nonequilibrium thermodynamics

非平衡热力学
  • 文章类型: Journal Article
    进化需要选择。分子/化学/前达尔文进化论也不例外。必须选择一个分子而不是另一个分子才能发生和推进分子进化。Evolution,然而,没有目标。物理定律没有功利的欲望,意图或熟练程度。法律和约束对“有用性”视而不见。“那么潜在的多步骤过程是如何被预期的,无生命性质的重视和追求?正式系统的编排可以物理化学自发吗?混沌理论的纯物理动力学自排序和不可逆的非平衡热力学“不平衡转换引擎”既不能实现编排,也不能实现正式组织。自然选择是一种被动的、事后的选择。达尔文的选择减少了适者生存的差异和繁殖。在自然发生的情况下,选择必须是1)活跃的,2)Pre-Function,3)有效。选择必须在存在非平凡功能过程之前在分子水平上进行。它不可能是被动的或次要的。什么自然主义机制可能在起作用?
    Evolution requires selection. Molecular/chemical/preDarwinian evolution is no exception. One molecule must be selected over another for molecular evolution to occur and advance. Evolution, however, has no goal. The laws of physics have no utilitarian desire, intent or proficiency. Laws and constraints are blind to \"usefulness.\" How then were potential multi-step processes anticipated, valued and pursued by inanimate nature? Can orchestration of formal systems be physico-chemically spontaneous? The purely physico-dynamic self-ordering of Chaos Theory and irreversible non-equilibrium thermodynamic \"engines of disequilibria conversion\" achieve neither orchestration nor formal organization. Natural selection is a passive and after-the-fact-of-life selection. Darwinian selection reduces to the differential survival and reproduction of the fittest already-living organisms. In the case of abiogenesis, selection had to be 1) Active, 2) Pre-Function, and 3) Efficacious. Selection had to take place at the molecular level prior to the existence of non-trivial functional processes. It could not have been passive or secondary. What naturalistic mechanisms might have been at play?
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  • 文章类型: Journal Article
    经典热力学在处理处于平衡或接近平衡的系统方面取得了巨大成就。作为一个新兴领域,非平衡热力学为理解非平衡过程提供了一个通用框架,特别是在通常远离平衡且由热或量子波动主导的小系统中。腔光机械系统由于其高可控性,在研究非平衡热力学的各种实验平台中具有广阔的前景。优异的机械性能,以及在量子体系中深入运作的能力。这里,我们概述了腔光机械系统的非平衡热力学的最新进展。熵产评估的实验结果,波动定理,热传递,和热机突出显示。
    Classical thermodynamics has been a great achievement in dealing with systems that are in equilibrium or near equilibrium. As an emerging field, nonequilibrium thermodynamics provides a general framework for understanding the nonequilibrium processes, particularly in small systems that are typically far-from-equilibrium and are dominated by thermal or quantum fluctuations. Cavity optomechanical systems hold great promise among the various experimental platforms for studying nonequilibrium thermodynamics owing to their high controllability, excellent mechanical performance, and ability to operate deep in the quantum regime. Here, we present an overview of the recent advances in nonequilibrium thermodynamics with cavity optomechanical systems. The experimental results in entropy production assessment, fluctuation theorems, heat transfer, and heat engines are highlighted.
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  • 文章类型: Journal Article
    在广义公式中描述了三种确定不可逆过程热力学稳定性的方法。最简单的是Gibbs-Duhem理论,专门研究不可逆转的轨迹,它使用相反方向的虚拟位移的概念。其唯一的缺点是,甚至导致爆炸的轨迹也被认为是热力学稳定的运动。在第二种方法中,我们使用来自Lyapunov热力学稳定性理论的热力学Lyapunov函数及其时间速率(LTS,以前称为CTTSIP)。在这样做的时候,我们证明了熵的二阶微分,一个经常使用的Lyapunov函数,仅对研究平衡态的稳定性有用。非平衡稳态不合格。不使用明确的扰动坐标,我们进一步确定了渐近热力学稳定性和热力学稳定性,在不断作用的非扰动轨迹以及非平衡稳态的干扰下。第三种方法也基于LTS的Lyapunov函数,但是在这里我们还使用摄动坐标的速率,基于吉布斯关系,不使用它们的显式表达式,不仅要确定渐近的热力学稳定性,还要确定在不断作用的干扰下的热力学稳定性。只有那些导致熵产生率无限的轨迹(不稳定状态)被排除在这个结论之外。最后,我们利用这些发现来建立基于热力学稳定性的热力学第四定律。这是一份涵盖所有非平衡轨迹的全面声明,接近和远离平衡。与以前建议的“第四定律”不同,这一个符合与最初的第零到第三定律相关的一般性。使用在某些操作区域中具有多个稳态的Schl_gl反应来说明上文。
    Three approaches for determining the thermodynamic stability of irreversible processes are described in generalized formulations. The simplest is the Gibbs-Duhem theory, specialized to irreversible trajectories, which uses the concept of virtual displacement in the reverse direction. Its only drawback is that even a trajectory leading to an explosion is identified as a thermodynamically stable motion. In the second approach, we use a thermodynamic Lyapunov function and its time rate from the Lyapunov thermodynamic stability theory (LTS, previously known as CTTSIP). In doing so, we demonstrate that the second differential of entropy, a frequently used Lyapunov function, is useful only for investigating the stability of equilibrium states. Nonequilibrium steady states do not qualify. Without using explicit perturbation coordinates, we further identify asymptotic thermodynamic stability and thermodynamic stability under constantly acting disturbances of unperturbed trajectories as well as of nonequilibrium steady states. The third approach is also based on the Lyapunov function from LTS, but here we additionally use the rates of perturbation coordinates, based on the Gibbs relations and without using their explicit expressions, to identify not only asymptotic thermodynamic stability but also thermodynamic stability under constantly acting disturbances. Only those trajectories leading to an infinite rate of entropy production (unstable states) are excluded from this conclusion. Finally, we use these findings to formulate the Fourth Law of thermodynamics based on the thermodynamic stability. It is a comprehensive statement covering all nonequilibrium trajectories, close to as well as far from equilibrium. Unlike previous suggested \"fourth laws\", this one meets the same level of generality that is associated with the original zeroth to third laws. The above is illustrated using the Schlögl reaction with its multiple steady states in certain regions of operation.
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  • 文章类型: Journal Article
    在这项工作中,分析了云和地球辐射能量系统(CERES)和中分辨率成像光谱辐射计(MODIS)仪器的卫星数据,以确定从2002年到2023年,全球吸收的阳光和全球熵生产率如何变化。这些数据用于测试从最大功率原理(MPP)和最大熵产生原理(MEP)得出的有关地球表面和大气演化的假设。结果表明,在过去的20年中,吸收阳光的速率和全球熵的产生都有所增加。这与两个假设的预测是一致的。鉴于MPP或MEP的接受,讨论了一些外围扩展和细微差别。
    In this work, satellite data from the Clouds and Earth\'s Radiant Energy System (CERES) and Moderate Resolution Imaging Spectroradiometer (MODIS) instruments are analyzed to determine how the global absorbed sunlight and global entropy production rates have changed from 2002 to 2023. The data is used to test hypotheses derived from the Maximum Power Principle (MPP) and Maximum Entropy Production Principle (MEP) about the evolution of Earth\'s surface and atmosphere. The results indicate that both the rate of absorbed sunlight and global entropy production have increased over the last 20 years, which is consistent with the predictions of both hypotheses. Given the acceptance of the MPP or MEP, some peripheral extensions and nuances are discussed.
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  • 文章类型: Journal Article
    单细胞测序技术的最新进展使得能够获得整个转录组数据。直接从这些数据中了解潜在的机制并确定转录调节控制细胞功能的驱动力仍然具有挑战性。这项研究基于离散的单细胞RNA速度重建了细胞周期的连续矢量场,以量化单细胞全局非平衡动态景观通量。它揭示了巨大的波动破坏了全球景观,遗传扰动改变了景观通量,从而确定维持细胞周期动力学和预测相关功能效应的关键基因。此外,它量化了细胞周期启动的基本能量成本,并揭示了维持细胞周期需要卷曲通量和耗散来维持振荡相位相干性。这项研究可以直接从单细胞转录组数据中推断细胞周期基因调控网络,包括反馈机制和交互强度。这为实验验证景观通量理论并获得其相关量化提供了千载难逢的机会。它还提供了一个独特的框架,用于结合景观通量理论和单细胞高通量测序实验,以了解细胞周期的潜在机制,并可以扩展到其他非平衡生物过程。如分化发展和疾病发病机制。
    Recent developments in single-cell sequencing technology enable the acquisition of entire transcriptome data. Understanding the underlying mechanism and identifying the driving force of transcriptional regulation governing cell function directly from these data remains challenging. This study reconstructs a continuous vector field of the cell cycle based on discrete single-cell RNA velocity to quantify the single-cell global nonequilibrium dynamic landscape-flux. It reveals that large fluctuations disrupt the global landscape and genetic perturbations alter landscape-flux, thus identifying key genes in maintaining cell cycle dynamics and predicting associated functional effects. Additionally, it quantifies the fundamental energy cost of the cell cycle initiation and unveils that sustaining the cell cycle requires curl flux and dissipation to maintain the oscillatory phase coherence. This study enables the inference of the cell cycle gene regulatory networks directly from the single-cell transcriptomic data, including the feedback mechanisms and interaction intensity. This provides a golden opportunity to experimentally verify the landscape-flux theory and also obtain its associated quantifications. It also offers a unique framework for combining the landscape-flux theory and single-cell high-through sequencing experiments for understanding the underlying mechanisms of the cell cycle and can be extended to other nonequilibrium biological processes, such as differentiation development and disease pathogenesis.
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  • 文章类型: Journal Article
    我们使用自组织临界性和相干随机行为的概念,通过基因组表达作为集成的动力系统,研究了数千个基因在细胞命运转变中的协调行为。为了量化基因集体行为的影响,我们采用了通量平衡方法,并在称为表达式通量分析(EFA)的新工具中开发了它。在这里,我们描述了这个工具,并展示了它如何应用于特定的实验性全基因组表达数据,为细胞命运转变的动力学提供了新的见解。特别是,我们证明在细胞命运改变中,特定的随机扰动可以在整个系统中传播,以通过切换基因组引擎中的循环通量流来引导不同的细胞命运转变。EFA的利用使我们能够阐明统一的基因组机制,以确定何时以及如何通过关键过渡发生细胞命运变化。
    We examine the coordinated behavior of thousands of genes in cell fate transitions through genome expression as an integrated dynamical system using the concepts of self-organized criticality and coherent stochastic behavior. To quantify the effects of the collective behavior of genes, we adopted the flux balance approach and developed it in a new tool termed expression flux analysis (EFA). Here we describe this tool and demonstrate how its application to specific experimental genome-wide expression data provides new insights into the dynamics of the cell-fate transitions. Particularly, we show that in cell fate change, specific stochastic perturbations can spread over the entire system to guide distinct cell fate transitions through switching cyclic flux flow in the genome engine. Utilization of EFA enables us to elucidate a unified genomic mechanism for when and how cell-fate change occurs through critical transitions.
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  • 文章类型: Journal Article
    OmicronBA.2.75可能在2022年成为COVID-19的下一个全球优势菌株。与任何其他变体相比,BA.2.75亚变体在SARS-CoV-2的刺突蛋白和其他基因中获得了更多的突变(9)。因此,与早期的变体相比,其化学组成和热力学性质发生了变化。在本文中,报告了BA.2.75变体的结合的吉布斯能量和抗原-受体结合率。OmicronBA.2.75变体的结合的吉布斯能比竞争变体BA.2和BA.5的更负。
    Omicron BA.2.75 may become the next globally dominant strain of COVID-19 in 2022. The BA.2.75 sub-variant has acquired more mutations (9) in spike protein and other genes of SARS-CoV-2 than any other variant. Thus, its chemical composition and thermodynamic properties have changed compared with earlier variants. In this paper, the Gibbs energy of the binding and antigen-receptor binding rate was reported for the BA.2.75 variant. Gibbs energy of the binding of the Omicron BA.2.75 variant is more negative than that of the competing variants BA.2 and BA.5.
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  • 文章类型: Journal Article
    基于热力学变分原理,建立了过冷熔体结晶的新数学模型。该模型考虑了晶体形成和扩散生长规律,以及与表面局部平衡偏离的无扩散晶体生长。该模型还考虑了生长晶体对熔体中组分浓度的相互影响。对过冷共晶熔体Fe83B17的计算表明,熔体中发生了具有亚稳态相Fe3B的相Fe和Fe2B的成核和生长。生长的Fe3B晶体与熔体的表面上的局部平衡可能未保持。研究了相生长晶体的成核规律和相互影响。由于生长的Fe3B晶体表面对硼原子的无扩散捕获,因此Fe3B核的成核和生长速率与Fe和Fe2B核的生长不同。该模型将有助于计算在铜转鼓上生产非晶薄带的熔体冷却技术模式。该计算使得分析各种带层中的温度和结晶度的变化成为可能。计算结果已通过X射线衍射和量热研究进行了实验验证。计算与实验结果的对应关系证实了研究过冷熔体中晶体生长规律的有效方法。
    A new mathematical model of supercooled melt crystallization based on the variational principles of thermodynamics has been developed. The model takes into account the crystal formation and diffusion growth regularities, as well as the diffusionless crystal growth with the deviation from the local equilibrium at the surface. The model also takes into account the growing crystals mutual influence on the components concentration in the melt. The calculations for the supercooled eutectic melt Fe83B17showed that the nucleation and growth of the phases Fe and Fe2B with a metastable phase Fe3B occur in the melt. The local equilibrium on the surface of the growing Fe3B crystals with the melt probably does not maintained. The regularities of the nucleation and mutual influence of the growing crystals of the phases are studied. The nucleation and growth rate of the Fe3B nuclei differs from the growth of Fe and Fe2B nuclei due to the diffusionless capture of boron atoms by the growing Fe3B crystals surface. The model will help to calculate the melt cooling technology mode for producing amorphous ribbons on a copper rotating drum. The calculation made it possible to analyze changes in the temperature and the crystallization degree in the various ribbon layers. The calculation results have been verified experimentally by x-ray diffraction and calorimetric studies of the obtained ribbons. The correspondence of the calculation and the experimental results confirms the effectiveness developed methodology for studying the regularities of crystal growth in supercooled melts.
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  • 文章类型: Journal Article
    非平衡界面热力学对至关重要的生物,物理,和工业规模的运输过程。这里,我们讨论了多相多组分界面的局部平衡理论,该理论建立在吉布斯首先引入的“尖锐”界面概念的基础上,允许描述非平衡界面过程,例如在蒸发中产生的过程,冷凝,吸附,等。通过要求热力学对分隔面的精确位置不敏感,人们可以确定局部平衡的条件,并开发出测量界面上密集变量值的方法。然后我们使用广泛的,高精度非平衡分子动力学(NEMD)模拟验证理论,建立局部平衡假设的有效性。特别是,我们证明了平衡状态方程在不平衡状态下也是有效的,可用于确定与Clapeyron和Gibbs吸附方程的非平衡概括一致的界面温度和化学势。我们也展示,例如,That,远离平衡,温度或化学电位差不需要在界面上是均匀的,而是可以表现出明显的不连续性。然而,即使在这种情况下,我们证明了局部均衡假设及其含义仍然有效。这些结果为研究或重新研究各种界面传输现象提供了热力学基础和计算工具。
    Nonequilibrium interfacial thermodynamics has important implications for crucial biological, physical, and industrial-scale transport processes. Here, we discuss a theory of local equilibrium for multiphase multicomponent interfaces that builds upon the \"sharp\" interface concept first introduced by Gibbs, allowing for a description of nonequilibrium interfacial processes such as those arising in evaporation, condensation, adsorption, etc. By requiring that the thermodynamics be insensitive to the precise location of the dividing surface, one can identify conditions for local equilibrium and develop methods for measuring the values of intensive variables at the interface. We then use extensive, high-precision nonequilibrium molecular dynamics (NEMD) simulations to verify the theory and establish the validity of the local equilibrium hypothesis. In particular, we demonstrate that equilibrium equations of state are also valid out of equilibrium, and can be used to determine interfacial temperature and chemical potential(s) that are consistent with nonequilibrium generalizations of the Clapeyron and Gibbs adsorption equations. We also show, for example, that, far from equilibrium, temperature or chemical potential differences need not be uniform across an interface and may instead exhibit pronounced discontinuities. However, even in these circumstances, we demonstrate that the local equilibrium hypothesis and its implications remain valid. These results provide a thermodynamic foundation and computational tools for studying or revisiting a wide variety of interfacial transport phenomena.
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  • 文章类型: Journal Article
    此通讯解决了具有不同生长模式的球晶远非平衡生长的问题。生长发生在包含缺陷和凝聚态物质的环境中,涉及结果的(生物)聚合物和生物矿物。事实证明,有可能预料到,根据我们的考虑,在纯扩散控制(聚)晶体生长之前,有可能出现球晶。具体来说,我们已经证明了两种不同演化类型的球晶生长模式的出现因素,即,扩散控制生长和质量对流控制生长,出现。正如我们所命名的,单峰晶体Mullins-Sekerka型生长模式,局部曲率的特征\'存在,与所谓的双峰或Goldenfeld型增长模式相比,其新兴(结构)性质似乎更具熵生产力。在后者中,局部曲率不发挥任何关键作用。反过来,无定形和结晶相的联系使系统更好地妥协于热力学动力学条件,同时,follows.建模的无量纲特征表明,该系统不直接依赖于实验细节,以某种方式体现了它的准普遍性,即,缩放寻址字符。
    This communication addresses the question of the far-from-equilibrium growth of spherulites with different growing modes. The growth occurs in defects containing and condensed matter addressing environments of (bio)polymeric and biominerals involving outcomes. It turns out that it is possible to anticipate that, according to our considerations, there is a chance of spherulites\' emergence prior to a pure diffusion-controlled (poly)crystal growth. Specifically, we have shown that the emergence factors of the two different evolution types of spherulitic growth modes, namely, diffusion-controlled growth and mass convection-controlled growth, appear. As named by us, the unimodal crystalline Mullins-Sekerka type mode of growth, characteristic of local curvatures\' presence, seems to be more entropy-productive in its emerging (structural) nature than the so-named bimodal or Goldenfeld type mode of growth. In the latter, the local curvatures do not play any crucial roles. In turn, a liaison of amorphous and crystalline phases makes the system far better compromised to the thermodynamic-kinetic conditions it actually, and concurrently, follows. The dimensionless character of the modeling suggests that the system does not directly depend upon experimental details, manifesting somehow its quasi-universal, i.e., scaling addressing character.
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