Thermodynamic Insights into Symmetry Breaking: Exploring Energy Dissipation across Diverse Scales.

Symmetry breaking is a phenomenon that is observed in various contexts, from the early universe to complex organisms, and it is considered a key puzzle in understanding the emergence of life. The importance of this phenomenon is underscored by the prevalence of enantiomeric amino acids and proteins.The presence of enantiomeric amino acids and proteins highlights its critical role. However, the origin of symmetry breaking has yet to be comprehensively explained, particularly from an energetic standpoint. This article explores a novel approach by considering energy dissipation, specifically lost free energy, as a crucial factor in elucidating symmetry breaking. By conducting a comprehensive thermodynamic analysis applicable across scales, ranging from elementary particles to aggregated structures such as crystals, we present experimental evidence establishing a direct link between nonequilibrium free energy and energy dissipation during the formation of the structures. Results emphasize the pivotal role of energy dissipation, not only as an outcome but as the trigger for symmetry breaking. This insight suggests that understanding the origins of complex systems, from cells to living beings and the universe itself, requires a lens focused on nonequilibrium processes.

Field emission in vacuum resonant tunneling heterostructures with high current densities.

We analyse the steady-state thermal regime of a one-dimensional triode resonant tunnelling structure. The high currents generated by resonant tunnelling produce a large amount of heat that could damage the structure. Establishing the conditions under which it can operate at optimum efficiency is therefore a problem of great relevance for applications. The tunnel current is found via eigenvalues of the Schrödinger equation in quantum wells. By calculating the current generated in the device and using the energy conservation law in the electrodes, the temperature reached is obtained for different types of electrodes and the importance of heat conduction and thermal radiation is analysed. In the cases discussed, conduction is dominant. When the electrode material is copper, the temperature reached is similar to that of the thermostat for a wide range of electrode lengths, whereas when the cathode material is diamond-graphite and the anode material is copper, the temperature increases significantly as a function of length. The results obtained allow the temperature to be controlled for optimum performance of the field-emitting triode structures.

Radiative heat transfer between two carbon nanotubes.

We analyze the radiative heat transfer between two parallel and infinitely long carbon nanotubes (CNTs). The radiative heat exchange is due to the difference between the Poynting vectors generated by the fluctuating currents when the CNTs are at different temperatures. The radiated and absorbed Poynting vectors are expressed in terms of the correlations of the electromagnetic fields obtained from the Green's function and the fluctuation-dissipation theorem for the current density. The analysis takes into account the scattering of the fields by the nanotubes. We show that the radiative heat transfer depends not only on the distance between nanotubes, but also on their chiralities and thus on their semiconducting or metallic nature, which would allow the design of nanostructures for optimal radiative heat exchange.

Enhancing carrier flux for efficient drug delivery in cancer tissues.

Ultrasound focused toward tumors in the presence of circulating microbubbles improves the delivery of drug-loaded nanoparticles and therapeutic outcomes; however, the efficacy varies among the different properties and conditions of the tumors. Therefore, there is a need to optimize the ultrasound parameters and determine the properties of the tumor tissue important for the successful delivery of nanoparticles. Here, we propose a mesoscopic model considering the presence of entropic forces to explain the ultrasound-enhanced transport of nanoparticles across the capillary wall and through the interstitium of tumors. The nanoparticles move through channels of variable shape whose irregularities can be assimilated to barriers of entropic nature that the nanoparticles must overcome to reach their targets. The model assumes that focused ultrasound and circulating microbubbles cause the capillary wall to oscillate, thereby changing the width of transcapillary and interstitial channels. Our analysis provides values for the penetration distances of nanoparticles into the interstitium that are in agreement with experimental results. We found that the penetration increased significantly with increasing acoustic intensity as well as tissue elasticity, which means softer and more deformable tissue (Young modulus lower than 50 kPa), whereas porosity of the tissue and pulse repetition frequency of the ultrasound had less impact on the penetration length. We also considered that nanoparticles can be absorbed into cells and to extracellular matrix constituents, finding that the penetration length is increased when there is a low absorbance coefficient of the nanoparticles compared with their diffusion coefficient (close to 0.2). The model can be used to predict which tumor types, in terms of elasticity, will successfully deliver nanoparticles into the interstitium. It can also be used to predict the penetration distance into the interstitium of nanoparticles with various sizes and the ultrasound intensity needed for the efficient distribution of the nanoparticles.

Monte Carlo simulations in the unconstrained ensemble.

The unconstrained ensemble describes completely open systems whose control parameters are the chemical potential, pressure, and temperature. For macroscopic systems with short-range interactions, thermodynamics prevents the simultaneous use of these intensive variables as control parameters, because they are not independent and cannot account for the system size. When the range of the interactions is comparable with the size of the system, however, these variables are not truly intensive and may become independent, so equilibrium states defined by the values of these parameters may exist. Here, we derive a Monte Carlo algorithm for the unconstrained ensemble and show that simulations can be performed using the chemical potential, pressure, and temperature as control parameters. We illustrate the algorithm by applying it to physical systems where either the system has long-range interactions or is confined by external conditions. The method opens up an avenue for the simulation of completely open systems exchanging heat, work, and matter with the environment.

Antiresonant driven systems for particle manipulation.

We report on the onset of antiresonant behavior of mass transport systems driven by time-dependent forces. Antiresonances arise from the coupling of a sufficiently high number of space-time modes of the force. The presence of forces having a wide space-time spectrum, a necessary condition for the formation of an antiresonance, is typical of confined systems with uneven and deformable walls that induce entropic forces dependent on space and time. We have analyzed, in particular, the case of polymer chains confined in a flexible channel and shown how they can be sorted and trapped. The presence of resonance-antiresonance pairs found can be exploited to design protocols able to engineer optimal transport processes and to manipulate the dynamics of nano-objects.

Extrasynaptic Communication.

Streams of action potentials or long depolarizations evoke a massive exocytosis of transmitters and peptides from the surface of dendrites, axons and cell bodies of different neuron types. Such mode of exocytosis is known as extrasynaptic for occurring without utilization of synaptic structures. Most transmitters and all peptides can be released extrasynaptically. Neurons may discharge their contents with relative independence from the axon, soma and dendrites. Extrasynaptic exocytosis takes fractions of a second in varicosities or minutes in the soma or dendrites, but its effects last from seconds to hours. Unlike synaptic exocytosis, which is well localized, extrasynaptic exocytosis is diffuse and affects neuronal circuits, glia and blood vessels. Molecules that are liberated may reach extrasynaptic receptors microns away. The coupling between excitation and exocytosis follows a multistep mechanism, different from that at synapses, but similar to that for the release of hormones. The steps from excitation to exocytosis have been studied step by step for the vital transmitter serotonin in leech Retzius neurons. The events leading to serotonin exocytosis occur similarly for the release of other transmitters and peptides in central and peripheral neurons. Extrasynaptic exocytosis occurs commonly onto glial cells, which react by releasing the same or other transmitters. In the last section, we discuss how illumination of the retina evokes extrasynaptic release of dopamine and ATP. Dopamine contributes to light-adaptation; ATP activates glia, which mediates an increase in blood flow and oxygenation. A proper understanding of the workings of the nervous system requires the understanding of extrasynaptic communication.

A Criterion for the Formation of Nonequilibrium Self-Assembled Structures.

Is there a criterion able to determine the type of structures formed in a nonequilibrium self-assembly process? This important question has a clear answer when the process takes place under equilibrium conditions: structures emerge at minimum values of the free energy. Experiments, however, have shown that when self-assembly takes place outside equilibrium, they do not appear at those free energy minima but rather at optimal values of structural parameters. On the basis of these observations, we propose a selection criterion for which structures come up at the minima of a nonequilibrium free energy that takes into account the energy needed to change their configuration. The criterion is able to predict the formation and configuration of structures such as Liesegang rings and patterns in magnetic colloids and could constitute a powerful tool to understand the synthesis of advanced materials, enantiomers, and nanoparticles.

A Legendre-Fenchel Transform for Molecular Stretching Energies.

Single-molecular polymers can be used to analyze to what extent thermodynamics applies when the size of the system is drastically reduced. We have recently verified using molecular-dynamics simulations that isometric and isotensional stretching of a small polymer result in Helmholtz and Gibbs stretching energies, which are not related to a Legendre transform, as they are for sufficiently long polymers. This disparity has also been observed experimentally. Using molecular dynamics simulations of polyethylene-oxide, we document for the first time that the Helmholtz and Gibbs stretching energies can be related by a Legendre-Fenchel transform. This opens up a possibility to apply this transform to other systems which are small in Hill's sense.

Statistical Mechanics at Strong Coupling: A Bridge between Landsberg's Energy Levels and Hill's Nanothermodynamics.

We review and show the connection between three different theories proposed for the thermodynamic treatment of systems not obeying the additivity ansatz of classical thermodynamics. In the 1950s, Landsberg proposed that when a system comes into contact with a heat bath, its energy levels are redistributed. Based on this idea, he produced an extended thermostatistical framework that accounts for unknown interactions with the environment. A decade later, Hill devised his celebrated nanothermodynamics, where he introduced the concept of subdivision potential, a new thermodynamic variable that accounts for the vanishing additivity of increasingly smaller systems. More recently, a thermostatistical framework at strong coupling has been formulated to account for the presence of the environment through a Hamiltonian of mean force. We show that this modified Hamiltonian yields a temperature-dependent energy landscape as earlier suggested by Landsberg, and it provides a thermostatistical foundation for the subdivision potential, which is the cornerstone of Hill's nanothermodynamics.

Strong Coupling and Nonextensive Thermodynamics.

We propose a Hamiltonian-based approach to the nonextensive thermodynamics of small systems, where small is a relative term comparing the size of the system to the size of the effective interaction region around it. We show that the effective Hamiltonian approach gives easy accessibility to the thermodynamic properties of systems strongly coupled to their surroundings. The theory does not rely on the classical concept of dividing surface to characterize the system's interaction with the environment. Instead, it defines an effective interaction region over which a system exchanges extensive quantities with its surroundings, easily producing laws recently shown to be valid at the nanoscale.

Casimir forces exerted by epsilon-near-zero hyperbolic materials.

The Casimir force exerted on a gold dipolar nanoparticle by a finite-thickness slab of the natural hyperbolic material namely, the ortorhombic crystalline modification of boron nitride, is investigated. The main contribution to the force originates from the TM-polarized waves, for frequencies at which the parallel and perpendicular components of the dielectric tensor reach minimal values. These frequencies differ from those corresponding to the Lorentzian resonances for the permittivity components. We show that when the slab is made of an isotropic epsilon-near-zero absorbing material the force on the nanoparticle is larger than that induced by a hyperbolic material, for similar values of the characteristic parameters. This fact makes these materials optimal in the use of Casimir's forces for nanotechnology applications.

Entropy Production beyond the Thermodynamic Limit from Single-Molecule Stretching Simulations.

Single-molecular systems are a test bed to analyze to what extent thermodynamics applies when the size of the system is drastically reduced. Isometric and isotensional single-molecule stretching experiments and their theoretical interpretations have shown the lack of a thermodynamic limit at those scales and the nonequivalence between their corresponding statistical ensembles. This disparity between thermodynamic results obtained in both experimental protocols can also be observed in entropy production, as previous theoretical results have shown. In this work, we present results from molecular dynamics simulations of stretching of a typical polymer, polyethylene-oxide, where this framework is applied to obtain friction coefficients associated with stretching at the two different statistical ensembles for two different system sizes, from which the entropy production follows. In the smallest system, they are different up to a factor of 2, and for the bigger system, the difference is smaller, as predicted. In this way, we provide numerical evidence that a thermodynamic description is still meaningful for the case of single-molecule stretching.

Saturation of radiative heat transfer due to many-body thermalization.

Radiative heat transfer between two bodies saturates at very short separation distances due to the nonlocal optical response of the materials. In this work, we show that the presence of radiative interactions with a third body or external bath can also induce a saturation of the heat transfer, even at separation distances for which the optical response of the materials is purely local. We demonstrate that this saturation mechanism is a direct consequence of a thermalization process resulting from many-body interactions in the system. This effect could have an important impact in the field of nanoscale thermal management of complex systems and in the interpretation of measured signals in thermal metrology at the nanoscale.

Molecular fields and statistical field theory of fluids: Application to interface phenomena.

Using the integral transformation, the field-theoretical Hamiltonian of the statistical field theory of fluids is obtained along with the microscopic expressions for the coefficients of the Hamiltonian. Applying this approach to the liquid-vapor interface, we derive an explicit analytical expression for the surface tension in terms of temperature, density, and parameters of the intermolecular potential. We also demonstrate that a clear physical interpretation may be given to the formal statistical field arising in the integral transformation-it may be associated with the one-body local microscopic potential. The results of the theory, lacking any ad hoc or fitting parameters are in good agreement with available simulation data.

Negative Thermophoretic Force in the Strong Coupling Regime.

Negative thermophoresis (a particle moving up the temperature gradient) is a somewhat counterintuitive phenomenon which has thus far eluded a simple thermostatistical description. The purpose of this Letter is to show that a thermodynamic framework based on the formulation of a Hamiltonian of mean force has the descriptive ability to capture this interesting and elusive phenomenon in an unusually elegant and straightforward fashion. We propose a mechanism that describes the advent of a thermophoretic force acting from cold to hot on systems that are strongly coupled to a nonisothermal heat bath. When a system is strongly coupled to the heat bath, the system's eigenenergies E_{j} become effectively temperature dependent. This adjustment of the energy levels allows the system to take heat from the environment, +d⟨E_{j}⟩, and return it as work, -d⟨TdE_{j}/dT⟩. This effect can make the temperature dependence of the effective energy profile nonmonotonic. As a result, particles may experience a force in either direction depending on the temperature.

Driving an electrolyte through a corrugated nanopore.

We characterize the dynamics of a z - z electrolyte embedded in a varying-section channel. In the linear response regime, by means of suitable approximations, we derive the Onsager matrix associated with externally enforced gradients in electrostatic potential, chemical potential, and pressure, for both dielectric and conducting channel walls. We show here that the linear transport coefficients are particularly sensitive to the geometry and the conductive properties of the channel walls when the Debye length is comparable to the channel width. In this regime, we found that one pair of off-diagonal Onsager matrix elements increases with the corrugation of the channel transport, in contrast to all other elements which are either unaffected by or decrease with increasing corrugation. Our results have a possible impact on the design of blue-energy devices as well as on the understanding of biological ion channels through membranes.

Thermodynamic Efficiency of Somatic Exocytosis of Serotonin.

Through somatic exocytosis neurons liberate immense amounts of transmitter molecules that modulate the functioning of the nervous system. A stream of action potentials triggers an ATP-dependent transport of transmitter-containing vesicles to the plasma membrane, that ends with a large-scale exocytosis. It is commonly assumed that biological processes use metabolic energy with a high thermodynamic efficiency, meaning that most energy generates work with minor dissipation. However, the intricate ultrastructure underlying the pathway for the vesicle flow necessary for somatic exocytosis challenges this possibility. To study this problem here we first applied thermodynamic theory to quantify the efficiency of somatic exocytosis of the vital transmitter serotonin. Then we correlated the efficiency to the ultrastructure of the transport pathway of the vesicles. Exocytosis was evoked in cultured Retzius neurons of the leech by trains of 10 impulses delivered at 20 Hz. The kinetics of exocytosis was quantified from the gradual fluorescence increase of FM1-43 dye as it became incorporated into vesicles that underwent their exo-endocytosis cycle. By fitting a model of the vesicle transport carried by motor forces to the kinetics of exocytosis, we calculated the thermodynamic efficiency of the ATP expenses per vesicle, as the power of the transport divided by total energy ideally produced by the hydrolysis of ATP during the process. The efficiency was remarkably low (0.1-6.4%) and the values formed a W-shape distribution with the transport distances of the vesicles. Electron micrographs and fluorescent staining of the actin cortex indicated that the slopes of the W chart could be explained by the interaction of vesicles with the actin cortex and the calcium-releasing endoplasmic reticulum. We showed that the application of thermodynamic theory permitted to predict aspects of the intracellular structure. Our results suggest that the distribution of subcellular structures that are essential for somatic exocytosis abates the thermodynamic efficiency of the transport by hampering vesicle mobilization. It is remarkable that the modulation of the nervous system occurs at the expenses of an efficient use of metabolic energy.

The Role of Energy and Matter Dissipation in Determining the Architecture of Self-Assembled Structures.

We show how the architecture of self-assembled structures can be determined from the knowledge of the energy and matter dissipation inherent to its formation. When the amount of dissipation quantified by the total entropy produced in the process is represented in terms of parameters that describe the shape of the assembled structures, its extremes correspond to structures found in experimental situations such as in gelation and Liesegang ring formation. It is found that only a small amount of extra energy is needed to yield smooth changes in the form of the assembled structures. The connection found between the entropy produced and the type of structure formed may constitute a selection criterion, which shows why a set of disordered units may give rise to a determined self-assembled structure.