confinement

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  • 文章类型: Journal Article
    While lithium borohydride is one of the most promising hydrogen storage materials due to its ultrahigh hydrogen storage density, high thermodynamic stability, kinetic barriers, and poor reversibility, it is far from being used in practical applications. Herein, we prepare a cubic hollow carbon dodecahedron uniformly modified with a bimetallic CoNi alloy (CoNi/NC) for preserving the stable catalytic effect of CoNi alloys toward reversible hydrogen storage. It is theoretically confirmed that bimetallic CoNi alloys effectively weaken the B-H bonds of LiBH4 by extending their average length to 1.33, 0.09 and 0.04 Å longer than that of LiBH4 and LiBH4 under metallic Co, respectively. More importantly, the alloying of Co with Ni avoids the reattachment of H from LiBH4 to the Co surface, which prevents LiBH4 from dehydrogenation for the formation of H2 on the Co surface, thus resulting in an ultralow hydrogen desorption energy of 0.1, 1.85 and 0.52 eV lower than that of LiBH4 and LiBH4 under metallic Co. Therefore, the onset and peak hydrogen desorption temperatures decrease to 130 and 355 °C, respectively, 170 and 97 °C lower than that of bulk LiBH4. More importantly, a reversible H2 capacity of 9.4 wt % is achieved even after 10 cycles.
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  • 文章类型: Journal Article
    细胞迁移是一个基本的、功能性的细胞过程,由不同细胞和细胞外基质(ECM)组成的复杂微环境的影响。最近的研究强调,除了来自微环境的生化线索,物理线索也可以极大地改变细胞行为。然而,由于微环境的复杂性,关于迁移细胞和周围微环境之间的物理相互作用如何指导细胞运动,人们知之甚少。这里,我们探索了体外3D微环境重建模型的各种示例,并描述了迁移细胞与相邻微环境之间的物理相互作用如何控制细胞行为。了解这种机械合作将为器官发育提供关键见解,再生,和肿瘤转移。
    Cell migration is a fundamental and functional cellular process, influenced by complex microenvironment consisting of different cells and extracellular matrix (ECM). Recent research has highlighted that, besides biochemical cues from the microenvironment, physical cues can also greatly alter cellular behavior. However, due to the complexity of the microenvironment, little is known about how the physical interactions between migrating cells and surrounding microenvironment instruct cell movement. Here, we explore various examples of 3D microenvironment reconstruction models in vitro and describe how the physical interplay between migrating cells and the neighboring microenvironment controls cell behavior. Understanding this mechanical cooperation will provide key insights into organ development, regeneration, and tumor metastasis.
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  • 文章类型: Journal Article
    已经确定,通过在金属催化剂顶上堆叠二维(2D)表面而产生的受限空间用作纳米反应器。根据最近的研究,当石墨烯(Gr)覆盖层从上方包裹Pt催化剂时,水解离反应的活化屏障,具有重大工业意义的过程,减少。为了研究在不同的二维(2D)材料之间的限制效果如何变化,我们研究了石墨烯作用下水分子在Pt(111)上的吸附和解离障碍,六方氮化硼(h-BN),和七嗪基石墨碳氮化物(g-C3N4)层使用密度泛函理论计算。我们的发现表明,吸附强度不会随着2D覆盖层高度的降低而降低。此外,较小的屏障并不总是反应物吸附较差的结果。我们还研究了约束对反应路径形状的影响,关于振动模式的频率,以及使用谐波过渡态理论得出的速率常数。总的来说,所有三个2D表面都会导致势垒高度降低和吸附减弱,尽管由于机械的混合,几何和电子变量。
    It has been established that the  confined space created by stacking a two dimensional (2D) surface atop a metal catalyst serves as a nano-reactor. According to recent research, when a graphene (Gr) overlayer encloses a Pt catalyst from above, the activation barrier for the water dissociation reaction, a process with major industrial significance, decreases. In order to investigate how the effect of confinement varies among different two-dimensional (2D) materials, we study the adsorption and dissociation barriers of water molecule on Pt(111) under graphene, hexagonal boron nitride (h-BN), and heptazine-based graphitic carbon nitride (g-C3N4) layers using density functional theory calculations. Our findings reveal that the strength of adsorption does not decrease consistently with a reduction in the height of the 2D overlayer. Furthermore, a smaller barrier is not always the consequence of poorer adsorption of the reactant. We also examine the effect of confinement on the shape of the reaction path, on the frequencies of vibrational modes, and on the rate constants derived using the harmonic transition state theory. Overall, all three of the 2D surfaces cause a decrease in barrier height and a weakening of adsorption, though to differing degrees due to a mix of mechanical, geometric and electronic variables.
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  • 文章类型: Journal Article
    虽然不规则和几何形状复杂的孔隙网络在自然界和工业过程中无处不在,没有通用的模型描述纳米粒子在这些环境中的传输。3D超分辨率纳米粒子跟踪用于研究复杂网络中被动(布朗)和主动(自推进)物种的运动,并普遍确定了一种涉及连续空腔探索和逃逸的机制。在所有情况下,长时间集合平均扩散系数与涉及与微观空腔探索和逃逸相关的特征长度尺度和时间尺度的量成正比(D~r2/ttrap),其中比例系数反映了表观多孔网络连通性。对于被动纳米粒子,对于随机游走,这个系数总是低于理论上的预期,表示网络可访问性降低。相比之下,活性纳米马达的系数,在相同的孔隙中,与理论价值一致,表明活性粒子在多孔环境中“智能地”导航,与可变孔径网络中的动力学蒙特卡罗模拟一致。这些发现阐明了多孔网络中纳米颗粒传输的连续空腔探索和逃逸模型,其中孔隙可达性是动力的函数,提供与过滤应用相关的见解,控释,和超越。
    While irregular and geometrically complex pore networks are ubiquitous in nature and industrial processes, there is no universal model describing nanoparticle transport in these environments. 3D super-resolution nanoparticle tracking was employed to study the motion of passive (Brownian) and active (self-propelled) species within complex networks, and universally identified a mechanism involving successive cavity exploration and escape. In all cases, the long-time ensemble-averaged diffusion coefficient was proportional to a quantity involving the characteristic length scale and time scale associated with microscopic cavity exploration and escape (D ∼ r2/ttrap), where the proportionality coefficient reflected the apparent porous network connectivity. For passive nanoparticles, this coefficient was always lower than expected theoretically for a random walk, indicating reduced network accessibility. In contrast, the coefficient for active nanomotors, in the same pore spaces, aligned with the theoretical value, suggesting that active particles navigate \"intelligently\" in porous environments, consistent with kinetic Monte Carlo simulations in networks with variable pore sizes. These findings elucidate a model of successive cavity exploration and escape for nanoparticle transport in porous networks, where pore accessibility is a function of motive force, providing insights relevant to applications in filtration, controlled release, and beyond.
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  • 文章类型: Journal Article
    钠硒(Na-Se)电池是具有高能量密度的有前途的储能系统,安全性高,和低成本。然而,硒的巨大体积变化,聚硒化物的溶解穿梭,和低硒负荷需要解决。在这里,Cu纳米颗粒修饰的MXene纳米片复合材料(MXene/Cu)通过使用熔融盐蚀刻策略蚀刻Ti3AlC2来合成。Se负载的MXene/Cu(Se@MXene/Cu)电极即使具有〜74.3wt%的高Se负载,也可提供卓越的电化学性能,由于二维(2D)限制结构的协同作用和独特的MXene/Cu主体的催化作用。具体来说,获得的电极在0.2A/g时的可逆容量为587.3mAh/g,在50A/g的高倍率下,放电容量高达511.3mAh/g,并且即使在基于Se@MXene/Cu的质量的5000次循环之后仍保持471.9mAh/g的容量。具有如此优异的电化学动力学性能,这项研究强调了设计各种MXene基复合材料的重要性,这些复合材料具有2D约束结构和Cu催化中心的协同作用,对于开发高性能碱金属-硫属元素电池系统。
    Sodium-selenium (Na-Se) batteries are promising energy storage systems with high energy density, high safety, and low cost. However, the huge volume change of selenium, the dissolution shuttle of polyselenides, and low selenium loading need to be solved. Herein, Cu nanoparticles decorated MXene nanosheets composite (MXene/Cu) are synthesized by etching Ti3AlC2 using a molten salt etching strategy. The Se-loaded MXene/Cu (Se@MXene/Cu) electrode delivers superior electrochemical performance even with a high Se loading of ∼74.3 wt%, owing to the synergistic effect of the two-dimensional (2D) confined structure and catalytic role of the unique MXene/Cu host. Specifically, the obtained electrode provides a reversible capacity of 587.3 mAh/g at 0.2 A/g, a discharge capacity as high as 511.3 mAh/g at a high rate of 50 A/g, and still maintains a capacity of 471.9 mAh/g even after 5000 cycles based on the mass of Se@MXene/Cu. With such excellent electrochemical kinetic properties, this study highlights the importance of designing various MXene-based composites with synergistic effects of 2D confined structure and Cu catalytic center for the development of high-performance alkali metal-chalcogen battery systems.
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  • 文章类型: Journal Article
    在低雷诺活性流体中观察到湍流,表现出与经典惯性湍流相似的现象学,但性质不同。理解这种新型湍流对维度的依赖性是非平衡物理学中的一个基本挑战。从二维到三维实验测量了细菌湍流的实空间结构和动能谱。湍流显示了三个由两个临界限制高度隔开的状态,由于细菌长度的竞争,涡流的大小和限制高度。同时,动能谱在准2D和3D状态下显示出不同的通用标度定律,独立于细菌活动,长度,和禁闭高度,而缩放指数在临界高度周围分两步过渡。我们开发的水动力学模型很好地捕获了缩放行为,它采用图像系统来表示限制边界的效果。该研究提出了一个框架,用于研究维度对非平衡自组织系统的影响。
    Turbulent flows are observed in low-Reynolds active fluids, which display similar phenomenology to the classical inertial turbulence but are of a different nature. Understanding the dependence of this new type of turbulence on dimensionality is a fundamental challenge in non-equilibrium physics. Real-space structures and kinetic energy spectra of bacterial turbulence are experimentally measured from two to three dimensions. The turbulence shows three regimes separated by two critical confinement heights, resulting from the competition of bacterial length, vortex size and confinement height. Meanwhile, the kinetic energy spectra display distinct universal scaling laws in quasi-2D and 3D regimes, independent of bacterial activity, length, and confinement height, whereas scaling exponents transition in two steps around the critical heights. The scaling behaviors are well captured by the hydrodynamic model we develop, which employs image systems to represent the effects of confining boundaries. The study suggests a framework for investigating the effect of dimensionality on non-equilibrium self-organized systems.
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  • 文章类型: Journal Article
    COVID-19大流行引发了全球危机,对公共卫生造成严重后果。由于在这种情况下产生的各种压力源,对人们的生活质量和心理健康产生了负面影响,如物理,社会,经济,心理挑战。其中值得注意的是健康措施的间接影响,尤其是社交距离和禁闭,极大地改变了人们的日常生活和社会活动,产生高度焦虑,抑郁症,和压力。这项研究建议开发和验证称为“环境压力源量表(ECSS-20)”的横截面量表,以解决在限制期间测量环境压力源影响的需要。规模,这已经按照道德和方法准则进行了验证,由四个维度组成:经济压力源(EE)、社会活动(SA),可居住性(H),和接触虚拟媒体(EMV)。应用了一项初步研究(n=113)和一项主要研究(n=314)。结果表明,该仪器结构可靠、有效,具有令人满意的内部一致性和阶乘效度。同样,性别不变性测试支持其适用于女性和男性。总的来说,ECSS-20是一种有价值的工具,用于评估禁闭的影响,并提高人们在这种情况下的主观体验的理解。未来的研究可以进一步发展其在不同背景和人群中的适用性,以更好地了解其有用性和心理测量特性。
    The COVID-19 pandemic has generated a global crisis with severe consequences for public health. There have been negative impacts on people\'s quality of life and mental health due to various stressors arising in this context, such as physical, social, economic, and psychological challenges. Noteworthy among these are the indirect effects of health measures, especially social distancing and confinement, which have significantly altered people\'s daily lives and social activities, producing high levels of anxiety, depression, and stress. This study proposes developing and validating a cross-sectional scale called the \"Environmental Stressors Scale (ECSS-20)\" to address the need to measure the impact of environmental stressors during confinement. The scale, which has been validated following ethical and methodological guidelines, consists of four dimensions: economic stressors (EE), social activities (SA), habitability (H), and exposure to virtual media (EMV). A pilot study (n = 113) and a main study (n = 314) were applied. The results showed that the instrument has a reliable and valid structure, with satisfactory internal consistency and factorial validity. Likewise, gender invariance tests supported its suitability for its applicability to women and men. Overall, the ECSS-20 is a valuable instrument for assessing the impact of confinement and improving the understanding of people\'s subjective experiences in this situation. Future research could further develop its applicability in different contexts and populations to better understand its usefulness and psychometric properties.
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  • 文章类型: Journal Article
    细菌的染色体由一对大碱基对长的环状DNA组成,在微米大小的细菌细胞体积内自我组织,压缩自己三个数量级。与真核染色体不同,它缺乏核膜,自由漂浮在细胞膜限制的细胞溶质中。人们认为,强烈的禁闭,通过相关蛋白质交联,和分子拥挤都有助于确定染色体的大小和形态。将染色体简单地建模为圆形聚合物,该聚合物在圆柱形约束体积中装饰有封闭的侧环,已被证明已经重新捕获了实验观察到的一些显着的特性。在这里,我们描述了如何使用该模型设置计算机模拟来研究细菌染色体的结构和动力学。
    The chromosome of a bacterium consists of a mega-base pair-long circular DNA, which self-organizes within the micron-sized bacterial cell volume, compacting itself by three orders of magnitude. Unlike eukaryotic chromosomes, it lacks a nuclear membrane and freely floats in the cytosol confined by the cell membrane. It is believed that strong confinement, cross-linking by associated proteins, and molecular crowding all contribute to determine chromosome size and morphology. Modelling the chromosome simply as a circular polymer decorated with closed side loops in a cylindrical confining volume has been shown to already recapture some of the salient properties observed experimentally. Here we describe how a computer simulation can be set up to study structure and dynamics of bacterial chromosomes using this model.
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  • 文章类型: Journal Article
    这项研究建议使用天然大麻纤维增强绳索(FRR)聚合物来增强包含烧制粘土实心砖骨料的再生骨料方形混凝土柱,以降低与合成纤维增强聚合物(FRP)相关的高成本。为了进行这项研究,共制造了24根方形混凝土柱。在单调轴向压缩载荷下测试样品。感兴趣的变量是无约束混凝土的强度和FRR层数。根据结果,增强的试样显示出增加的抗压强度和延展性。值得注意的是,具有最小无侧限强度的试样在抗压强度和延展性方面表现出最大的改善。特别是,抗压强度和应变分别提高了181%和564%,分别。为了预测极限压缩应力和应变,这项研究调查了一些分析应力-应变模型。实验和理论结果的比较得出,只有有限数量的强度模型导致了接近的预测,而在应变预测中观察到了更大的散射。机器学习通过使用神经网络来预测抗压强度。从文献中提取了一个由142个用大麻FRP强化的标本组成的数据集。神经网络是在提取的数据集上训练的,并根据本研究的实验结果评估了其性能,这表明了一个紧密的协议。
    This research suggested natural hemp fiber-reinforced ropes (FRR) polymer usage to reinforce recycled aggregate square concrete columns that contain fired-clay solid brick aggregates in order to reduce the high costs associated with synthetic fiber-reinforced polymers (FRPs). A total of 24 square columns of concrete were fabricated to conduct this study. The samples were tested under a monotonic axial compression load. The variables of interest were the strength of unconfined concrete and the number of FRR layers. According to the results, the strengthened specimens demonstrated an increased compressive strength and ductility. Notably, the specimens with the smallest unconfined strength demonstrated the largest improvement in compressive strength and ductility. Particularly, the compressive strength and strain were enhanced by up to 181% and 564%, respectively. In order to predict the ultimate confined compressive stress and strain, this study investigated a number of analytical stress-strain models. A comparison of experimental and theoretical findings deduced that only a limited number of strength models resulted in close predictions, whereas an even larger scatter was observed for strain prediction. Machine learning was employed by using neural networks to predict the compressive strength. A dataset comprising 142 specimens strengthened with hemp FRP was extracted from the literature. The neural network was trained on the extracted dataset, and its performance was evaluated for the experimental results of this study, which demonstrated a close agreement.
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  • 文章类型: Journal Article
    虽然在经典液体中的伊辛临界性已经在理论和实验上得到了牢固的确立,对液体中的临界性知之甚少,在液体中,有限尺寸效应阻碍了相关长度的增长。处理此问题的理论方法是随机场伊辛模型(RFIM)。虽然已经报道了磁性样品的实验临界指数值(这里,我们考虑γ,ν和η),对于相应液体系统中的临界波动,几乎没有实验信息可用。在本文中,我们对由3-甲基吡啶和重水组成的二元液体在非常轻质的多孔凝胶中进行了研究。我们发现实验结果与RFIM的理论预测一致。
    While Ising criticality in classical liquids has been firmly established both theoretically and experimentally, much less is known about criticality in liquids in which the growth of the correlation length is frustrated by finite-size effects. A theoretical approach for dealing with this issue is the random-field Ising model (RFIM). While experimental critical-exponent values have been reported for magnetic samples (here, we consider γ, ν and η), little experimental information is available for critical fluctuations in corresponding liquid systems. In this paper, we present a study on a binary liquid consisting of 3-methyl pyridine and heavy water in a very light-weight porous gel. We find that the experimental results are in agreement with the theoretical predictions from the RFIM.
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