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A Poly(amino acid)-Based Nanomedicine Strategy: Telomere-Telomerase Axis Targeting and Magnetic Resonance Imaging in Hepatocellular Carcinoma Treatment. 基于聚氨基酸的纳米药物策略:端粒-端粒酶轴靶向和磁共振成像在肝细胞癌治疗中的应用。
IF 9.6 1区 材料科学 Q1 Engineering Pub Date : 2024-06-25 DOI: 10.1021/acs.nanolett.4c01767
Jinguo Zhang, Xiao-Yan Yang, Jiayi Chen, Qiaomei Zhou, Guohua Pan, Yining Wang, Wangping Luo, Jue Hou, Hanxiao Bao, Guoqiao Xu, Guping Tang, Hongzhen Bai, Risheng Yu

Targeting telomere maintenance has emerged as a promising strategy for hepatocellular carcinoma (HCC) treatment. However, given the duality of the telomere-telomerase axis in telomere maintenance, a comprehensive strategy is urgently needed. Herein, we develop a poly(amino acid) (D-PAAs)-based strategy for spatiotemporal codelivery of telomerase inhibitor, BIBR1523, and AKT inhibitor, isobavachalcone. By leveraging D-PAAs' modifiability, we synthesize polymer-inhibitor conjugates (PB and PI) and a folic acid-decorated tumor-targeting vector (PF). These building blocks undergo micellization to fabricate a codelivery nanomedicine (P-BI@P-FA) by exploiting D-PAAs' noncovalent assembly. P-BI@P-FA improves the pharmacokinetics, tumor selectivity, and bioavailability of small molecule inhibitors and initiates a dual telomere-specific inhibition by combining telomerase deactivation with telomere disruption. Furthermore, a hybrid tumor-targeting magnetic nanosystem is designed using D-PAAs and manganese dioxide to showcase magnetic resonance imaging capacities. Our D-PAAs-based strategy addresses the pressing need for telomere-specific HCC treatment while allowing for diagnostic application, presenting a promising avenue for nanomedicine design.

以端粒维持为靶点已成为治疗肝细胞癌(HCC)的一种前景广阔的策略。然而,鉴于端粒-端粒酶轴在端粒维持中的双重性,迫切需要一种全面的策略。在此,我们开发了一种基于聚氨基酸(D-PAAs)的策略,用于端粒酶抑制剂BIBR1523和AKT抑制剂异巴伐醌的时空编码递送。利用 D-PAAs 的可调控性,我们合成了聚合物-抑制剂共轭物(PB 和 PI)和叶酸装饰的肿瘤靶向载体(PF)。通过利用 D-PAAs 的非共价组装,这些构件经过胶束化后制成了一种编码递送纳米药物(P-BI@P-FA)。P-BI@P-FA 改善了小分子抑制剂的药代动力学、肿瘤选择性和生物利用度,并通过结合端粒酶失活和端粒破坏,启动了双重端粒特异性抑制。此外,我们还利用 D-PAAs 和二氧化锰设计了一种混合肿瘤靶向磁性纳米系统,以展示磁共振成像能力。我们基于 D-PAAs 的策略既能满足端粒特异性 HCC 治疗的迫切需要,又能进行诊断应用,为纳米药物设计提供了一个前景广阔的途径。
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引用次数: 0
Atomic-Site-Dependent Pairing Gap in Monolayer FeSe/SrTiO3(001)–(√13 × √13) 单层 FeSe/SrTiO3(001)-(√13 × √13) 中原子-位点相关的配对间隙
IF 10.8 1区 材料科学 Q1 Engineering Pub Date : 2024-06-25 DOI: 10.1021/acs.nanolett.4c02627
Cui Ding, Zhongxu Wei, Wenfeng Dong, Hai Feng, Mingxia Shi, Lili Wang, Jin-Feng Jia, Qi-Kun Xue
The interfacial FeSe/TiO2−δ coupling induces high-temperature superconductivity in monolayer FeSe films. Using cryogenic atomically resolved scanning tunneling microscopy/spectroscopy, we obtained atomic-site dependent surface density of states, work function, and the pairing gap in the monolayer FeSe on the SrTiO3(001)–(√13 × √13)–R33.7° surface. Our results disclosed the out-of-plane Se–Fe–Se triple layer gradient variation, switched DOS for Fe sites on and off TiO5□, and inequivalent Fe sublattices, which gives global spatial modulation of pairing gap contaminants with the (√13 × √13) pattern. Moreover, the coherent lattice coupling induces strong inversion asymmetry and in-plane anisotropy in the monolayer FeSe, which is demonstrated to correlate with the particle–hole asymmetry in coherence peaks. These results disclose delicate atomic-scale correlations between pairing and lattice-electronic coupling in the Bardeen–Cooper–Schrieffer to Bose–Einstein condensation crossover regime, providing insights into understanding the pairing mechanism of multiorbital superconductivity.
FeSe/TiO2-δ界面耦合诱导了单层FeSe薄膜的高温超导性。利用低温原子分辨扫描隧道显微镜/光谱仪,我们获得了SrTiO3(001)-(√13 × √13)-R33.7°表面上单层FeSe的原子位依赖表面态密度、功函数和配对间隙。我们的研究结果揭示了面外硒-铁-硒三层梯度变化、TiO5□上和TiO5□外铁位点的DOS切换以及不等价的铁亚晶格,这使得配对间隙污染物与(√13 × √13)模式产生了全局空间调制。此外,相干晶格耦合在单层硒化铁中引起了强烈的反转不对称和面内各向异性,这被证明与相干峰中的粒子-空穴不对称相关。这些结果揭示了在巴丁-库珀-施里弗到玻色-爱因斯坦凝聚交叉机制中配对与晶格电子耦合之间微妙的原子尺度相关性,为理解多轨道超导的配对机制提供了启示。
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引用次数: 0
Bioclay Enzyme with Bimetal Synergistic Sterilization and Infectious Wound Regeneration 具有双金属协同杀菌和感染性伤口再生功能的生物粘土酶。
IF 9.6 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-24 DOI: 10.1021/acs.nanolett.4c01671
Ying Chen, Shiqi Wei, Rui Li, Weimin Xie and Huaming Yang*, 

Bacteria invasion is the main factor hindering the wound-healing process. However, current antibacterial therapies inevitably face complex challenges, such as the abuse of antibiotics or severe inflammation during treatment. Here, a drug-free bioclay enzyme (Bio-Clayzyme) consisting of Fe2+-tannic acid (TA) network-coated kaolinite nanoclay and glucose oxidase (GOx) was reported to destroy harmful bacteria via bimetal antibacterial therapy. At the wound site, Bio-Clayzyme was found to enhance the generation of toxic hydroxyl radicals for sterilization via cascade catalysis of GOx and Fe2+-mediated peroxidase mimetic activity. Specifically, the acidic characteristics of the infection microenvironment accelerated the release of Al3+ from kaolinite, which further led to bacterial membrane damage and amplified the antibacterial toxicity of Fe2+. Besides, Bio-Clayzyme also performed hemostasis and anti-inflammatory functions inherited from Kaol and TA. By the combination of hemostasis and anti-inflammatory and bimetal synergistic sterilization, Bio-Clayzyme achieves efficient healing of infected wounds, providing a revolutionary approach for infectious wound regeneration.

细菌入侵是阻碍伤口愈合的主要因素。然而,目前的抗菌疗法不可避免地面临着复杂的挑战,如抗生素的滥用或治疗过程中的严重炎症。据报道,一种不含药物的生物陶土酶(Bio-Clayzyme)由Fe2+-单宁酸(TA)网络包覆的高岭石纳米陶土和葡萄糖氧化酶(GOx)组成,可通过双金属抗菌疗法消灭有害细菌。研究发现,在伤口部位,Bio-Clayzyme 可通过 GOx 的级联催化和 Fe2+ 介导的过氧化物酶模拟活性,增强有毒羟基自由基的生成,从而达到杀菌的目的。具体来说,感染微环境的酸性特征加速了高岭石中 Al3+ 的释放,从而进一步导致细菌膜损伤,放大了 Fe2+ 的抗菌毒性。此外,生物黏土酶还继承了高岭石和 TA 的止血和抗炎功能。通过止血消炎和双金属协同杀菌的结合,生物粘土酶实现了感染伤口的高效愈合,为感染性伤口再生提供了一种革命性的方法。
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引用次数: 0
Disparate External Electric Field Effect on the Adsorption and Shear Behavior of Monovalent and Trivalent Ions in Electrolyte Solution 外加电场对电解质溶液中一价离子和三价离子的吸附和剪切行为的不同影响
IF 9.6 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-24 DOI: 10.1021/acs.nanolett.4c01312
Ruiqi Zhao, Tianyi Han*, Chenhui Zhang* and Qingyuan Yu, 

Reducing friction is of great interest, and an external potential applied to the friction pair can regulate lubricity. Electrochemical atomic force microscopy (EC-AFM) is used to study the tribological and adsorption behavior of monovalent and trivalent ionic solutions between charged surfaces. An opposite trend of coefficient of friction (COF) and normal force that varies with the applied electric potential is witnessed. Direct force measurements and theoretical models have disclosed that, for the NaCl solution, the negative electric field reduces the COF by increasing cation adsorption. As for LaCl3 solution, the positive electric field promotes the primary adsorption of anions on HOPG, resulting in the disappearance of the attractive ion–ion correlation between the trivalent ions, thereby reducing the COF. The shear behavior of adsorbed ions in electrolyte solution is sensitive to their valence, because of their different surface force contribution. The study further provides a framework to optimize the design of hydration lubrication.

减少摩擦是人们非常关心的问题,而施加在摩擦副上的外部电势可以调节润滑性。电化学原子力显微镜(EC-AFM)用于研究带电表面之间一价和三价离子溶液的摩擦学和吸附行为。摩擦系数(COF)和法向力的变化趋势与外加电势相反。直接测力和理论模型表明,对于 NaCl 溶液,负电场会增加阳离子吸附力,从而降低 COF。至于 LaCl3 溶液,正电场会促进阴离子在 HOPG 上的主要吸附,导致三价离子之间的吸引力离子-离子相关性消失,从而降低 COF。吸附离子在电解质溶液中的剪切行为对其价态很敏感,因为它们的表面力贡献不同。这项研究进一步为优化水合润滑设计提供了一个框架。
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引用次数: 0
Cavitation-on-a-Chip Enabled Size-Specific Liposomal Drugs for Selective Pharmacokinetics and Pharmacodynamics 芯片空化技术可实现尺寸特异性脂质体药物的选择性药代动力学和药效学。
IF 9.6 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-24 DOI: 10.1021/acs.nanolett.4c02114
Han Shan, Nianzhou Yu, Maike Chen, Qi Sun, Xin Sun, Changsheng Du, Wansong Shang, Zhaoxi Li, Xiongwei Wei, Qibo Lin, Zixi Jiang, Ziyan Chen, Benpeng Zhu, Shuang Zhao*, Zeyu Chen* and Xiang Chen*, 

The size of liposomal drugs has been demonstrated to strongly correlate with their pharmacokinetics and pharmacodynamics. While the microfluidic method successfully achieves the production of liposomes with well-controlled sizes across various buffer/lipid flow rate ratio (FRR) settings, any adjustments to the FRR inevitably influence the concentration, encapsulation efficiency (EE), and stability of liposomal drugs. Here we describe a controllable cavitation-on-a-chip (CCC) strategy that facilitates the precise regulation of liposomal drug size at any desired FRR. The CCC-enabled size-specific liposomes exhibited striking differences in uptake and biodistribution behaviors, thereby demonstrating distinct antitumor efficacy in both tumor-bearing animal and melanoma patient-derived organoid (PDO) models. Intriguingly, as the liposome size decreased to approximately 80 nm, the preferential accumulation of liposomal drugs in the liver transitioned to a predominant enrichment in the kidneys. These findings underscore the considerable potential of our CCC approach in influencing the pharmacokinetics and pharmacodynamics of liposomal nanomedicines.

事实证明,脂质体药物的大小与其药代动力学和药效学密切相关。虽然微流控方法能在不同的缓冲液/脂质流速比(FRR)设置下成功制备出尺寸控制良好的脂质体,但对FRR的任何调整都不可避免地会影响脂质体药物的浓度、包封效率(EE)和稳定性。在此,我们介绍了一种可控的芯片空化(CCC)策略,该策略有助于在任何所需的流速比下精确调节脂质体药物的大小。由 CCC 实现大小特异性的脂质体在吸收和生物分布行为上表现出惊人的差异,从而在肿瘤动物和黑色素瘤患者衍生类器官(PDO)模型中显示出不同的抗肿瘤疗效。耐人寻味的是,当脂质体的尺寸减小到大约 80 纳米时,脂质体药物在肝脏的优先富集转变为在肾脏的主要富集。这些发现强调了我们的 CCC 方法在影响脂质体纳米药物的药代动力学和药效学方面的巨大潜力。
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引用次数: 0
Self-Powered Engineering of Cell Membrane Receptors to On-Demand Regulate Cellular Behaviors 按需调节细胞行为的细胞膜受体自供电工程。
IF 9.6 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-24 DOI: 10.1021/acs.nanolett.4c01080
Hongyan Geng, Shuangcheng Zhi, Xuemin Zhou, Yongcun Yan, Guofang Zhang, Senquan Dai, Shuzhen Lv and Sai Bi*, 

On-demand engineering of cell membrane receptors to nongenetically intervene in cellular behaviors is still a challenge. Herein, a membraneless enzyme biofuel cell-based self-powered biosensor (EBFC-SPB) was developed for autonomously and precisely releasing Zn2+ to initiate DNAzyme-based reprogramming of cell membrane receptors, which further mediates signal transduction to regulate cellular behaviors. The critical component of EBFC-SPB is a hydrogel film on a biocathode which is prepared using a Fe3+-cross-linked alginate hydrogel film loaded with Zn2+ ions. In the working mode in the presence of glucose/O2, the hydrogel is decomposed due to the reduction of Fe3+ to Fe2+, accompanied by rapid release of Zn2+ to specifically activate a Zn2+-responsive DNAzyme nanodevice on the cell surface, leading to the dimerization of homologous or nonhomologous receptors to promote or inhibit cell proliferation and migration. This EBFC-SPB platform provides a powerful “sensing–actuating–treating” tool for chemically regulating cellular behaviors, which holds great promise in precision biomedicine.

按需设计细胞膜受体以非遗传地干预细胞行为仍是一项挑战。在此,我们开发了一种基于无膜酶生物燃料电池的自供电生物传感器(EBFC-SPB),可自主、精确地释放 Zn2+,启动基于 DNA 酶的细胞膜受体重编程,从而进一步介导信号转导,调节细胞行为。EBFC-SPB 的关键部件是生物阴极上的水凝胶膜,该膜是用含有 Zn2+ 离子的 Fe3+ 交联藻酸盐水凝胶膜制备的。在葡萄糖/O2 存在的工作模式下,水凝胶会因 Fe3+ 还原成 Fe2+ 而分解,同时 Zn2+ 快速释放,特异性激活细胞表面的 Zn2+ 响应 DNA 酶纳米器件,导致同源或非同源受体二聚化,从而促进或抑制细胞增殖和迁移。这种 EBFC-SPB 平台为化学调控细胞行为提供了一种强大的 "传感-激活-治疗 "工具,在精准生物医学领域大有可为。
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引用次数: 0
Dielectric Screening inside Carbon Nanotubes 碳纳米管内部的介电屏蔽
IF 9.6 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-24 DOI: 10.1021/acs.nanolett.4c01668
Georgy Gordeev*, Sören Wasserroth, Han Li, Ado Jorio, Benjamin S. Flavel and Stephanie Reich*, 

Dielectric screening plays a vital role in determining physical properties at the nanoscale and affects our ability to detect and characterize nanomaterials using optical techniques. We study how dielectric screening changes electromagnetic fields and many-body effects in nanostructures encapsulated inside carbon nanotubes. First, we show that metallic outer walls reduce the scattering intensity of the inner tube by 2 orders of magnitude compared to that of air-suspended inner tubes, in line with our local field calculations. Second, we find that the dielectric shift of the optical transition energies in the inner walls is greater when the outer tube is metallic than when it is semiconducting. The magnitude of the shift suggests that the excitons in small-diameter inner metallic tubes are thermally dissociated at room temperature if the outer tube is also metallic, and in essence, we observe band-to-band transitions in thin metallic double-walled nanotubes.

介电屏蔽在确定纳米尺度的物理性质方面起着至关重要的作用,并影响着我们利用光学技术检测和表征纳米材料的能力。我们研究了介电屏蔽如何改变封装在碳纳米管内的纳米结构的电磁场和多体效应。首先,我们发现与悬浮在空气中的内管相比,金属外壁将内管的散射强度降低了 2 个数量级,这与我们的局部场计算结果一致。其次,我们发现金属外管比半导体外管的内壁光学转变能量的介电位移更大。转变的幅度表明,如果外管也是金属的,那么小直径金属内管中的激子在室温下会发生热解离,从本质上讲,我们观察到了薄金属双壁纳米管中的带间转变。
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引用次数: 0
Hot Carrier Nanowire Transistors at the Ballistic Limit 弹道极限的热载流子纳米线晶体管
IF 9.6 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-24 DOI: 10.1021/acs.nanolett.4c01197
Mukesh Kumar, Ali Nowzari, Axel R. Persson, Sören Jeppesen, Andreas Wacker, Gerald Bastard, Reine L. Wallenberg, Federico Capasso, Ville F. Maisi and Lars Samuelson*, 

We demonstrate experimentally nonequilibrium transport in unipolar quasi-1D hot electron devices reaching the ballistic limit at room temperature. The devices are realized with heterostructure engineering in nanowires to obtain dopant- and dislocation-free 1D-epitaxy and flexible bandgap engineering. We show experimentally the control of hot electron injection with a graded conduction band profile and the subsequent filtering of hot and relaxed electrons with rectangular energy barriers. The number of electrons passing the barrier depends exponentially on the transport length with a mean-free path of 200–260 nm, and the electrons reach the ballistic transport regime for the shortest devices with 70% of the electrons flying freely through the base electrode and the barrier reflections limiting the transport to the collector.

我们通过实验证明了在室温下达到弹道极限的单极准一维热电子器件的非平衡传输。该器件通过纳米线异质结构工程实现了无掺杂和无位错的一维外延和灵活的带隙工程。我们在实验中展示了利用分级导带轮廓对热电子注入的控制,以及随后利用矩形能垒对热电子和弛豫电子的过滤。通过势垒的电子数量与平均自由路径为 200-260 nm 的传输长度成指数关系,在最短的器件中,电子达到弹道传输状态,70% 的电子自由飞过基极,势垒反射限制了向集电极的传输。
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引用次数: 0
Supertough MXene/Sodium Alginate Composite Fiber Felts Integrated with Outstanding Electromagnetic Interference Shielding and Heating Properties 超级坚韧的 MXene/Sodium Alginate 复合纤维毡集成了出色的电磁干扰屏蔽和加热性能。
IF 9.6 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-24 DOI: 10.1021/acs.nanolett.4c01920
Guoxin Zhao, Chao Sui*, Chenxi Zhao, Yushun Zhao, Gong Cheng, Junjiao Li, Lei Wen, Weizhe Hao, Yuna Sang, Yingchun Zhou, Xiaodong He and Chao Wang*, 

The development of multifunctional MXene-based fabrics for smart textiles and portable devices has garnered significant attention. However, very limited studies have focused on their structure design and associated mechanical properties. Here, the supertough MXene fiber felts composed of MXene/sodium alginate (SA) fibers were fabricated. The fracture strength and bending stiffness of felts can be up to 97.8 MPa and 1.04 N mm2, respectively. Besides, the fracture toughness of felts was evaluated using the classic Griffith theory, yielding to a critical stress intensity factor of 1.79 MPam. In addition, this kind of felt presents outstanding electrothermal conversion performance (up to 119 °C at a voltage of 2.5 V), high cryogenic and high-temperature tolerance of photothermal conversion performance (−196 to 160 °C), and excellent electromagnetic interference (EMI) shielding effectiveness (54.4 dB in the X-band). This work provides new structural design concepts for high-performance MXene-based textiles, broadening their future applications.

用于智能纺织品和便携式设备的基于 MXene 的多功能织物的开发备受关注。然而,对其结构设计和相关机械性能的研究却非常有限。本文制备了由 MXene/海藻酸钠(SA)纤维组成的超韧 MXene 纤维毡。纤维毡的断裂强度和弯曲刚度分别高达 97.8 MPa 和 1.04 N mm2。此外,还利用经典的格里菲斯理论评估了毛毡的断裂韧性,得出临界应力强度因子为 1.79 MPam。此外,这种毛毡还具有出色的电热转换性能(电压为 2.5 V 时温度可达 119 ℃)、高低温和高温光热转换性能(-196 至 160 ℃)以及出色的电磁干扰(EMI)屏蔽效果(X 波段 54.4 dB)。这项工作为基于 MXene 的高性能纺织品提供了新的结构设计理念,拓宽了其未来的应用领域。
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引用次数: 0
Nondefective Vacancy Enhanced Resistive Switching Reliability in Emergent van der Waals Metal Phosphorus Trisulfide-Based Memristive In-Memory Computing Hardware 基于范德华金属三硫化磷的新兴内存计算硬件中的非缺陷空位增强型电阻开关可靠性。
IF 9.6 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-24 DOI: 10.1021/acs.nanolett.4c00212
Yesheng Li*, Yao Xiong, Baoxing Zhai, Lei Yin, Yiling Yu, Hao Wang and Jun He*, 

Two-dimensional-material-based memristors are emerging as promising enablers of new computing systems beyond von Neumann computers. However, the most studied anion-vacancy-enabled transition metal dichalcogenide memristors show many undesirable performances, e.g., high leakage currents, limited memory windows, high programming currents, and limited endurance. Here, we demonstrate that the emergent van der Waals metal phosphorus trisulfides with unconventional nondefective vacancy provide a promising paradigm for high-performance memristors. The different vacancy types (i.e., defective and nondefective vacancies) induced memristive discrepancies are uncovered. The nondefective vacancies can provide an ultralow diffusion barrier and good memristive structure stability giving rise to many desirable memristive performances, including high off-state resistance of 1012 Ω, pA-level programming currents, large memory window up to 109, more than 7-bit conductance states, and good endurance. Furthermore, a high-yield (94%) memristor crossbar array is fabricated and implements multiple image processing successfully, manifesting the potential for in-memory computing hardware.

基于二维材料的忆阻器正在成为超越冯-诺依曼计算机的新型计算系统的有力推动者。然而,研究得最多的阴离子空位过渡金属二掺杂忆阻器显示出许多不理想的性能,例如高漏电流、有限的存储窗口、高编程电流和有限的续航时间。在这里,我们证明了具有非常规非缺陷空位的范德华金属磷三硫化物为高性能忆阻器提供了一种前景广阔的范例。我们揭示了不同空位类型(即缺陷空位和非缺陷空位)引起的忆阻器差异。非缺陷空位能提供超低的扩散势垒和良好的忆阻结构稳定性,从而产生许多理想的忆阻性能,包括 1012 Ω 的高离态电阻、pA 级编程电流、高达 109 的大存储窗口、超过 7 位的电导状态和良好的耐用性。此外,还制造出了一个高产率(94%)的忆阻器横杆阵列,并成功实现了多种图像处理,体现了内存计算硬件的潜力。
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引用次数: 0
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Nano Letters
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