锂+传输速率和均匀性,以及对电极友好的特性,可承受电极的还原和氧化。从而提高了锂金属电池的循环稳定性和安全性。利用阵列毛细管技术,在聚丙烯(PP)膜的表面和孔隙上均匀涂覆一层薄薄的聚偏二氟乙烯(PVDF)和聚丙烯腈(PAN)复合材料,总厚度为 30 µm。在依次用正丁锂和 LiNO3 对其进行处理后,制备出了具有高效、均匀离子传输的化学惰性膜,锂||锂对称电池的循环稳定性高达 1500 h,是 PP 膜的 4 倍。此外,在电流密度为3.6 mA cm-2、容量为3.6 mAh cm-2的条件下,使用制备的膜的Li||LiFePO4电池在循环190次后的容量保持率达到92%,而Li||NCM721电池在电流密度为1.8 mA cm-2、循环600次后的容量保持率达到71%。
{"title":"Electrolyte Superwetting and Electrode Friendly of Porous Membrane for Better Cycling Stability of Lithium Metal Batteries.","authors":"Yunchong Feng, Xuebing Zhu, Tengfei Bian, Zewen Liu, Long Zhao, Jinhao Wang, Jinling He, Yong Zhao","doi":"10.1002/smll.202401940","DOIUrl":"10.1002/smll.202401940","url":null,"abstract":"<p><p>Porous polymer membranes as separator plays important roles in separating cathode and anode, storing electrolytes, and transporting ions in energy storage devices. Here, an effective strategy is reported to prepare an electrolyte superwetting membrane, which shows good Li<sup>+</sup> transport rate and uniformity, as well as electrode-friendly properties to afford the reduction and oxidation of electrodes. It thereby improves the cycle stability and safety of Li metal batteries. With the arrayed capillaries technique, a thin layer of polyvinylidene fluoride (PVDF) and polyacrylonitrile (PAN) composite is uniformly coated on the surface and pores of polypropylene (PP) membrane with a total thickness of 30 µm. After treating it with n-butyllithium and LiNO<sub>3</sub> in turn, a chemically inert membrane with efficient and uniform ion transport is prepared, and the cycle stability of Li||Li symmetric cells is up to 1500 h, 4 times higher than that of PP membrane. Moreover, the Li||LiFePO<sub>4</sub> with as-prepared membranes achieve a higher capacity retention rate of 92% after 190 cycles at a current density of 3.6 mA cm<sup>-2</sup> and a capacity of 3.6 mAh cm<sup>-2</sup>, and the Li||NCM721 batteries achieve a capacity retention rate of 71% after 600 cycles at a current density of 1.8 mA cm<sup>-2</sup>.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141282572","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01Epub Date: 2024-06-06DOI: 10.1002/smll.202400882
Patrick C Hall, Harrison W Reid, Ievgenii Liashenko, Biranche Tandon, Kelly L O'Neill, Naomi C Paxton, Gabriella C J Lindberg, Ramesh Jasti, Paul D Dalton
Fluorescent probes are an indispensable tool in the realm of bioimaging technologies, providing valuable insights into the assessment of biomaterial integrity and structural properties. However, incorporating fluorophores into scaffolds made from melt electrowriting (MEW) poses a challenge due to the sustained, elevated temperatures that this processing technique requires. In this context, [n]cycloparaphenylenes ([n]CPPs) serve as excellent fluorophores for MEW processing with the additional benefit of customizable emissions profiles with the same excitation wavelength. Three fluorescent blends are used with distinct [n]CPPs with emission wavelengths of either 466, 494, or 533 nm, identifying 0.01 wt% as the preferred concentration. It is discovered that [n]CPPs disperse well within poly(ε-caprolactone) (PCL) and maintain their fluorescence even after a week of continuous heating at 80 °C. The [n]CPP-PCL blends show no cytotoxicity and support counterstaining with commonly used DAPI (Ex/Em: 359 nm/457 nm), rhodamine- (Ex/Em: 542/565 nm), and fluorescein-tagged (Ex/Em: 490/515 nm) phalloidin stains. Using different color [n]CPP-PCL blends, different MEW fibers are sequentially deposited into a semi-woven scaffold and onto a solution electrospun membrane composed of [8]CPP-PCL as a contrasting substrate for the [10]CPP-PCL MEW fibers. In general, [n]CPPs are potent fluorophores for MEW, providing new imaging options for this technology.
{"title":"[n]Cycloparaphenylenes as Compatible Fluorophores for Melt Electrowriting.","authors":"Patrick C Hall, Harrison W Reid, Ievgenii Liashenko, Biranche Tandon, Kelly L O'Neill, Naomi C Paxton, Gabriella C J Lindberg, Ramesh Jasti, Paul D Dalton","doi":"10.1002/smll.202400882","DOIUrl":"10.1002/smll.202400882","url":null,"abstract":"<p><p>Fluorescent probes are an indispensable tool in the realm of bioimaging technologies, providing valuable insights into the assessment of biomaterial integrity and structural properties. However, incorporating fluorophores into scaffolds made from melt electrowriting (MEW) poses a challenge due to the sustained, elevated temperatures that this processing technique requires. In this context, [n]cycloparaphenylenes ([n]CPPs) serve as excellent fluorophores for MEW processing with the additional benefit of customizable emissions profiles with the same excitation wavelength. Three fluorescent blends are used with distinct [n]CPPs with emission wavelengths of either 466, 494, or 533 nm, identifying 0.01 wt% as the preferred concentration. It is discovered that [n]CPPs disperse well within poly(ε-caprolactone) (PCL) and maintain their fluorescence even after a week of continuous heating at 80 °C. The [n]CPP-PCL blends show no cytotoxicity and support counterstaining with commonly used DAPI (Ex/Em: 359 nm/457 nm), rhodamine- (Ex/Em: 542/565 nm), and fluorescein-tagged (Ex/Em: 490/515 nm) phalloidin stains. Using different color [n]CPP-PCL blends, different MEW fibers are sequentially deposited into a semi-woven scaffold and onto a solution electrospun membrane composed of [8]CPP-PCL as a contrasting substrate for the [10]CPP-PCL MEW fibers. In general, [n]CPPs are potent fluorophores for MEW, providing new imaging options for this technology.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141282559","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01Epub Date: 2024-06-11DOI: 10.1002/smll.202401472
Sebastian Karpf, Nina Glöckner Burmeister, Laurence Dubreil, Shayantani Ghosh, Reka Hollandi, Julien Pichon, Isabelle Leroux, Alessandra Henkel, Valerie Lutz, Jonas Jurkevičius, Alexandra Latshaw, Vasyl Kilin, Tonio Kutscher, Moritz Wiggert, Oscar Saavedra-Villanueva, Alfred Vogel, Robert A Huber, Peter Horvath, Karl Rouger, Luigi Bonacina
The pre-clinical validation of cell therapies requires monitoring the biodistribution of transplanted cells in tissues of host organisms. Real-time detection of these cells in the circulatory system and identification of their aggregation state is a crucial piece of information, but necessitates deep penetration and fast imaging with high selectivity, subcellular resolution, and high throughput. In this study, multiphoton-based in-flow detection of human stem cells in whole, unfiltered blood is demonstrated in a microfluidic channel. The approach relies on a multiphoton microscope with diffractive scanning in the direction perpendicular to the flow via a rapidly wavelength-swept laser. Stem cells are labeled with metal oxide harmonic nanoparticles. Thanks to their strong and quasi-instantaneous second harmonic generation (SHG), an imaging rate in excess of 10 000 frames per second is achieved with pixel dwell times of 1 ns, a duration shorter than typical fluorescence lifetimes yet compatible with SHG. Through automated cell identification and segmentation, morphological features of each individual detected event are extracted and cell aggregates are distinguished from isolated cells. This combination of high-speed multiphoton microscopy and high-sensitivity SHG nanoparticle labeling in turbid media promises the detection of rare cells in the bloodstream for assessing novel cell-based therapies.
{"title":"Harmonic Imaging of Stem Cells in Whole Blood at GHz Pixel Rate.","authors":"Sebastian Karpf, Nina Glöckner Burmeister, Laurence Dubreil, Shayantani Ghosh, Reka Hollandi, Julien Pichon, Isabelle Leroux, Alessandra Henkel, Valerie Lutz, Jonas Jurkevičius, Alexandra Latshaw, Vasyl Kilin, Tonio Kutscher, Moritz Wiggert, Oscar Saavedra-Villanueva, Alfred Vogel, Robert A Huber, Peter Horvath, Karl Rouger, Luigi Bonacina","doi":"10.1002/smll.202401472","DOIUrl":"10.1002/smll.202401472","url":null,"abstract":"<p><p>The pre-clinical validation of cell therapies requires monitoring the biodistribution of transplanted cells in tissues of host organisms. Real-time detection of these cells in the circulatory system and identification of their aggregation state is a crucial piece of information, but necessitates deep penetration and fast imaging with high selectivity, subcellular resolution, and high throughput. In this study, multiphoton-based in-flow detection of human stem cells in whole, unfiltered blood is demonstrated in a microfluidic channel. The approach relies on a multiphoton microscope with diffractive scanning in the direction perpendicular to the flow via a rapidly wavelength-swept laser. Stem cells are labeled with metal oxide harmonic nanoparticles. Thanks to their strong and quasi-instantaneous second harmonic generation (SHG), an imaging rate in excess of 10 000 frames per second is achieved with pixel dwell times of 1 ns, a duration shorter than typical fluorescence lifetimes yet compatible with SHG. Through automated cell identification and segmentation, morphological features of each individual detected event are extracted and cell aggregates are distinguished from isolated cells. This combination of high-speed multiphoton microscopy and high-sensitivity SHG nanoparticle labeling in turbid media promises the detection of rare cells in the bloodstream for assessing novel cell-based therapies.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141305017","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Integrating lithium-ion and metal storage mechanisms to improve the capacity of graphite anode holds the potential to boost the energy density of lithium-ion batteries. However, this approach, typically plating lithium metal onto traditional graphite anodes, faces challenges of safety risks of severe lithium dendrite growth and short circuits due to restricted lithium metal accommodation space and unstable lithium plating in commercial carbonate electrolytes. Herein, a slightly expanded spherical graphite anode is developed with a precisely adjustable expanded structure to accommodate metallic lithium, achieving a well-balanced state of high capacity and stable lithium-ion/metal storage in commercial carbonate electrolytes. This structure also enables fast kinetics of both Li intercalation/de-intercalation and plating/stripping. With a total anode capacity of 1.5 times higher (558 mAh g-1) than graphite, the full cell coupled with a high-loading LiNi0.8Co0.1Mn0.1O2 cathode (13 mg cm-2) under a low N/P ratio (≈1.15) achieves long-term cycling stability (75% of capacity after 200 cycles, in contrast to the fast battery failure after 50 cycles with spherical graphite anode). Furthermore, the capacity of the full cell also reaches a low capacity decay rate of 0.05% per cycle at 0.2 C under the low temperature of -20 °C.
{"title":"A Slightly Expanded Graphite Anode with High Capacity Enabled By Stable Lithium-Ion/Metal Hybrid Storage.","authors":"Tong Li, Yun Cao, Qiuchen Song, Linkai Peng, Xianying Qin, Wei Lv, Feiyu Kang","doi":"10.1002/smll.202403057","DOIUrl":"10.1002/smll.202403057","url":null,"abstract":"<p><p>Integrating lithium-ion and metal storage mechanisms to improve the capacity of graphite anode holds the potential to boost the energy density of lithium-ion batteries. However, this approach, typically plating lithium metal onto traditional graphite anodes, faces challenges of safety risks of severe lithium dendrite growth and short circuits due to restricted lithium metal accommodation space and unstable lithium plating in commercial carbonate electrolytes. Herein, a slightly expanded spherical graphite anode is developed with a precisely adjustable expanded structure to accommodate metallic lithium, achieving a well-balanced state of high capacity and stable lithium-ion/metal storage in commercial carbonate electrolytes. This structure also enables fast kinetics of both Li intercalation/de-intercalation and plating/stripping. With a total anode capacity of 1.5 times higher (558 mAh g<sup>-1</sup>) than graphite, the full cell coupled with a high-loading LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> cathode (13 mg cm<sup>-2</sup>) under a low N/P ratio (≈1.15) achieves long-term cycling stability (75% of capacity after 200 cycles, in contrast to the fast battery failure after 50 cycles with spherical graphite anode). Furthermore, the capacity of the full cell also reaches a low capacity decay rate of 0.05% per cycle at 0.2 C under the low temperature of -20 °C.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141160861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01Epub Date: 2024-05-30DOI: 10.1002/smll.202403170
Haipeng Wang, Chao Zhang, Delu Zhang, Lulu Jiang, Yongsheng Gao, Tao Zhuang, Zhiguo Lv
Constructing I single-atom (ISA) doped CoP electrocatalyst for HER is extremely challenging and has not been reported to date. Herein, an ISA doping-phosphatization strategy is proposed to prepare a novel I single-atom doped P-rich CoPn nanocluster@CoP electrocatalyst (ISA-CoPn/CoP) with enhanced HER performance first. ISA-CoPn/CoP shows a low overpotential of only 44 and 81 mV in 0.5 m H2SO4 solution, to drive a current density of 10 and 100 mA cm-2. ISA and P-rich CoPn nanocluster show unique synergies, which can optimize the H adsorption energy and accelerate the kinetics of HER in the CoP system. The intermediate I─H bond vibration peak is directly observed through in situ Raman testing, demonstrating that ISA doping helps accelerate the HER process. Additionally, the ΔGH of ISA-CoPn/CoP is only 0.05 eV by density functional theory (DFT) calculation, which is conducive to H2 evolution.
构建 I 单原子(ISA)掺杂 CoP 的 HER 电催化剂极具挑战性,迄今为止尚未有相关报道。本文提出了一种 ISA 掺杂-磷化策略,首先制备了一种新型的 I 单原子掺杂富 P CoPn 纳米簇@CoP 电催化剂(ISA-CoPn/CoP),其 HER 性能得到了增强。在 0.5 m H2SO4 溶液中,ISA-CoPn/CoP 的过电位仅为 44 mV 和 81 mV,可驱动 10 mA 和 100 mA cm-2 的电流密度。ISA 和富含 P 的 CoPn 纳米团簇显示出独特的协同作用,可以优化 CoP 系统中 H 的吸附能量并加速 HER 的动力学。通过原位拉曼测试可直接观察到中间的 I─H 键振动峰,这表明 ISA 掺杂有助于加速 HER 过程。此外,通过密度泛函理论(DFT)计算,ISA-CoPn/CoP 的 ΔGH 值仅为 0.05 eV,这有利于 H2 的演化。
{"title":"I Single-Atom Doped P-Rich CoP<sub>n</sub> Nanocluster@CoP with Enhanced HER.","authors":"Haipeng Wang, Chao Zhang, Delu Zhang, Lulu Jiang, Yongsheng Gao, Tao Zhuang, Zhiguo Lv","doi":"10.1002/smll.202403170","DOIUrl":"10.1002/smll.202403170","url":null,"abstract":"<p><p>Constructing I single-atom (I<sub>SA</sub>) doped CoP electrocatalyst for HER is extremely challenging and has not been reported to date. Herein, an I<sub>SA</sub> doping-phosphatization strategy is proposed to prepare a novel I single-atom doped P-rich CoP<sub>n</sub> nanocluster@CoP electrocatalyst (I<sub>SA</sub>-CoP<sub>n</sub>/CoP) with enhanced HER performance first. I<sub>SA</sub>-CoP<sub>n</sub>/CoP shows a low overpotential of only 44 and 81 mV in 0.5 m H<sub>2</sub>SO<sub>4</sub> solution, to drive a current density of 10 and 100 mA cm<sup>-2</sup>. I<sub>SA</sub> and P-rich CoP<sub>n</sub> nanocluster show unique synergies, which can optimize the H adsorption energy and accelerate the kinetics of HER in the CoP system. The intermediate I─H bond vibration peak is directly observed through in situ Raman testing, demonstrating that I<sub>SA</sub> doping helps accelerate the HER process. Additionally, the ΔG<sub>H</sub> of I<sub>SA</sub>-CoP<sub>n</sub>/CoP is only 0.05 eV by density functional theory (DFT) calculation, which is conducive to H<sub>2</sub> evolution.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141174066","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}