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Living systems are usually maintained out of equilibrium and exhibit complex dynamical behaviors. The external energy supply often comes from chemical fluxes that can keep some species concentrations constant. Furthermore, the properties of the underlying chemical reaction networks (CRNs) are also instrumental in establishing robust biological functioning. Hence, capturing the emergent complexity of living systems and the role of their non-equilibrium nature is fundamental to uncover constraints and properties of the CRNs underpinning their functions. In particular, while kinetics plays a key role in shaping detailed dynamical phenomena, the range of operations of any CRN must be fundamentally constrained by thermodynamics, as they necessarily operate with a given energy budget. Here, we derive universal thermodynamic upper and lower bounds for the accessible space of species concentrations in a generic CRN. The resulting region determines the "thermodynamic space" of the CRN, a concept we introduce in this work. Moreover, we obtain similar bounds also for the affinities, shedding light on how global thermodynamic properties can limit local non-equilibrium quantities. We illustrate our results in two paradigmatic examples, the Schl\"ogl model for bistability and a minimal self-assembly process, demonstrating how the onset of complex behaviors is intimately tangled with the presence of non-equilibrium driving. In summary, our work unveils the exact form of the accessible space in which a CRN must work as a function of its energy budget, shedding light on the non-equilibrium origin of a variety of phenomena, from amplification to pattern formation. Ultimately, by providing a general tool for analyzing CRNs, the presented framework constitutes a stepping stone to deepen our ability to predict complex out-of-equilibrium behaviors and design artificial chemical reaction systems.

Carnot efficiency sets a fundamental upper bound on the heat engine efficiency, attainable in the quasi-static limit, albeit at the cost of completely sacrificing power output. In this Letter, we present a minimal heat engine model that can attain Carnot efficiency while achieving maximum power output. We unveil the potential of intrinsic divergent physical quantities within the working substance, such as degeneracy, as promising thermodynamic resources to break through the universal power-efficiency trade-off imposed by nonequilibrium thermodynamics for conventional heat engines. Our findings provide novel insights into the collective advantage in harnessing energy of many-body interacting systems., Comment: 6+6 pages, 4 figures

Quantifying irreversibility of a system using finite information constitutes a major challenge in stochastic thermodynamics. We introduce an observable that measures the time-reversal asymmetry between two states after a given time lag. Our central result is a bound on the time-reversal asymmetry in terms of the total cycle affinity driving the system out of equilibrium. This result leads to further thermodynamic bounds on the asymmetry of directed fluxes; on the asymmetry of finite-time cross-correlations; and on the cycle affinity of coarse-grained dynamics., Comment: 5 pages, 4 figures

Living systems are maintained out-of-equilibrium by external driving forces. At stationarity, they exhibit emergent selection phenomena that break equilibrium symmetries and originate from the expansion of the accessible chemical space due to non-equilibrium conditions. Here, we use the matrix-tree theorem to derive universal thermodynamic bounds on these symmetry-breaking features in biochemical systems. Our bounds are independent of the kinetics and hold for both closed and open reaction networks. We also extend our results to master equations in the chemical space. Using our framework, we recover the thermodynamic constraints in kinetic proofreading. Finally, we show that the contrast of reaction-diffusion patterns can be bounded only by the non-equilibrium driving force. Our results provide a general framework for understanding the role of non-equilibrium conditions in shaping the steady-state properties of biochemical systems.

When exposed to a thermal gradient, reaction networks can convert thermal energy into the chemical selection of states that would be unfavourable at equilibrium. The kinetics of reaction paths, and thus how fast they dissipate available energy, might be dominant in dictating the stationary populations of all chemical states out-of-equilibrium. This phenomenology has been theoretically explored mainly in the infinite diffusion limit. Here, we show that the regime in which the diffusion rate is finite, and also slower than some chemical reactions, might give birth to interesting features, as the maximization of selection, or the switch of the selected state at stationarity. We introduce a framework, rooted in a time-scale separation analysis, which is able to capture leading non-equilibrium features using only equilibrium arguments under well-defined conditions. In particular, it is possible to identify fast-dissipation subnetworks of reactions whose Boltzmann equilibrium dominates the steady-state of the entire system as a whole. Finally, we also show that the dissipated heat (and so the entropy production) can be estimated, under some approximations, through the heat capacity of fast-dissipation subnetworks. This work provides a tool to develop an intuitive equilibrium-based grasp on complex non-isothermal reaction networks, which are important paradigms to understand the emergence of complex structures from basic building blocks.

Exposing a solution to a temperature gradient can lead to the accumulation of particles on either the cold or warm side. This phenomenon, known as thermophoresis, has been discovered more than a century ago, and yet its microscopic origin is still debated. Here, we show that thermophoresis can be observed in any system such that the transitions between different internal states are modulated by temperature and such that different internal states have different transport properties. We establish thermophoresis as a genuine non-equilibrium effect, whereby a system of currents in real and internal space that is consistent with the thermodynamic necessity of transporting heat from warm to cold regions. Our approach also provides an expression for the Soret coefficient, which decides whether particles accumulate on the cold or on the warm side, that is associated with the correlation between the energies of the internal states and their transport properties, that instead remain system-specific quantities. Finally, we connect our results to previous approaches based on close-to-equilibrium energetics. Our thermodynamically consistent approach thus encompasses and generalizes previous findings.

The exclusive presence of $\beta$-D-ribofuranose in nucleic acids is still a conundrum in prebiotic chemistry, given that pyranose species are substantially more stable at equilibrium. However, a precise characterisation of the relative furanose/pyranose fraction at temperatures higher than about 50$^{\,\rm o}$C is still lacking. Here, we employ a combination of NMR measurements and statistical mechanics modelling to predict a population inversion between furanose and pyranose at equilibrium at high temperatures. More importantly, we show that a steady temperature gradient may steer an open isomerisation network into a non-equilibrium steady state where furanose is boosted beyond the limits set by equilibrium thermodynamics. Moreover, we demonstrate that nonequilibrium selection of furanose is maximum at optimal dissipation, as gauged by the temperature gradient and energy barriers for isomerisation. The predicted optimum is compatible with temperature drops found in hydrothermal vents associated with extremely fresh lava flows on the seafloor., Comment: Main manuscript + supplementary information