The idea that organic chemistry can gradually self‐organize towards the emergence of life has been challenged by views considering that the most important driver should be the existence of a crucial thermodynamic disequilibrium. In this work, past views are critically addressed and a mechanism through which disequilibrium can promote the emergence and development of organized systems is suggested. This analysis is based on the propensity of carbon to form covalent bonds with other elements, which usually corresponds to deep energy wells generating high kinetic barriers hindering reactions. Potential energy wells and the associated kinetic barriers are considered as storing a prepaid entropy loss within a potential energy surface and therefore constitute a potential giving room for subsequent self‐organization processes. This potential associated with the notion of Kinetically Stable Thermodynamically Activated (KSTA) compounds gives rise to the possibility of alternative pathways based on non‐linear autocatalytic processes. As other systems working in a far‐from‐equilibrium context, like molecular machines, kinetic parameters are crucial for determining how they proceed and how they change, which suggests that interactions between the fields of molecular machines and of the emergence of life could be mutually beneficial.

Both the emergence and sustainability of dissipative chemical systems, such as protometabolisms, require a constant flow of free energy, which can, among other possibilities, be provided by chemical activating agents. Several prebiotically plausible candidates have been identified, but none are flawless or even sufficiently efficient to consider this question resolved. This study revisits and extends previous work on amino acid activation and peptide elongation promoted by carbonyl sulfide in aqueous medium which proceeds via the formation of N‐carboxyanhydrides (NCAs). Through an approach aimed at providing new mechanistic insights, it demonstrates that oxidation of the thiocarbamate adduct is mandatory for subsequent NCA and peptide bond formation and that ferricyanide, as an oxidizing agent example, efficiently promotes the reaction even at mild pH. However, side reactions, such as urea/hydantoin formation, were confirmed to strongly limit the prebiotic scope of this N‐terminal peptide elongation route.

The presence of minerals in the prebiotic environment likely shaped the evolution of organic matter, thereby contributing to the emergence of prebiotic systems. Records of such systems are lacking and the interactions between abiotic organic matter and primary minerals remain poorly understood. Here, we demonstrate the ability of olivine silicates, in simulated early Earth or planetary aqueous environments, to catalyse glycolaldehyde formation from only formaldehyde, and help producing sugars that are essential components for life, through the formose reaction. By combining comprehensive gas chromatography analyses on experimental samples with quantum chemical simulations, we provide a mechanism for an olivine-catalyzed glycolaldehyde formation. Our findings suggest that olivine plays a triple role in the formose chemical network: maintaining an alkaline pH, enabling the initiation step towards the formation of glycoladehyde (which is typically the most challenging step) and promoting the autocatalytic cycle. These results open-up new scenarios on the impact of primary minerals on the evolution of chemical pathways in aqueous environments that were probably essential for the emergence of the first biomolecules.

The ability of living organisms to persist, grow, evolve and invade environments seemingly challenges physical laws. Emerging Autonomous Systems representing autocatalytic cycles constituted of energized components in a state of Dynamic Kinetic Stability feature some of these properties. These simple theoretical models can grow, can be transferred but need an initiation to emerge and can collapse. Moreover, they can undergo kinetic selection in a way consistent with Darwinian behaviour, though they lack the ability to undergo change. The mere existence of these systems and their open-ended growth potential are proposed to constitute a transmissible factor of a non-coded kind. The onset and selection of epigenetic factors may therefore have preceded that of genetic polymers. Here is addressed the question of how these systems may arise from the diversity exhibited by abiotic organic matter, sometimes associated with intractable mixtures, which may actually be useful in providing initiators. The Darwinian description of evolution may therefore be merged without critical discontinuity within an origin scenario. Accordingly, such a theory would rests solely on physicochemical laws beginning with the potential of emerging autonomous systems to compete and invade the space dimension, and to further develop along other available dimensions including variability and, possibly, cognition.

One of life's most extraordinary features is its mental dimension, one whose origin and essence remain a deep scientific mystery. Given the modern scientific view that life emerged from non-life, how was 'dead' matter able to take on mental capabilities? In this Review we report on two recent scientific discoveries, which together offer new insights into the possible physical basis of mind and the origin of 'self'. First, recent thinking in microbiology now contends that simplest life manifests highly developed cognitive capabilities, suggesting that such capabilities were initiated early in the evolutionary process, likely within chemistry. Second, the recent discovery of a new dimension within chemical space of energized dynamic kinetically stable (DKS) chemical systems appears able to explain the emergence of systems with distinct non-physical characteristics, including cognition and 'self'. These two developments, when coupled to a physically based description of the evolutionary process, offer a feasible means of outlining the physical/chemical basis for life's mental state and a means for its emergence. A door toward resolution of the seemingly intractable 'mind from matter' problem may have opened up.

This work addresses the kinetic requirements for compensating the entropic cost of self-organization and natural selection, thereby revealing a fundamental principle in biology. Metabolic and evolutionary features of life cannot therefore be separated from an origin of life perspective. Growth, self-organization, evolution and dissipation processes need to be metabolically coupled and fueled by low-entropy energy harvested from the environment. The evolutionary process requires a reproduction cycle involving out-of-equilibrium intermediates and kinetic barriers that prevent the reproductive cycle from proceeding in reverse. Model analysis leads to the unexpectedly simple relationship that the system should be fed energy with a potential exceeding a value related to the ratio of the generation time to the transition state lifetime, thereby enabling a process mimicking natural selection to take place. Reproducing life’s main features, in particular its Darwinian behavior, therefore requires satisfying constraints that relate to time and energy. Irreversible reaction cycles made only of unstable entities reproduce some of these essential features, thereby offering a physical/chemical basis for the possible emergence of autonomy. Such Emerging Autonomous Systems (EASs) are found to be capable of maintaining and reproducing their kind through the transmission of a stable kinetic state, thereby offering a physical/chemical basis for what could be deemed an epigenetic process.

The high‐energy‐density synthesis of NxOy species is simulated in gas mixtures representing an O2‐free early‐Earth atmosphere by terawatt‐kilojoule‐class laser‐induced dielectric breakdown (LIDB). These experiments differ from previous LIDB experiments due to the 100 times greater energy delivered per pulse and sensitive analysis of products by high‐resolution infrared spectroscopy. The measured yields of NO, N2O, and NO2 are 0.08–8 × 1015, 5 × 1012, and 0.03–7 × 1014 molec J −1. The high N2O yield is above the upper‐limit constraint of previous tabletop LIDB experiments and the expected yield of a thermochemical freeze‐out at any temperature between 2000 and 5000 K, while the NO and NO2 yields are in broad agreement with freeze‐out models. Using a one dimensional chemical model of the Hadean atmosphere and a simple model of late bombardment, we compute the source flux of N2O assuming the same high production yield as measured experimentally and find the steady‐state partial pressure of N2O is insufficient to warm the climate.

One of life's most striking characteristics is its mental dimension, one whose very existence within a material system has long been a deep scientific mystery. Given the current scientific view that life emerged from non-life, how was it possible for 'dead' matter to have taken on mental capabilities? In this Perspective we describe the existence of a recently discovered non-equilibrium state of matter, an energized dynamic kinetic state, and demonstrate how particular chemical systems once activated into that kinetic state could manifest rudimentary cognitive behavior. Thus, contrary to a common view that biology is not reducible to physics and chemistry, recent findings in both chemistry and biology suggest that life's mental state is an outcome of its physical state, and therefore may be explicable in physical/chemical terms. Such understanding offers added insight into the physico-chemical process by which life was able to emerge from non-life and the perennial 'what is life?' question. Most remarkably, it appears that Darwin, through his deep understanding of the evolutionary process, already sensed the existence of a connection between life's physical and mental states.

In the processes of carbon capture and storage, sulfur and nitrogen oxides (SOx and NOx) would be possibly injected with CO2 depending on the origin of CO2. The thermodynamic properties of these gases in saline aquifer are poorly known. Solubility is one of the key parameter to be implemented in geochemical codes modelling long-term evolution of the aquifer after injection. The solubility of NO is known only at atmospheric pressure. In this study, the solubility of NO in water and NaCl solutions was measured by Raman spectroscopy in the ranges 295-373 K and 2-60 MPa using a high pressure optical cell and after calibration on a few data from molecular simulations. The results show a decrease of solubility when temperature increases and when salinity increases. No modification of NO speciation was observed.

Organic matter is formed in molecular clouds from which planetary systems arise as well as in planetary environments. Most of these locations are not likely to harbour life, questioning the genuine prebiotic character of the corresponding chemistry and its relevance to the origin of life. The formation of organic matter does therefore not necessarily constitute a systemic trend towards life in our Universe. However, its sluggish reactivity at low temperatures is likely to have allowed the delivery of volatile elements essential for life at the surface of planets like the Earth. Kinetic selection may also have played a role for sorting specific active species or complex catalytic processes during the self-organization preceding life owing to the kinetic barriers hindering the reactions of covalent bonds and holding the system in a far-from-equilibrium state. As a result of both processes, early environments on telluric planets that exhibit other essential factors, namely, liquid water and light as an energy source, may then become favourable to the origin of life. In both processes, reactivity matters as much, if not more, than structures. Next to focusing on the synthesis of building blocks, emphasis must be placed on reactivity for identifying networks involving autocatalysis, replication, or positive feedback.

The P-V-X properties of two-component fluid inclusions (FIs) are generally determined from microthermometry data using appropriate thermodynamic models (i.e., VX diagrams) and/or equations of state (EoS). However, some limitations can hamper the applicability of this technique such as the small size, low density or complex composition of the analyzed FI. Raman spectroscopy is known as the best-suited alternative method to microthermometry for the investigation of natural FIs because it can provide simultaneously non-destructive qualitative and possible quantitative analyses after specific calibrations. The present work aims to provide calibration data to directly determine the P-V-X properties of binary or ternary mixtures of CH4, CO2, and N-2. The variation of spectral features as a function of composition and pressure (or density) was investigated by using Raman spectroscopy coupled with an improved High-Pressure Optical Cell (HPOC) system and a customized heating-cooling stage. From our experimental data, the relative Raman scattering cross-section (RRSCS) of CH4 (nu(CH4)*) was demonstrated to be constant at 7.73 +/- 0.16 over the investigated range of pressure (5-600 bars) and for any composition. This parameter can thus be used for the determination of composition with an uncertainty of similar to 0.5 mol%. Several calibration equations were calculated for different PX domains, linking the Fermi diad splitting of CO2 (Delta) or the relative variation of the CH4 peak position (Delta(CH4)*) to the pressure (or density) and composition of CO2-CH4, CH4-N-2, and CO2-N-2-CH4 mixtures at 22 and 32 degrees C. The pressure and density of the fluids can henceforth be directly measured from Raman spectra with an uncertainty of similar to 20 bars and similar to 0.01 g.cm(-3), respectively. Our calibration equations were then validated on natural FIs by comparing the results obtained from Raman and microthermometry. We also interpreted the variation of the peak position of CH4 based on the change of intermolecular interaction. Finally, we discussed the applicability of the obtained calibration data into another laboratory by comparing it with the data of pure CO2 and CH4 published in literature. A small shift between calibration curves implies a systematic error which is perhaps due to the difference in the configuration or the day-to-day deviation of the instruments. Therefore, standards of well-known P-V-X properties should be regularly measured to prevent and to correct any variation or shifting of the instrumental responses.

The emergence of natural selection, requiring that reproducing entities present variations that may be inherited and passed on, was arguably the most important breakthrough in the self-organization of life. In this Perspective, the assumptions governing biological reproduction are confronted with physico-chemical principles that control the evolution of material systems. In biology, the reproduction of living organisms is never considered to be reversible, whereas microscopic reversibility is an essential principle in the physical description of matter. Here, we show that this discrepancy places constraints on the possibility of finding kinetic processes in the chemical world that are equivalent to natural selection in the biological one. Chemical replicators can behave in a similar fashion to living entities, provided that the reproduction cycle proceeds in a unidirectional way. For this to be the case, kinetic barriers must hinder the reverse process. The system must, thus, be held far from equilibrium and fed with a non-degraded (low-entropy) form of energy. The ensuing constraints must be factored in when proposing scenarios that account for the origin of life at the molecular level.

How ribosomal translation could have evolved remains an open question in most available scenarios for the early developments of life. Rather than considering RNA and peptides as two independent systems, this work is aimed at assessing the possibility of formation and stability of co-polymers or co-oligomers of α-amino acids and nucleotides from which translation might have evolved. Here we show that the linkages required to build such mixed structures have lifetimes of several weeks to months at neutral pH and 20 °C owing to the mutual protecting effect of both neighboring phosphoramidate and ester functional groups increasing their stability by factors of about 1 and 3 orders of magnitude, respectively. This protecting effect is reversible upon hydrolysis allowing the possibility of subsequent reactions. These copolymer models, for which an abiotic synthesis pathway is supported by experiments, form a basis from which both polymerization and translation could have logically evolved. Low temperatures were identified as a critical parameter for the kinetic stability of the aminoacylated nucleotide facilitating the synthesis of the model. This observation independently supports the views that any process involving RNA aminoacyl esters, outstandingly including the emergence of translation, was more probable at 0 °C or below and might be considered a kinetic marker constraining the environment in which translation has evolved.

It is becoming increasingly apparent that a generalized thermodynamic approach to chemical reactivity, in place since the pioneering contributions of Boltzmann and Gibbs a century ago, is unable to adequately explain, let alone predict, the entire space of chemical potentiality, and that more extensive exploration of the kinetic domain may be required. The relatively recent discovery of kinetically-governed processes, such as those observed in dissipative self-assembly, reveals the existence of a largely undiscovered kinetic domain for which we propose the general term dynamic kinetic chemistry. Our analysis suggests that all biological systems and associated sub-systems belong to this distinct kinetic domain, thereby enabling the placement of biological systems within a coherent physical/chemical framework. Such a classification appears to assist in bridging the problematic animate– inanimate conceptual gap as well as offering new insights into the origin of life (OOL) process. Additionally, the discovery of this kinetic domain has opened the door toward the preparation of active materials able to self-heal, adapt to environmental changes, and even communicate, mimicking what transpires routinely in the biological world.

Quantitative analysis of gases by Raman spectroscopy is based on relative Raman scattering cross sections (RRSCS) and the evolution of different spectral parameters (peak position, peak area, peak intensity, etc.). However, most of the calibration data were established at low pressure (low density) and without evaluating the effect of the composition. Using these data may lead to considerable errors, especially when applied to gas mixtures at high pressure as found in natural fluid inclusions. The aim of this study is to reevaluate the RRSCS of CO2 and to establish new calibration data based on the variation of CO2 Fermi diad splitting as a function of pressure (density) and composition over a pressure range of 5-600 bar at 22 and 32 °C. A high-pressure optical cell system (HPOC) and a heating-cooling stage were used for Raman in situ analyses at controlled PTX conditions. Our experimental results show that the RRSCS of CO2 varies slightly with pressure but can be considered constant over the studied pressure range. It can be used to measure the proportion of CO2 in gas mixtures with an uncertainty of about ±0.5 mol%. Different polynomial equations were provided to calculate pressure and density of CO2-N2 gas mixtures with an uncertainty of ±20 bar or 0.01 g·cm-3. A comparison of PVTX properties of natural CO2-N2 fluid inclusions hosted in quartz from the Central Alps (Switzerland) obtained by Raman measurement and as derived from phase transition temperatures by microthermometry experiments shows comparable values.

Early life forms established a network of reactions for converting carbon dioxide into organic compounds. A non-biological system of reactions that could have formed the network's core on ancient Earth has been reported. SEE LETTER P.104