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Tumor-Microenvironment-Responsive Nanosystem for Enhanced Melanoma Immunotherapy via Dual Epigenetic Regulation and Cuproptosis 肿瘤-微环境响应纳米系统通过双表观遗传调控和cuprotosis增强黑色素瘤免疫治疗
IF 5.8 2区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-10-23 Epub Date: 2026-10-09 DOI: 10.1021/acsanm.6c03725
Yuezhu Zhao, Jie Ma, Yue Xu, Zhou Li, Zhaoxu Meng, He Lian, Yiping Mu

As a highly malignant tumor, melanoma is associated with poor prognosis and high recurrence rates. Despite advances in surgery, radiotherapy, chemotherapy, and immunotherapy, drug resistance and immune evasion remain major obstacles. Epigenetic dysregulationsuch as aberrant DNA methylation and histone deacetylationplays a pivotal role in melanoma progression by silencing tumor suppressor genes and promoting immune escape. Although epigenetic therapies have shown promise, single-target strategies often lead to limited efficacy and acquired resistance. Moreover, emerging evidence suggests that cuproptosis, a copper-triggered, mitochondria-dependent cell death modality, is an effective immunogenic mechanism that synergizes with epigenetic reprogramming. Here, we designed a tumor microenvironment-responsive nanosystem (SAHA-CaCO3@DMY-Cu), which can combine dual epigenetic modulation with cuproptosis to overcome tumor immunosuppression. This nanosystem can simultaneously deliver the histone deacetylation inhibitor vorinostat (SAHA) and the DNA methylation inhibitor dihydromyricetin (DMY) and release copper ions to trigger cuproptosis. This nanosystem achieved an 80.7% reduction in tumor growth and triggered a strong immune activation effect, significantly promoting the maturation of dendritic cells and the intratumoral infiltration of CD4+ and CD8+T cells while reducing Treg cells. Transcriptomics analysis confirmed the enrichment of immune-related pathways (for example, the cytokine−cytokine receptor interactions and the TNF signaling pathway) as well as ribosome generation, thereby verifying the dual epigenetic regulation−cuproptosis mechanism. This study demonstrates that the constructed nanosystem can overcome tumor immune evasion, thereby providing a “trinity” model (epigenetic reprogramming, cuproptosis, and immune activation) for enhancing immunotherapy for melanoma, which also provides a valuable paradigm for the treatment of other tumors.

黑色素瘤是一种高度恶性的肿瘤,预后差,复发率高。尽管手术、放疗、化疗和免疫治疗取得了进展,但耐药性和免疫逃避仍然是主要障碍。表观遗传失调,如异常的DNA甲基化和组蛋白去乙酰化,通过沉默肿瘤抑制基因和促进免疫逃逸,在黑色素瘤的进展中起关键作用。虽然表观遗传疗法已显示出希望,但单靶点策略往往导致有限的疗效和获得性耐药性。此外,新出现的证据表明,铜增生是一种铜触发的线粒体依赖性细胞死亡方式,是一种有效的免疫原性机制,可与表观遗传重编程协同作用。在这里,我们设计了一个肿瘤微环境响应纳米系统(SAHA-CaCO3@DMY-Cu),它可以结合双表观遗传调节和铜生长来克服肿瘤免疫抑制。该纳米系统可以同时递送组蛋白去乙酰化抑制剂伏立诺他(SAHA)和DNA甲基化抑制剂二氢杨梅素(DMY),并释放铜离子触发铜还原。该纳米系统使肿瘤生长降低了80.7%,并引发了强烈的免疫激活效应,显著促进了树突状细胞的成熟和肿瘤内CD4+和CD8+T细胞的浸润,同时减少了Treg细胞。转录组学分析证实了免疫相关途径(如细胞因子-细胞因子受体相互作用和TNF信号通路)和核糖体生成的富集,从而验证了双表观遗传调控- cuprotosis机制。本研究表明,构建的纳米系统可以克服肿瘤的免疫逃避,从而为增强黑色素瘤的免疫治疗提供了“三位一体”模型(表观遗传重编程,cupropsis和免疫激活),这也为其他肿瘤的治疗提供了有价值的范例。
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引用次数: 0
Na+-Intercalated Ti3C2Tx/P(VDF-TrFE) Nanofibers Composite for Selective Room-Temperature NO2 Sensing Na+-插层Ti3C2Tx/P(VDF-TrFE)纳米复合纤维选择性室温NO2传感
IF 5.8 2区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-10-23 Epub Date: 2026-10-14 DOI: 10.1021/acsanm.6c03815
Dokyung Kim, Wooyoung Jang, Seungjin Yang, Bosun Lee, Byeong-Sun Park, Jongbaeg Kim, Jaesam Sim

Herein, Na+-intercalated Ti3C2Tx MXene/poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) Nanofiber (NMN) composite gas sensor was fabricated through systematic surface and structural engineering strategies to achieve enhanced NO2 sensing performance at room temperature. NaOH treatment of Ti3C2Tx MXene simultaneously facilitated the replacement of −F surface terminations with O-containing species, resulting in a higher density of O-containing species that serve as active adsorption sites for NO2 molecules, and expanded the interlayer spacing of the MXene sheets through Na+ intercalation, thereby enlarging the physical accessible surface area for NO2 adsorption. Specifically, Na+-intercalation increased the basal d-spacing of Ti3C2Tx from 1.064 to 1.162 nm, demonstrating nanoscale expansion of the layered MXene structure. The functionalized MXene nanosheets are assembled onto electrospun P(VDF-TrFE) nanofibers via dip-coating to further increase surface-to-volume ratio through the three-dimensional porous structure. In this process, the cetyltrimethylammonium bromide (CTAB) is optimized to impart a positive surface charge to the P(VDF-TrFE) nanofibers, thereby enabling robust electrostatic interaction of the negatively charged MXene nanosheets onto the P(VDF-TrFE) nanofiber surface. As a result of these synergistic strategies, the fabricated NMN sensor successfully demonstrated reliable NO2 detection at a concentration as low as 500 ppb at room temperature with a 45.9-fold higher response than its pristine MXene. Furthermore, the sensor exhibited outstanding NO2 selectivity over interfering gases, confirming that the proposed surface and structural engineering optimized the NMN sensor for NO2 detection.

通过系统的表面和结构工程策略,制备了Na+插层Ti3C2Tx MXene/聚偏氟乙烯-共三氟乙烯(P(VDF-TrFE))纳米纤维(NMN)复合气体传感器,提高了室温下NO2的传感性能。NaOH处理Ti3C2Tx MXene同时促进了- F表面末端被含o物质取代,从而使含o物质密度更高,作为NO2分子的活性吸附位点,并通过Na+插入扩大了MXene片的层间距,从而扩大了NO2吸附的物理可达表面积。具体来说,Na+的插入使Ti3C2Tx的基底d间距从1.064 nm增加到1.162 nm,表明层状MXene结构的纳米级扩展。将功能化的MXene纳米片通过浸涂的方式组装到电纺P(VDF-TrFE)纳米纤维上,通过三维多孔结构进一步提高了表面体积比。在这个过程中,十六烷基三甲基溴化铵(CTAB)被优化为赋予P(VDF-TrFE)纳米纤维表面正电荷,从而使带负电荷的MXene纳米片在P(VDF-TrFE)纳米纤维表面产生强大的静电相互作用。由于这些协同策略,制造的NMN传感器成功地证明了在室温下低至500 ppb的浓度下可靠的NO2检测,其响应速度比原始MXene高45.9倍。此外,该传感器对干扰气体表现出出色的NO2选择性,证实了所提出的表面和结构工程优化了NMN传感器对NO2的检测。
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引用次数: 0
Non-Thermal Solid-State Nanojoining of CuO Nanowires Enabled by Femtosecond Laser Shock Waves for Nanoscale Electronic Interconnects 飞秒激光激波实现CuO纳米线非热固态纳米连接的纳米级电子互连
IF 5.8 2区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-10-23 Epub Date: 2026-09-21 DOI: 10.1021/acsanm.6c03426
Xinlan Hu, Maryam Soleimani, Walter Duley, Y. Norman Zhou, Peng Peng

Nanojoining of one-dimensional metal-oxide nanostructures remains challenging because their high melting temperatures and intrinsic brittleness hinder reliable integration into nanoscale electronic systems. Here, we present a two-step femtosecond-laser strategy for predominantly solid-state nanojoining of CuO nanowires through nonequilibrium defect engineering followed by shock-assisted mechanical activation. In the first step, femtosecond-laser pretreatment increases the oxygen-vacancy-related defect density, as supported by XPS measurements, which is associated with lattice softening and enhanced nanoscale plasticity. Quantitative nanoindentation shows corresponding reductions in elastic modulus and hardness, together with an increase in the H/Py ratio from approximately 2.2 to 3.1, indicating a transition toward a more plastic deformation response. In the second step, femtosecond-laser shock peening under the optimized condition generates transient compressive loading that promotes intimate inter-nanowire contact and interfacial bonding. TEM, HRTEM, localized FFT, and SAED analyses of X-type, Y-type, and end-to-end junctions reveal direct atomic-scale contact, preservation of the monoclinic CuO structure, and no observable thick amorphous interlayer, melt−resolidification morphology, or bulk phase transformation. Single-junction electrical measurements further show a current enhancement of up to approximately 35% after optimized shock peening, demonstrating improved electrical transport across the formed junctions. These results establish a vacancy-assisted, shock-mediated solid-state route for integrating brittle CuO nanowires into conductive nanoscale architectures and electronic interconnects.

一维金属氧化物纳米结构的纳米连接仍然具有挑战性,因为它们的高熔化温度和固有的脆性阻碍了可靠地集成到纳米级电子系统中。在这里,我们提出了一种两步飞秒激光策略,通过非平衡缺陷工程和冲击辅助机械激活,以固态为主的CuO纳米线的纳米连接。在第一步中,飞秒激光预处理增加了氧空位相关的缺陷密度,这与XPS测量结果一致,这与晶格软化和纳米级塑性增强有关。定量纳米压痕显示相应的弹性模量和硬度降低,同时H/Py比值从大约2.2增加到3.1,表明向更塑性的变形响应过渡。第二步,在优化条件下,飞秒激光冲击强化产生瞬态压缩载荷,促进纳米线间的紧密接触和界面结合。对x型、y型和端到端结的TEM、HRTEM、局部FFT和SAED分析显示了直接的原子尺度接触,保留了单斜CuO结构,没有观察到厚的非晶间层、熔融再凝固形态或体相转变。单结电测量进一步显示,经过优化的冲击强化后,电流增强了约35%,表明在形成的结之间的电传输得到了改善。这些结果为将脆性CuO纳米线集成到导电纳米级结构和电子互连中建立了一种空位辅助、冲击介导的固态途径。
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引用次数: 0
Magnetic Nanoparticle Transducers for Magnetogenetics: Materials Design, Biointerfaces, and Transduction Mechanisms 磁性纳米粒子换能器的磁遗传学:材料设计,生物界面,和转导机制
IF 5.8 2区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-10-23 Epub Date: 2026-10-09 DOI: 10.1021/acsanm.6c02937
Hanlei Wang, Hansong Zuo, Rui He, Kai Wu

Over the years, magnetic nanoparticles (MNPs) have evolved from passive imaging and delivery agents into active transducers that convert externally applied magnetic fields into localized biological stimuli. This transition has created opportunities for magnetogenetics, in which MNPs serve as remotely controlled biointerfaces for regulating cellular activity, tissue function, and therapeutic responses. In this review, we discuss MNP transducers for magnetogenetics from the perspective of materials design, biointerface engineering, and transduction mechanisms. We start with magnetothermal transduction, where nanoparticles dissipate heat under alternating magnetic fields (AMFs) to activate thermosensitive ion channels such as TRPV1, enabling wireless neuronal activation, deep brain stimulation (DBS), regenerative signaling, and disease therapy. We then discuss magnetomechanical transduction, where nanoparticles, nano/micro-discs, nanochains, etc., generate forces, torques, oscillations, or matrix deformation to activate mechanosensitive channels, integrin-mediated pathways, stem cell differentiation, immune modulation, and tumor inhibition. Next, we examine magnetoelectric transduction, where magnetostrictive-piezoelectric materials convert magnetic inputs into local electric fields or surface potentials for neural stimulation, DBS, nerve regeneration, and wound healing. Across these modalities, biological outcomes are governed by intrinsic magnetic properties and several other factors, including particle geometry, anisotropy, surface chemistry, protein corona formation, tissue retention, field waveform, and proximity to the biological target. We further comment on key design principles, including mechanism-specific dosimetry, geometry-field co-design, biointerface localization, targeting specificity, clearance, and chronic safety. Finally, we highlight opportunities for purpose-built, programmable, and closed-loop magnetic biointerfaces that integrate material architecture, magnetic-field input, and biological target selection for precise control of cellular and tissue function.

多年来,磁性纳米颗粒(MNPs)已经从被动成像和递送剂演变为主动换能器,将外部施加的磁场转化为局部生物刺激。这种转变为磁遗传学创造了机会,在磁遗传学中,MNPs作为远程控制的生物界面来调节细胞活性、组织功能和治疗反应。本文从材料设计、生物界面工程和转导机制等方面对磁遗传学用MNP换能器进行了综述。我们从磁热转导开始,其中纳米颗粒在交变磁场(AMFs)下耗散热量以激活热敏离子通道(如TRPV1),从而实现无线神经元激活、深部脑刺激(DBS)、再生信号传导和疾病治疗。然后我们讨论磁机械转导,其中纳米颗粒、纳米/微盘、纳米链等产生力、扭矩、振荡或基质变形,以激活机械敏感通道、整合素介导的途径、干细胞分化、免疫调节和肿瘤抑制。接下来,我们将研究磁电转导,其中磁致伸缩压电材料将磁输入转换为局部电场或表面电位,用于神经刺激,DBS,神经再生和伤口愈合。在这些模式中,生物结果受固有磁性和其他几个因素的影响,包括颗粒几何形状、各向异性、表面化学、蛋白质电晕形成、组织保留、场波形和与生物靶点的接近程度。我们进一步评论了关键的设计原则,包括机制特异性剂量测定、几何场协同设计、生物界面定位、靶向特异性、清除率和慢性安全性。最后,我们强调了为精确控制细胞和组织功能而集成材料结构、磁场输入和生物靶点选择的专用、可编程和闭环磁性生物接口的机会。
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引用次数: 0
Cellulose Acetate-Based Janus Membrane with Dual-Mode Switching for On-Demand Radiative Cooling and Solar Heating 醋酸纤维素基Janus膜,用于按需辐射冷却和太阳能加热的双模式切换
IF 5.8 2区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-10-23 Epub Date: 2026-10-14 DOI: 10.1021/acsanm.6c03288
Zhi Zhang, Li Lv, Jing Li, Luwen Zhao, Boxuan Zhu, Mingzhu Li, Jinlin Shen, Liangmiao Zhang, Yaping Zhao

Conventional static thermal management materials incur overcooling penalties in cold seasons. In this study, we develop a cellulose acetate-based Janus bilayer membrane that enables on-demand switching between radiative cooling and solar heating via mechanical flipping. Fabricated through a scalable non-solvent-induced phase separation and lamination strategy employing bio-renewable materials, the membrane integrates a BaSO4 cooling side (97.1% solar reflectance, 96.5% mid-infrared emissivity) and an activated carbon heating side (94.0% solar absorptance). multiscale simulationsMie scattering, finite-difference time-domain (FDTD), and COMSOL phase-field and heat-transfer modelingreveal the underlying mechanisms of resonant scattering and hierarchical light-trapping absorption. The dual-mode performance is systematically validated through outdoor ice-melting experiments and small-scale building model tests under real sunlight and xenon-lamp irradiation; in the latter, the two sides maintain a stable 12 °C temperature differential on the same roof. Durability tests confirm >95% optical retention after 1000 abrasion cycles and <4% loss after UV aging. EnergyPlus simulations covering all 34 provincial-level administrative divisions in China demonstrate average cooling and heating energy savings of 68.2% and 39.8%, respectively. This work offers a sustainable, durable, and practically viable solution for year-round building energy conservation.

传统的静态热管理材料在寒冷的季节会导致过冷。在这项研究中,我们开发了一种基于醋酸纤维素的Janus双层膜,可以通过机械翻转在辐射冷却和太阳能加热之间按需切换。该膜采用可扩展的非溶剂诱导相分离和生物可再生材料的层压策略制造,集成了BaSO4冷却侧(97.1%的太阳反射率,96.5%的中红外发射率)和活性炭加热侧(94.0%的太阳吸收率)。多尺度散射模拟、时域有限差分(FDTD)和COMSOL相场和传热模型揭示了共振散射和分层光捕获吸收的潜在机制。通过室外融冰实验和真实阳光和氙灯照射下的小型建筑模型试验,系统验证了双模性能;在后者中,双方在同一屋顶上保持稳定的12°C温差。耐久性测试证实,经过1000次磨损循环后光学保持率为95%,紫外线老化后光学保持率为4%。EnergyPlus覆盖中国所有34个省级行政区划的模拟显示,制冷和供暖平均节能分别为68.2%和39.8%。这项工作为全年的建筑节能提供了一个可持续、持久、实际可行的解决方案。
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引用次数: 0
Peptide-Directed Nanomaterials to Elucidate Compositional Effects in Bimetallic Nanoparticle Catalysts 多肽定向纳米材料阐明双金属纳米颗粒催化剂的组成效应
IF 5.8 2区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-10-23 Epub Date: 2026-10-14 DOI: 10.1021/acsanm.6c04222
Jessen Mathew, Joseph M. Slocik, Krishnamurthy Mahalingam, David M. Phillips, Marc R. Knecht

Multimetallic nanoparticle catalysts present exciting opportunities to achieve sustainable chemical transformations based on their unique structure that can lead to enhanced reactivity, especially when a blend of functional metal atoms is incorporated. The fundamental science regarding the interaction between the metal types and the role of the surface ligands is developing, especially as the number of constituent atom types increases. To investigate these effects, a set of three different bimetallic nanoparticles were prepared (PdAu, AuAg, and PdAg) using the same peptide capping agent (the AuBP1 peptide). Simplified bimetallic materials were probed with a similar interfacial ligand to explore the effect of switching metal composition on catalytic activity, as well as the breadth of compositions that could be prepared using the same peptide ligand. Characterization of the stable structures indicated that bimetallic alloy nanocatalysts were generated with sizes of less than 5 nm in diameter. Catalytic analysis for the reduction of 4-nitrophenol revealed enhanced reactivity for nanoparticles prepared with PdAu and AuAg at metal/metal ratios of 3:2 and 4:1, respectively. These results demonstrate key structural and compositional effects in the materials, which could be used to design different particles of increased complexity for further reactivity enhancement.

多金属纳米颗粒催化剂提供了令人兴奋的机会,基于其独特的结构,可以提高反应活性,特别是当功能金属原子的混合物被掺入时,实现可持续的化学转化。关于金属类型和表面配体作用之间相互作用的基础科学正在发展,特别是随着组成原子类型数量的增加。为了研究这些影响,使用相同的肽盖剂(AuBP1肽)制备了三种不同的双金属纳米颗粒(PdAu, AuAg和PdAg)。用类似的界面配体对简化的双金属材料进行了探测,以探索切换金属组成对催化活性的影响,以及使用相同的肽配体可以制备的组合物的宽度。结构稳定表征表明,制备的双金属合金纳米催化剂的直径小于5 nm。对4-硝基苯酚还原的催化分析表明,在金属/金属比分别为3:2和4:1时,PdAu和AuAg制备的纳米颗粒的反应性增强。这些结果证明了材料中关键的结构和组成效应,可以用来设计不同的颗粒,增加复杂性,进一步提高反应性。
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引用次数: 0
Magnetic Iron Oxide-Decorated Nitrogen-Doped Carbon Nanotube Cups for Drug Delivery 磁性氧化铁修饰氮掺杂碳纳米管杯的药物递送
IF 5.8 2区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-10-23 Epub Date: 2026-10-06 DOI: 10.1021/acsanm.6c02014
Jieyu Wang, Hsuan-Yu Lin, Samia Afrin, Lauren Hino, Faezeh Askari, Sachchidanand Soaham Gupta, Ganesh Kesavan, Paul R. Ohodnicki, Yulia Nefedova, Alexander Star

Nitrogen-doped carbon nanotube cups (NCNCs) exhibited significant potential as drug carriers owing to their unique cup-shaped and hollow nanostructures. To improve the biocompatibility of individual NCNCs, this study employed a bath sonicator and performed a methodical examination of ultrasonic frequency to optimize oxidation and separation efficiency. The NCNCs were further decorated with iron oxide nanoparticles (Fe3O4-NPs) via a co-precipitation method to impart magnetic property to this NCNC-based composite. The biocompatibility of Fe3O4-NCNCs was further confirmed by exposing the composites to hydrogen peroxide (H2O2), triggering the Fenton reaction to achieve degradation. Ultimately, the practicality of Fe3O4-NCNCs as drug delivery carriers was demonstrated by loading the nanocomposites with the ferroptosis inducer RSL3. The in vitro experimental results indicated that the drug-loaded Fe3O4-NCNCs have considerable anti-tumor activity, suggesting Fe3O4-NCNC as a superior drug delivery platform.

氮掺杂碳纳米管杯(NCNCs)由于其独特的杯状和中空纳米结构,在药物载体方面表现出巨大的潜力。为了提高单个NCNCs的生物相容性,本研究采用了浴声器,并对超声频率进行了系统的检查,以优化氧化和分离效率。通过共沉淀法进一步用氧化铁纳米颗粒(Fe3O4-NPs)修饰ncnc,使其具有磁性。通过将fe3o4 - ncnc暴露于过氧化氢(H2O2)中,触发Fenton反应实现降解,进一步证实了Fe3O4-NCNCs的生物相容性。最后,通过将铁下垂诱导剂RSL3加载到纳米复合材料中,证明了Fe3O4-NCNCs作为药物递送载体的实用性。体外实验结果表明,载药Fe3O4-NCNC具有较强的抗肿瘤活性,提示Fe3O4-NCNC是一种较好的给药平台。
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引用次数: 0
Nanoscale Anisotropy of SWCNTs Promotes Enhanced Diffusion in Heterogeneous Complex Fluids 纳米尺度SWCNTs的各向异性促进了非均质复杂流体中的扩散
IF 5.8 2区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-10-23 Epub Date: 2026-10-07 DOI: 10.1021/acsanm.6c03452
Sepehr Yari, Mohammadjavad Haji Rezaei, Leila Chowning, Daniel Roxbury, Ryan Poling-Skutvik

Single-walled carbon nanotubes (SWCNTs) are anisotropic nanoparticles with unique mechanical, electrical, and optical properties. These properties have enabled applications in reinforcing nanocomposites, drug delivery, biosensing, and biomedical imaging, where their performance depends on transport through complex fluids. The mechanisms governing SWCNT transport in structured heterogeneous fluids, however, remain poorly understood because of their multiple characteristic length scales that can be smaller than or comparable to the structural length scales of the surrounding fluid. Here, we investigate the dynamics of SWCNTs in semidilute poly(ethylene oxide) solutions by systematically varying polymer concentration and molecular weight. We directly compare their transport with that of spherical nanoparticles (SNPs) with comparable characteristic dimensions to isolate the effect of particle anisotropy. SWCNTs exhibit substantially enhanced diffusivities up to 300× faster than Stokes−Einstein predictions. These deviations emerge at lower polymer molecular weights and are considerably larger than those observed for SNPs. SWCNT dynamics collapse onto a single curve when plotted as a function of the ratio of nanotube length to the polymer correlation length even well into the entangled regime, whereas SNPs exhibit a steeper power-law decrease that reflects coupling to entanglement dynamics. Moreover, SWCNTs exhibit pronounced non-Gaussian distributions of particle displacements, which confirm that SWCNTs experience different viscosities when transporting along or perpendicular to their length. Our results show that the nanoscale diameter of SWCNTs enables them to avoid constraints imposed by the polymer network and that their anisotropic geometry gives rise to distinct coupling to polymer microstructure and multiple diffusive modes. These findings reveal the mechanisms governing enhanced SWCNT transport and non-Gaussian statistics in structured complex media and provide a framework for predicting SWCNT dynamics in soft matter and biological environments.

单壁碳纳米管(SWCNTs)是具有独特力学、电学和光学特性的各向异性纳米颗粒。这些特性已经应用于增强纳米复合材料、药物输送、生物传感和生物医学成像等领域,它们的性能依赖于通过复杂流体的传输。然而,由于swcnts在结构非均质流体中的多个特征长度尺度可能小于或与周围流体的结构长度尺度相当,因此对其在结构非均质流体中运移的机制仍然知之甚少。在这里,我们通过系统地改变聚合物浓度和分子量来研究SWCNTs在半稀聚环氧乙烷溶液中的动力学。我们直接将它们的输运与具有相似特征尺寸的球形纳米粒子(snp)的输运进行比较,以分离粒子各向异性的影响。SWCNTs的扩散率比Stokes - Einstein预测的要快300倍。这些偏差出现在较低的聚合物分子量上,并且比snp所观察到的偏差大得多。当绘制成纳米管长度与聚合物相关长度之比的函数时,即使进入纠缠状态,swcnts动力学也会崩溃到一条曲线上,而snp则表现出更陡峭的幂律下降,这反映了与纠缠动力学的耦合。此外,SWCNTs表现出明显的颗粒位移非高斯分布,这证实了SWCNTs在沿其长度或垂直于其长度运输时具有不同的粘度。我们的研究结果表明,SWCNTs的纳米级直径使它们能够避免聚合物网络施加的约束,其各向异性几何结构导致了与聚合物微观结构的明显耦合和多种扩散模式。这些发现揭示了结构复杂介质中swcnts输运增强和非高斯统计的机制,并为预测软物质和生物环境中的swcnts动力学提供了框架。
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引用次数: 0
Investigating Competing Effects of Pore Size and Hydrophobicity on Water Adsorption in Nanoporous Metal−Organic Frameworks 研究孔径和疏水性对纳米多孔金属-有机骨架水吸附的影响
IF 5.8 2区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-10-23 Epub Date: 2026-10-08 DOI: 10.1021/acsanm.6c03023
Manel A. Eddaoudi, Courtney S. Smoljan, Julian S. Magdalenski, Owen J. Bailey, Haomiao Xie, Shengyi Su, Kent O. Kirlikovali, Randall Q. Snurr, Omar K. Farha

Metal−organic frameworks (MOFs) are a highly tunable class of porous materials with potential in various applications. One promising area of research is water adsorption, but challenges remain related to stability and control over water uptake properties. In this study, we report the synthesis of NU-2020, which is structurally analogous to MIL-101 but incorporates a ditopic three-dimensional linker (3DL), bicyclo[2.2.2]octane-1,4-dicarboxylic acid (BODCA), with a sterically bulky and higher symmetry core. We investigated how incorporating a 3DL affects both the stability and water adsorption capacity of MIL-101. The incorporation of BODCA is expected to uniformly decrease pore sizes and increase pore hydrophobicity due to increased linker protrusion into the pore space and the presence of additional hydrophobic carbon and hydrogen atoms. These two modifications to the pores are competing effects that drive the relative humidity at which water uptake occurs in different directions. Decreasing the pore sizes is expected to shift the adsorption step to lower relative humidity, and increasing hydrophobicity is expected to shift the step to higher relative humidity. We employed a combination of thermogravimetric analysis, variable-temperature X-ray diffraction, and porosity measurements to characterize the thermal stability of MIL-101 and NU-2020 and evaluated the water uptake properties through a combination of standardized accelerated aging, contact angle measurements, and water sorption isotherms. Our findings indicate that incorporating a 3DL increases the framework’s thermal stability and increases the water adsorption capacity in NU-2020 relative to MIL-101. Moreover, in this system, the two competing effects appear to be negating one another, resulting in minimal shifts in the water isotherm steps.

金属-有机框架(mof)是一类高度可调的多孔材料,在各种应用中具有潜力。一个有前途的研究领域是水吸附,但挑战仍然与稳定性和控制有关的吸水性。在这项研究中,我们报道了NU-2020的合成,它在结构上类似于MIL-101,但包含一个双位三维连接体(3DL),双环[2.2.2]辛烷-1,4-二羧酸(BODCA),具有空间体积大和更高对称性的核心。我们研究了加入3DL如何影响MIL-101的稳定性和水吸附能力。BODCA的掺入有望均匀地减小孔隙尺寸并增加孔隙疏水性,这是由于连接剂向孔隙空间的突出增加以及额外的疏水碳和氢原子的存在。这两种对孔隙的修改是相互竞争的影响,它们驱动着相对湿度,在相对湿度下,水的吸收发生在不同的方向上。减小孔径有望将吸附步骤转移到较低的相对湿度,增加疏水性有望将吸附步骤转移到较高的相对湿度。我们采用热重分析、变温x射线衍射和孔隙度测量相结合的方法来表征MIL-101和NU-2020的热稳定性,并通过标准化加速老化、接触角测量和吸水等温线的组合来评估其吸水性能。我们的研究结果表明,与MIL-101相比,加入3DL增加了框架的热稳定性,并增加了NU-2020中的水吸附能力。此外,在这个系统中,这两种相互竞争的影响似乎是相互抵消的,导致水等温线步骤的最小变化。
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引用次数: 0
Morphotropic Phase Boundary Engineering in HfO2-Based High-k Dielectric Nanosystems for Dynamic Random-Access Memory Capacitors: A Review 基于hfo2的高k介电纳米系统动态随机存取存储器的相变边界工程研究进展
IF 5.8 2区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-10-23 Epub Date: 2026-10-09 DOI: 10.1021/acsanm.6c02035
Hsien-Yang Liu, Thi Minh Thuan Nguyen, Prasannajeet Singh, Sourav De, Yannick Raffel, Maximilian Lederer, Yogesh Singh Chauhan, Chiung-Yuan Lin, Tian-Li Wu

HfO2-based dielectrics engineered into an MPB-like regime have emerged as promising candidates for next-generation dynamic random-access memory (DRAM) capacitors because they offer enhanced dielectric permittivity while preserving the wide bandgap and CMOS compatibility of fluorite-structured oxides. At the nanometer-scale film thicknesses and grain dimensions relevant to DRAM, surface and interface energies, electrode confinement, stress, and defect distributions strongly reshape the relative stability and accessibility of fluorite-derived phases. However, the physical origin of the high-k response and its relationship with leakage current and reliability remain under active discussion. In this review, we summarize recent progress in HfO2-based MPB dielectrics from three perspectives. First, we discuss two complementary interpretations of dielectric enhancement: spatial phase coexistence between orthorhombic and tetragonal phases at the MPB, and dynamic nonlinear dielectric response associated with low transition barriers and field-induced structural evolution. Second, we review major engineering strategies for achieving MPB-like behavior, including stoichiometric and oxygen-vacancy control, advanced annealing processes, doping, bilayer and superlattice heterostructures, and electrode/interface engineering. Third, we evaluate the practical performance and reliability requirements for DRAM applications, with emphasis on the coupled trade-offs among dielectric constant, leakage current, equivalent oxide thickness, and time-dependent dielectric breakdown. Representative reports include k ≈ 67 with a leakage current density of 3 × 10−8 A/cm2 at 0.8 V and, in a separate ultrathin HZO device, an EOT of approximately 2.42 Å with k ≈ 64.24. Finally, we highlight that the optimization of MPB HfO2-based dielectrics requires a holistic design framework that simultaneously considers phase stability, defect dynamics, interface quality, and realistic low-voltage benchmarking conditions.

基于hfo2的电介质被设计成类似mpb的结构,已经成为下一代动态随机存取存储器(DRAM)电容器的有希望的候选者,因为它们提供了增强的介电常数,同时保持了萤石结构氧化物的宽带隙和CMOS兼容性。在纳米尺度上,与DRAM相关的薄膜厚度和晶粒尺寸、表面和界面能量、电极约束、应力和缺陷分布强烈地重塑了萤石衍生相的相对稳定性和可及性。然而,高k响应的物理来源及其与漏电流和可靠性的关系仍在积极讨论中。本文从三个方面综述了基于hfo2的MPB介电材料的研究进展。首先,我们讨论了介电增强的两种互补解释:在MPB中正交和四方相之间的空间相共存,以及与低跃迁势垒和场致结构演化相关的动态非线性介电响应。其次,我们回顾了实现类mpb行为的主要工程策略,包括化学计量学和氧空位控制、先进的退火工艺、掺杂、双层和超晶格异质结构以及电极/界面工程。第三,我们评估了DRAM应用的实际性能和可靠性要求,重点是介电常数、泄漏电流、等效氧化物厚度和随时间变化的介电击穿之间的耦合权衡。代表性的报告包括在0.8 V时k≈67,泄漏电流密度为3 × 10−8 a /cm2,在单独的超薄HZO器件中,EOT约为2.42 Å, k≈64.24。最后,我们强调了MPB hfo2介电材料的优化需要一个整体的设计框架,同时考虑相位稳定性、缺陷动力学、界面质量和现实的低压基准条件。
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