Van Du Nguyen, Jieun Park, Seoyeon Choi, Kim Tien Nguyen, Hyungwoo Kim, Jong-Oh Park, Eunpyo Choi
Adoptive cell therapy using natural killer (NK) cells emerges as the next-generation cancer immunotherapy. Based on the intrinsic capability of direct cancer cell necrosis without prior education, a chemotherapeutic, free-drug delivery, NK-cell-based platform can be developed. However, weak targeting of NK cells to solid tumors is observed. In addition, to boost the tumor-killing efficiency, another immune-regulating function should be added to the cells. Herein, a NK-cell-based hybrid system (NK-Robot) conjugated with magnetic nanoparticles (MNPs) that provides 1) efficient guidance of NK cells and 2) targeted delivery of MNPs in situ is demonstrated, taking advantage of a newly designed, stimuli-responsive polymeric linker. Thus, NK cells are allowed to target tumors under magnetic control conditions, and the liberated MNPs effectively reeducate the tumor-associated macrophages (M2) to antitumor macrophages (M1), beneficial for the immunotherapy of tumors. In vivo experiments on BALB/c nude mice further support the finding that NK-Robots effectively inhibit tumor growth.
使用自然杀伤（NK）细胞的适应性细胞疗法已成为下一代癌症免疫疗法。基于 NK 细胞无需事先教育即可直接杀死癌细胞的内在能力，可以开发出一种基于 NK 细胞的化疗、自由给药平台。然而，NK 细胞对实体瘤的靶向性较弱。此外，要想提高杀灭肿瘤的效率，还需要在细胞中加入另一种免疫调节功能。本文展示了一种基于 NK 细胞的混合系统（NK-Robot），该系统与磁性纳米粒子（MNPs）连接，利用新设计的刺激响应型聚合物连接体，可提供：1）NK 细胞的高效引导；2）MNPs 的原位靶向递送。这样，NK 细胞就能在磁控制条件下靶向肿瘤，而释放的 MNPs 能有效地将肿瘤相关巨噬细胞（M2）再教育为抗肿瘤巨噬细胞（M1），从而有利于肿瘤的免疫治疗。在 BALB/c 裸鼠身上进行的体内实验进一步证实了 NK-Robots 能有效抑制肿瘤生长的结论。
{"title":"pH-Sensitive Magnetic Nanoparticle-Mediated Natural-Killer-Cell-Based Microrobots for Dual-Targeted Delivery and Induction of Pro-Inflammatory Macrophage Polarization","authors":"Van Du Nguyen, Jieun Park, Seoyeon Choi, Kim Tien Nguyen, Hyungwoo Kim, Jong-Oh Park, Eunpyo Choi","doi":"10.1002/sstr.202400149","DOIUrl":"https://doi.org/10.1002/sstr.202400149","url":null,"abstract":"Adoptive cell therapy using natural killer (NK) cells emerges as the next-generation cancer immunotherapy. Based on the intrinsic capability of direct cancer cell necrosis without prior education, a chemotherapeutic, free-drug delivery, NK-cell-based platform can be developed. However, weak targeting of NK cells to solid tumors is observed. In addition, to boost the tumor-killing efficiency, another immune-regulating function should be added to the cells. Herein, a NK-cell-based hybrid system (NK-Robot) conjugated with magnetic nanoparticles (MNPs) that provides 1) efficient guidance of NK cells and 2) targeted delivery of MNPs in situ is demonstrated, taking advantage of a newly designed, stimuli-responsive polymeric linker. Thus, NK cells are allowed to target tumors under magnetic control conditions, and the liberated MNPs effectively reeducate the tumor-associated macrophages (M2) to antitumor macrophages (M1), beneficial for the immunotherapy of tumors. In vivo experiments on BALB/c nude mice further support the finding that NK-Robots effectively inhibit tumor growth.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218358","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Naresh-Kumar Pendyala, Cedric Gonzales, Antonio Guerrero
Halide perovskite is very attractive for the fabrication of energy-efficient memristors for neuromorphic applications. However, reproducibility, stability, and understanding the switching behavior still lag in comparison to other technologies. Herein, a deep-level understanding of perovskite memristors is obtained by the development of highly reproducible devices. The approach is based on a highly stable perovskite formulation (MAPbBr3) and the use of preoxidized silver (AgI) as a buffer layer. Here, reliable perovskite memristors with device yields approaching 100%, stabilities of >104 cycles for volatile response, and adequate conditions for linear potentiation/depression for nonvolatile response are demonstrated. Using these devices, the nature of the dual volatile and nonvolatile response is understood. It is shown that applying short SET voltage (VSET) pulses leads to ion displacement inside the perovskite material with the formation of an ionic double layer close to the contacts. The displacement of the ions contributes to the series resistance of the device and to a volatile response with ions diffusing back to the perovskite at V < VSET. Alternatively, long VSET pulses lead to a gradual increase in current, the appearance of a chemical inductor, and a nonvolatile response. The observed nonvolatile regime is related to the formation of Ag+ conductive filaments.
卤化物包晶对于制造用于神经形态应用的高能效忆阻器极具吸引力。然而，与其他技术相比，可重复性、稳定性和对开关行为的理解仍然落后。在本文中，通过开发高度可重现的器件，我们对包晶体忆阻器有了深层次的了解。该方法基于一种高度稳定的过氧化物配方（MAPbBr3），并使用预氧化银（AgI）作为缓冲层。在这里，我们展示了可靠的过氧化物忆阻器，其器件产量接近 100%，挥发性响应的稳定性达到 104 个周期，非挥发性响应的线性增效/抑制条件充分。通过使用这些器件，我们了解了易失性和非易失性双响应的性质。研究表明，施加短 SET 电压（VSET）脉冲会导致过氧化物材料内部的离子位移，并在触点附近形成离子双层。离子的位移会增加器件的串联电阻，并导致离子在 V < VSET 时扩散回包晶的波动响应。另一种情况是，长 VSET 脉冲导致电流逐渐增加，出现化学感应和非挥发性响应。观察到的非挥发性机制与 Ag+ 导电丝的形成有关。
{"title":"Decoupling Volatile and Nonvolatile Response in Reliable Halide Perovskite Memristors","authors":"Naresh-Kumar Pendyala, Cedric Gonzales, Antonio Guerrero","doi":"10.1002/sstr.202400380","DOIUrl":"https://doi.org/10.1002/sstr.202400380","url":null,"abstract":"Halide perovskite is very attractive for the fabrication of energy-efficient memristors for neuromorphic applications. However, reproducibility, stability, and understanding the switching behavior still lag in comparison to other technologies. Herein, a deep-level understanding of perovskite memristors is obtained by the development of highly reproducible devices. The approach is based on a highly stable perovskite formulation (MAPbBr<sub>3</sub>) and the use of preoxidized silver (AgI) as a buffer layer. Here, reliable perovskite memristors with device yields approaching 100%, stabilities of >10<sup>4</sup> cycles for volatile response, and adequate conditions for linear potentiation/depression for nonvolatile response are demonstrated. Using these devices, the nature of the dual volatile and nonvolatile response is understood. It is shown that applying short SET voltage (<i>V</i><sub>SET</sub>) pulses leads to ion displacement inside the perovskite material with the formation of an ionic double layer close to the contacts. The displacement of the ions contributes to the series resistance of the device and to a volatile response with ions diffusing back to the perovskite at <i>V</i> < <i>V</i><sub>SET</sub>. Alternatively, long <i>V</i><sub>SET</sub> pulses lead to a gradual increase in current, the appearance of a chemical inductor, and a nonvolatile response. The observed nonvolatile regime is related to the formation of Ag<sup>+</sup> conductive filaments.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218332","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jun-Woo Lee, Jong Ho Won, Woosup Kim, Jwa-Bin Jeon, Myung-Yeon Cho, Sunghoon Kim, Minkyung Kim, Chulhwan Park, Weon Ho Shin, Kanghee Won, Sang-Mo Koo, Jong-Min Oh
With the increasing demand for modern high-voltage electronic devices in electric vehicles and renewable-energy systems, power semiconductor devices with high breakdown fields are becoming essential. β-Gallium oxide (Ga2O3), which has a theoretical breakdown field of 8 MV cm−1, is being studied as a next-generation power-switch material. However, realizing a breakdown field close to this theoretical value remains challenging. In this study, an aerosol deposition-manufactured Ga2O3 film boasting an extremely high breakdown field, achieved through thickness optimization, heat treatment, and a unique nozzle-tilting method, is developed. This study explores the effect of oxygen vacancies on the dielectric constant, breakdown field, and microstructure of Ga2O3 films. Through these methods, Ga2O3 films with a denser (98.88%) and uniform surface, made less affected by oxygen vacancies through nozzle tilting and post-annealing at 800 °C, are produced, resulting in appropriate dielectric constants (9.3 at 10 kHz), low leakage currents (5.8 × 10−11 A cm−2 at 20 kV cm−1), and a very high breakdown field of 5.5 MV cm−1. The results of this study suggest that aerosol-deposited Ga2O3 layers have great potential to enable power switches with reliable switching.
{"title":"Ultrahigh Breakdown Field in Gallium (III) Oxide Dielectric Structure Fabricated by Novel Aerosol Deposition Method","authors":"Jun-Woo Lee, Jong Ho Won, Woosup Kim, Jwa-Bin Jeon, Myung-Yeon Cho, Sunghoon Kim, Minkyung Kim, Chulhwan Park, Weon Ho Shin, Kanghee Won, Sang-Mo Koo, Jong-Min Oh","doi":"10.1002/sstr.202400321","DOIUrl":"https://doi.org/10.1002/sstr.202400321","url":null,"abstract":"With the increasing demand for modern high-voltage electronic devices in electric vehicles and renewable-energy systems, power semiconductor devices with high breakdown fields are becoming essential. β-Gallium oxide (Ga<sub>2</sub>O<sub>3</sub>), which has a theoretical breakdown field of 8 MV cm<sup>−1</sup>, is being studied as a next-generation power-switch material. However, realizing a breakdown field close to this theoretical value remains challenging. In this study, an aerosol deposition-manufactured Ga<sub>2</sub>O<sub>3</sub> film boasting an extremely high breakdown field, achieved through thickness optimization, heat treatment, and a unique nozzle-tilting method, is developed. This study explores the effect of oxygen vacancies on the dielectric constant, breakdown field, and microstructure of Ga<sub>2</sub>O<sub>3</sub> films. Through these methods, Ga<sub>2</sub>O<sub>3</sub> films with a denser (98.88%) and uniform surface, made less affected by oxygen vacancies through nozzle tilting and post-annealing at 800 °C, are produced, resulting in appropriate dielectric constants (9.3 at 10 kHz), low leakage currents (5.8 × 10<sup>−11 </sup>A cm<sup>−2</sup> at 20 kV cm<sup>−1</sup>), and a very high breakdown field of 5.5 MV cm<sup>−1</sup>. The results of this study suggest that aerosol-deposited Ga<sub>2</sub>O<sub>3</sub> layers have great potential to enable power switches with reliable switching.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218334","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qile Li, Shuochen Fan, Xiaodong Luan, Ke Xu, Xianqi Wei, Qinlin Shao, Huaping Peng, Linxing Shi
All-inorganic perovskite CsPbBr3 (CPB) nanocrystals (NCs) are not widely applied in aqueous environments due to their readily decomposable nature. Therefore, the aqueous-phase preparation of CPB NCs has been a considerable challenge. In this work, a feasible method is proposed for preparing aqueous-phase core–shell CPB nanorods (NRs) encapsulated with polydopamine (PDA) by employing a multifunctional additive cesium trifluoroacetate (Cs-TFA). Highly luminescent TFA-CPB NRs are obtained via a chemical transformation of Cs4PbBr6 NCs in water. Subsequently, PDA constitutes a robust shell on the surface of TFA-CPB NRs through the covalent oxidative polymerization, which effectively reduces the original dynamic properties of surface ligands, retards the decomposition of ligands and inhibits the leakage of Pb2+ ions. The results demonstrate that the fluorescence intensity of TFA-CPB@PDA NRs maintains 49.3% of the initial intensity after 136 days. Meanwhile, the NRs exhibit low cytotoxicity, and the cell viability remains at 80% when the concentration of the NRs is 200 μg mL−1. The reliable preparation of aqueous-phase core–shell perovskite NRs (PNRs) will facilitate their development in many fields, such as materials science, biology, medicine, and their applications in aqueous environments.
{"title":"Aqueous-Phase Preparation of Core–Shell Perovskite Nanorods Encapsulated in Polydopamine with Ultrahigh Water Stability","authors":"Qile Li, Shuochen Fan, Xiaodong Luan, Ke Xu, Xianqi Wei, Qinlin Shao, Huaping Peng, Linxing Shi","doi":"10.1002/sstr.202400182","DOIUrl":"https://doi.org/10.1002/sstr.202400182","url":null,"abstract":"All-inorganic perovskite CsPbBr<sub>3</sub> (CPB) nanocrystals (NCs) are not widely applied in aqueous environments due to their readily decomposable nature. Therefore, the aqueous-phase preparation of CPB NCs has been a considerable challenge. In this work, a feasible method is proposed for preparing aqueous-phase core–shell CPB nanorods (NRs) encapsulated with polydopamine (PDA) by employing a multifunctional additive cesium trifluoroacetate (Cs-TFA). Highly luminescent TFA-CPB NRs are obtained via a chemical transformation of Cs<sub>4</sub>PbBr<sub>6</sub> NCs in water. Subsequently, PDA constitutes a robust shell on the surface of TFA-CPB NRs through the covalent oxidative polymerization, which effectively reduces the original dynamic properties of surface ligands, retards the decomposition of ligands and inhibits the leakage of Pb<sup>2+</sup> ions. The results demonstrate that the fluorescence intensity of TFA-CPB@PDA NRs maintains 49.3% of the initial intensity after 136 days. Meanwhile, the NRs exhibit low cytotoxicity, and the cell viability remains at 80% when the concentration of the NRs is 200 μg mL<sup>−1</sup>. The reliable preparation of aqueous-phase core–shell perovskite NRs (PNRs) will facilitate their development in many fields, such as materials science, biology, medicine, and their applications in aqueous environments.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218333","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mingliang He, Jia Qiao, Binghua Zhou, Jie Wang, Shien Guo, Gan Jet Hong Melvin, Mingxi Wang, Hironori Ogata, Yoong Ahm Kim, Masaki Tanemura, Shuwen Wang, Mauricio Terrones, Morinobu Endo, Fei Zhang, Zhipeng Wang
Layered double hydroxide (LDH) is considered a highly promising electrode material for supercapacitors (SCs) due to its high theoretical specific capacitance. However, LDH powders often suffer from poor electrical conductivity, structure pulverization, slow charge transport, and insufficient active sites. Herein, a self-supporting electrode with a Mott–Schottky heterostructure has been designed for high-performance SCs. The electrode consists of low crystallinity NiCo-LDH nanosheets and vertical graphene (VG) directly grown on carbon cloth. The LDH was converted from a metal–organic framework (MOF) by the sol–gel method. This self-supporting electrode provides fast charge transfer, reducing the pulverization effect and energy barrier. The Mott–Schottky heterostructure of LDH@VG regulates electron density and enhances electron transfer, as confirmed by density functional theory calculation. The optimized LDH@VG heterostructure electrode exhibits an excellent areal capacitance of 5513.8 mF cm−2 and rate capability of 82.1%. Furthermore, the fabricated hybrid SC demonstrates excellent energy density of 404.8 μWh cm−2 at 1.6 mW cm−2 and a remarkable cycling life, with a capacitance of 92.0% after 10 000 cycles. This work not only provides a simple dip-coating and MOF conversion method to synthesize heterojunction-based electrodes, but also broadens the horizon for designing advanced electrode materials for SCs.
{"title":"Controllable Metal–Organic Framework-Derived NiCo-Layered Double Hydroxide Nanosheets on Vertical Graphene as Mott–Schottky Heterostructure for High-Performance Hybrid Supercapacitor","authors":"Mingliang He, Jia Qiao, Binghua Zhou, Jie Wang, Shien Guo, Gan Jet Hong Melvin, Mingxi Wang, Hironori Ogata, Yoong Ahm Kim, Masaki Tanemura, Shuwen Wang, Mauricio Terrones, Morinobu Endo, Fei Zhang, Zhipeng Wang","doi":"10.1002/sstr.202400207","DOIUrl":"https://doi.org/10.1002/sstr.202400207","url":null,"abstract":"Layered double hydroxide (LDH) is considered a highly promising electrode material for supercapacitors (SCs) due to its high theoretical specific capacitance. However, LDH powders often suffer from poor electrical conductivity, structure pulverization, slow charge transport, and insufficient active sites. Herein, a self-supporting electrode with a Mott–Schottky heterostructure has been designed for high-performance SCs. The electrode consists of low crystallinity NiCo-LDH nanosheets and vertical graphene (VG) directly grown on carbon cloth. The LDH was converted from a metal–organic framework (MOF) by the sol–gel method. This self-supporting electrode provides fast charge transfer, reducing the pulverization effect and energy barrier. The Mott–Schottky heterostructure of LDH@VG regulates electron density and enhances electron transfer, as confirmed by density functional theory calculation. The optimized LDH@VG heterostructure electrode exhibits an excellent areal capacitance of 5513.8 mF cm<sup>−2</sup> and rate capability of 82.1%. Furthermore, the fabricated hybrid SC demonstrates excellent energy density of 404.8 μWh cm<sup>−2</sup> at 1.6 mW cm<sup>−2</sup> and a remarkable cycling life, with a capacitance of 92.0% after 10 000 cycles. This work not only provides a simple dip-coating and MOF conversion method to synthesize heterojunction-based electrodes, but also broadens the horizon for designing advanced electrode materials for SCs.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218352","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Subin Kim, Ki-Yeop Cho, JunHwa Kwon, Kiyeon Sim, KwangSup Eom, Thomas F. Fuller
Lithium-metal anodes (LMAs) are the ultimate choice for realizing high-energy-density batteries; however, its use is hindered by problematic Li growth in the form of dendrites. To alleviate dendritic Li growth, the preparation of LMAs with a lithiophilic current collector (CC) is effective; however, applying a lithiophilic CC to LMAs is still challenging due to the manufacturing complexity involved in the separate lithiophilic treatment and lithiation processes. Herein, a facile one-pot LMA fabrication method by utilizing thiourea (TU) as a precursor is proposed. A lithiophilic Cu2S layer is formed on Cu foam (CF) by the in situ electrochemical oxidation of TU (CuxSCF), and the lithiation of CC is performed via subsequent Li electrodeposition (Li@CuxSCF). The Cu2S on CuxSCF can lead to uniform Li deposition by providing lithiophilic sites, and it is converted to form ionic-conductive Li2S-rich solid electrolyte interphase layer. Resultantly, CuxSCF significantly enhances the cycling performance of LMAs compared to CF. Specifically, a LiFePO4/Li@CuxSCF full-cell lithium-metal battery (LMB) with a low n/p ratio (1.6) exhibits capacity retention of 95.6% at 0.5 C (220 cycles) and can maintain 85.0% of initial capacity (425 cycles, n/p = 4) at 2.0 C. LMBs with LiNi0.6Co0.2Mn0.2 and LiNi0.8Co0.1Mn0.1 also exhibit improved electrochemical performance.
{"title":"In Situ Electrochemical Interfacial Manipulation Enabling Lithiophilic Li Metal Anode with Inorganic-Rich Solid Electrolyte Interphases for Stable Li Metal Batteries","authors":"Subin Kim, Ki-Yeop Cho, JunHwa Kwon, Kiyeon Sim, KwangSup Eom, Thomas F. Fuller","doi":"10.1002/sstr.202400254","DOIUrl":"https://doi.org/10.1002/sstr.202400254","url":null,"abstract":"Lithium-metal anodes (LMAs) are the ultimate choice for realizing high-energy-density batteries; however, its use is hindered by problematic Li growth in the form of dendrites. To alleviate dendritic Li growth, the preparation of LMAs with a lithiophilic current collector (CC) is effective; however, applying a lithiophilic CC to LMAs is still challenging due to the manufacturing complexity involved in the separate lithiophilic treatment and lithiation processes. Herein, a facile one-pot LMA fabrication method by utilizing thiourea (TU) as a precursor is proposed. A lithiophilic Cu<sub>2</sub>S layer is formed on Cu foam (CF) by the in situ electrochemical oxidation of TU (Cu<sub><i>x</i></sub>SCF), and the lithiation of CC is performed via subsequent Li electrodeposition (Li@Cu<sub><i>x</i></sub>SCF). The Cu<sub>2</sub>S on Cu<sub><i>x</i></sub>SCF can lead to uniform Li deposition by providing lithiophilic sites, and it is converted to form ionic-conductive Li<sub>2</sub>S-rich solid electrolyte interphase layer. Resultantly, Cu<sub><i>x</i></sub>SCF significantly enhances the cycling performance of LMAs compared to CF. Specifically, a LiFePO<sub>4</sub>/Li@Cu<sub><i>x</i></sub>SCF full-cell lithium-metal battery (LMB) with a low <i>n</i>/<i>p</i> ratio (1.6) exhibits capacity retention of 95.6% at 0.5 C (220 cycles) and can maintain 85.0% of initial capacity (425 cycles, <i>n</i>/<i>p</i> = 4) at 2.0 C. LMBs with LiNi<sub>0.6</sub>Co<sub>0.2</sub>Mn<sub>0.2</sub> and LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub> also exhibit improved electrochemical performance.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218354","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jeongha Eom, Yun Seong Cho, Jihun Lee, Jae Won Heo, Iva Plutnarová, Zdeněk Sofer, In Soo Kim, Dongjoon Rhee, Joohoon Kang
Electrochemical water splitting has received tremendous attention as an eco-friendly approach to produce hydrogen. Noble metals and their oxides are commonly used as electrocatalysts to reduce activation energy barriers for hydrogen and oxygen evolution reactions in high-performance electrodes, but their cost, scarcity, and limited stability hinder widespread adoption of electrochemical water splitting. Further advancements are therefore needed to reduce reliance on noble metals and improve the long-term stability. Herein, solution-processed 2D van der Waals (vdW) p–n heterostructures as an interfacial layer between catalysts and the electrode are introduced to enhance the catalytic performance. These heterostructures are formed by sequentially assembling electrochemically exfoliated black phosphorus and molybdenum disulfide nanosheets into electronic-grade p- and n-type semiconductor thin films, with the scalability extending across tens-of-centimeter scale areas. Benefiting from the charge distribution and built-in electric field developed upon heterojunction formation, the vdW heterostructure interfacial layer increases both the catalytic activity and stability of commercial Pt/C and Ir/C catalysts compared to when these catalysts are directly loaded onto electrodes. Additionally, the vdW heterostructure also serves as a template for synthesizing nanostructured Pt and Ir catalysts through electrodeposition, further enhancing the catalytic performance in terms of mass activity and stability.
电化学水分离作为一种生态友好型制氢方法受到了极大关注。贵金属及其氧化物通常用作电催化剂，以降低高性能电极中氢和氧进化反应的活化能障碍，但其成本、稀缺性和有限的稳定性阻碍了电化学分水技术的广泛应用。因此，需要进一步的进步来减少对贵金属的依赖，并提高其长期稳定性。本文引入溶液加工的二维范德华（vdW）p-n 异质结构作为催化剂与电极之间的界面层，以提高催化性能。这些异质结构是通过将电化学剥离的黑磷和二硫化钼纳米片依次组装成电子级 p 型和 n 型半导体薄膜而形成的，其可扩展性可延伸至数十厘米的区域。得益于异质结形成时产生的电荷分布和内置电场，vdW 异质结构界面层提高了商用 Pt/C 和 Ir/C 催化剂的催化活性和稳定性，而不是直接将这些催化剂装载到电极上。此外，vdW 异质结构还可作为通过电沉积合成纳米结构铂和铱催化剂的模板，进一步提高催化活性和稳定性。
{"title":"Scalable 2D Semiconductor-Based van der Waals Heterostructure Interface with Built-in Electric Field for Enhanced Electrochemical Water Splitting","authors":"Jeongha Eom, Yun Seong Cho, Jihun Lee, Jae Won Heo, Iva Plutnarová, Zdeněk Sofer, In Soo Kim, Dongjoon Rhee, Joohoon Kang","doi":"10.1002/sstr.202400257","DOIUrl":"https://doi.org/10.1002/sstr.202400257","url":null,"abstract":"Electrochemical water splitting has received tremendous attention as an eco-friendly approach to produce hydrogen. Noble metals and their oxides are commonly used as electrocatalysts to reduce activation energy barriers for hydrogen and oxygen evolution reactions in high-performance electrodes, but their cost, scarcity, and limited stability hinder widespread adoption of electrochemical water splitting. Further advancements are therefore needed to reduce reliance on noble metals and improve the long-term stability. Herein, solution-processed 2D van der Waals (vdW) p–n heterostructures as an interfacial layer between catalysts and the electrode are introduced to enhance the catalytic performance. These heterostructures are formed by sequentially assembling electrochemically exfoliated black phosphorus and molybdenum disulfide nanosheets into electronic-grade p- and n-type semiconductor thin films, with the scalability extending across tens-of-centimeter scale areas. Benefiting from the charge distribution and built-in electric field developed upon heterojunction formation, the vdW heterostructure interfacial layer increases both the catalytic activity and stability of commercial Pt/C and Ir/C catalysts compared to when these catalysts are directly loaded onto electrodes. Additionally, the vdW heterostructure also serves as a template for synthesizing nanostructured Pt and Ir catalysts through electrodeposition, further enhancing the catalytic performance in terms of mass activity and stability.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218356","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Gwan Hyeon Park, Won-Gwang Lim, Yun Ho Jeong, Song Kyu Kang, Minho Kim, Junhyuk Ji, Jungseub Ha, Sandya Rani Mangishetti, Subin Kim, Yeji Park, Changshin Jo, Won Bae Kim
Electrolyte modification with a high donor-number solvent is necessary to increase sulfur utilization, but it also presents poor compatibility with lithium metal. The amount of the solvent should be optimized to maximize sulfur utilization at the cathode and minimize side reactions with Li metal at the anode. An electrolyte solution comprising 1 vol% N,N-dimethylacetamide (DMA) in a 1,2-dimethoxyethane (DME)/1,3-dioxolane (DOL) co-solvent demonstrated increased discharge capacity and reduced overpotential compared to DME/DOL and DMA/DOL. In addition to electrolyte, modification that creates radical-mediated pathways from a high donor-number solvent, long-cycle performance is achieved by effectively mitigating the shuttling effect and enhancing reaction kinetics with an efficient electrocatalyst. Cobalt doping into TiN introduced an upshift of the d-band center with ferromagnetic properties that suppressed the shuttling effect, activated radical-mediated pathways, and facilitated the Li2S conversion. A multifunctional separator fabricated with N-doped carbon-embedded cobalt-doped titanium nitride nanowires (NC-Ti0.95Co0.05N NWs) under 1 vol% DMA electrolyte achieved a discharge capacity of 464.4 mA h g−1 even after 200 cycles at a decay rate of 0.093% per cycle through the synergistic effects of electrolyte and electrocatalyst modifications. This work highlights the importance of ferromagnetic catalysts with a high donor-number solvent for lithium–sulfur (Li–S) batteries.
为了提高硫的利用率，有必要使用高供体数溶剂对电解质进行改性，但这种溶剂与锂金属的兼容性较差。应优化溶剂的用量，以最大限度地提高硫在阴极的利用率，并尽量减少与锂金属在阳极的副反应。与 DME/DOL 和 DMA/DOL 相比，1vol% N,N-二甲基乙酰胺（DMA）与 1,2-二甲氧基乙烷（DME）/1,3-二氧戊环（DOL）共溶剂的电解质溶液提高了放电容量，降低了过电位。除了对电解质进行改性，从高供体数溶剂中创建以自由基为介导的途径外，还通过有效减轻穿梭效应和利用高效电催化剂增强反应动力学来实现长周期性能。在 TiN 中掺入钴会使具有铁磁性的 d 带中心上移，从而抑制穿梭效应，激活以自由基为媒介的途径，促进 Li2S 的转化。通过电解质和电催化剂改性的协同作用，在 1 vol% DMA 电解质下用掺杂 N 的碳嵌入掺钴氮化钛纳米线（NC-Ti0.95Co0.05N NWs）制造的多功能分离器在 200 个循环后仍能达到 464.4 mA h g-1 的放电容量，衰减率为 0.093%/循环。这项工作凸显了具有高供体数溶剂的铁磁催化剂对锂硫（Li-S）电池的重要性。
{"title":"Activation of the Radical-Mediated Pathway and Facilitation of the Li2S Conversion by N-Doped Carbon-Embedded Ti1–xCoxN Nanowires as a Multifunctional Separator with a High Donor-Number Solvent toward Advanced Lithium–Sulfur Batteries","authors":"Gwan Hyeon Park, Won-Gwang Lim, Yun Ho Jeong, Song Kyu Kang, Minho Kim, Junhyuk Ji, Jungseub Ha, Sandya Rani Mangishetti, Subin Kim, Yeji Park, Changshin Jo, Won Bae Kim","doi":"10.1002/sstr.202400293","DOIUrl":"https://doi.org/10.1002/sstr.202400293","url":null,"abstract":"Electrolyte modification with a high donor-number solvent is necessary to increase sulfur utilization, but it also presents poor compatibility with lithium metal. The amount of the solvent should be optimized to maximize sulfur utilization at the cathode and minimize side reactions with Li metal at the anode. An electrolyte solution comprising 1 vol% <i>N</i>,<i>N</i>-dimethylacetamide (DMA) in a 1,2-dimethoxyethane (DME)/1,3-dioxolane (DOL) co-solvent demonstrated increased discharge capacity and reduced overpotential compared to DME/DOL and DMA/DOL. In addition to electrolyte, modification that creates radical-mediated pathways from a high donor-number solvent, long-cycle performance is achieved by effectively mitigating the shuttling effect and enhancing reaction kinetics with an efficient electrocatalyst. Cobalt doping into TiN introduced an upshift of the d-band center with ferromagnetic properties that suppressed the shuttling effect, activated radical-mediated pathways, and facilitated the Li<sub>2</sub>S conversion. A multifunctional separator fabricated with N-doped carbon-embedded cobalt-doped titanium nitride nanowires (NC-Ti<sub>0.95</sub>Co<sub>0.05</sub>N NWs) under 1 vol% DMA electrolyte achieved a discharge capacity of 464.4 mA h g<sup>−1</sup> even after 200 cycles at a decay rate of 0.093% per cycle through the synergistic effects of electrolyte and electrocatalyst modifications. This work highlights the importance of ferromagnetic catalysts with a high donor-number solvent for lithium–sulfur (Li–S) batteries.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Elham Lori Zoudani, Nam-Trung Nguyen, Navid Kashaninejad
Microneedles hold remarkable potential for providing convenient and unique solutions for disease diagnosis and therapy. However, their integration into clinical practices has been slow, primarily due to the challenge of developing models that meet the criteria of a particular application. A comprehensive and systematic analysis of all aspects of microneedle platforms is imperative to overcome this bottleneck. The analysis involves gathering performance-related information and understanding the factors affecting the functionality of microneedles. The performance of microneedles is heavily influenced by parameters such as dimensions, needle shape, array arrangement, and materials (flexible, stretchable, stimuli-responsive, biodegradable). This article presents a fresh perspective on microneedles, introducing concepts toward optimal designs across various microneedle platforms. This includes application, design, fabrication techniques, and understanding how a specific microneedle design can effectively meet the requirements of a particular application. By addressing these crucial issues, further advancement of microneedle technology occurs.
{"title":"Microneedle Optimization: Toward Enhancing Microneedle's Functionality and Breaking the Traditions","authors":"Elham Lori Zoudani, Nam-Trung Nguyen, Navid Kashaninejad","doi":"10.1002/sstr.202400121","DOIUrl":"https://doi.org/10.1002/sstr.202400121","url":null,"abstract":"Microneedles hold remarkable potential for providing convenient and unique solutions for disease diagnosis and therapy. However, their integration into clinical practices has been slow, primarily due to the challenge of developing models that meet the criteria of a particular application. A comprehensive and systematic analysis of all aspects of microneedle platforms is imperative to overcome this bottleneck. The analysis involves gathering performance-related information and understanding the factors affecting the functionality of microneedles. The performance of microneedles is heavily influenced by parameters such as dimensions, needle shape, array arrangement, and materials (flexible, stretchable, stimuli-responsive, biodegradable). This article presents a fresh perspective on microneedles, introducing concepts toward optimal designs across various microneedle platforms. This includes application, design, fabrication techniques, and understanding how a specific microneedle design can effectively meet the requirements of a particular application. By addressing these crucial issues, further advancement of microneedle technology occurs.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218335","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jayasmita Jana, Tata Sanjay Kanna Sharma, Beena Mol Babu, Sabah Ansar, Somnath Chowdhury, Balasubramanian Sriram, Sea-Fue Wang, Sung Gu Kang, Jin Suk Chung, Won Mook Choi, Seung Hyun Hur
In this study, a composite comprising a rare-earth metal, samarium vanadate (SmVO4, SmV), anchored to halloysite nanotube (HNT) making SmV/HNT nanocomposite is synthesized for the sensitive electrochemical determination of furaltadone (FLD) through differential pulse voltammetry analysis based on the synergistic effect of SmV/HNT (the catalytic activity and chemical stability of SmV, which was further boosted by the improved surface area and conductance of HNT). Further, in the microscopic studies, it is revealed that SmV exhibits a tetragonal zircon-type crystalline structure, with I41/amd (141) space group, whereas HNT comprises a multiphase kaolin composition as a gibbsite-like octahedral sheet with multivalency, and the morphological irregularities of the individual constituents are rectified in the composite. The SmV/HNT composite is spray-coated on polyethylene terephthalate sheet, which delivered a promising trace level limit of detection (0.009 μm) over a wide working range (0.05–194.4 μm) for FLD. Furthermore, real sample analysis is performed using human serum, and pharmaceutical tablet and the results reveal exceptional repeatability and sensitivity, indicating the real-time application of SmV/HNT in the pharmaceutical domain.
{"title":"Integration of Samarium Vanadate/Halloysite Nanotubes: Electrochemical Determination of Furaltadone Using Flexible Electrode","authors":"Jayasmita Jana, Tata Sanjay Kanna Sharma, Beena Mol Babu, Sabah Ansar, Somnath Chowdhury, Balasubramanian Sriram, Sea-Fue Wang, Sung Gu Kang, Jin Suk Chung, Won Mook Choi, Seung Hyun Hur","doi":"10.1002/sstr.202400287","DOIUrl":"https://doi.org/10.1002/sstr.202400287","url":null,"abstract":"In this study, a composite comprising a rare-earth metal, samarium vanadate (SmVO<sub>4</sub>, SmV), anchored to halloysite nanotube (HNT) making SmV/HNT nanocomposite is synthesized for the sensitive electrochemical determination of furaltadone (FLD) through differential pulse voltammetry analysis based on the synergistic effect of SmV/HNT (the catalytic activity and chemical stability of SmV, which was further boosted by the improved surface area and conductance of HNT). Further, in the microscopic studies, it is revealed that SmV exhibits a tetragonal zircon-type crystalline structure, with I4<sub>1</sub>/<i>amd</i> (141) space group, whereas HNT comprises a multiphase kaolin composition as a gibbsite-like octahedral sheet with multivalency, and the morphological irregularities of the individual constituents are rectified in the composite. The SmV/HNT composite is spray-coated on polyethylene terephthalate sheet, which delivered a promising trace level limit of detection (0.009 μ<span>m</span>) over a wide working range (0.05–194.4 μ<span>m</span>) for FLD. Furthermore, real sample analysis is performed using human serum, and pharmaceutical tablet and the results reveal exceptional repeatability and sensitivity, indicating the real-time application of SmV/HNT in the pharmaceutical domain.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218346","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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