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The secular debate on the origin of life on our planet represents one of the open challenges for the scientific community. In this endeavour, chemistry has a pivotal role in disclosing novel scenarios that allow us to understand how the formation of simple organic molecules would be possible in the early primitive geological ages of Earth. Amino acids play a crucial role in biological processes. They are known to be formed in experiments simulating primitive conditions and were found in meteoric samples retrieved throughout the years. Understanding their formation is a key step for prebiotic chemistry. Following this reasoning, we performed a computational investigation over 100′000 structural isomers of natural amino acids. The results we have found suggest that natural amino acids are among the most thermodynamically stable structures and, therefore, one of the most probable ones to be synthesised among their possible isomers.

Earth is one of the inner planets of the Solar System, but – unlike the others – it has an oxidising atmosphere, relatively stable temperature, and a constant geomagnetic field (GMF). The GMF does not only protect life on Earth against the solar wind and cosmic rays, but it also shields the atmosphere itself, thus creating relatively stable environmental conditions. What is more, the GMF could have influenced the origins of life: organisms from archaea to plants and animals may have been using the GMF as a source of spatial information since the very beginning. Although the GMF is constant, it does undergo various changes, some of which, e.g. a reversal of the poles, weaken the field significantly or even lead to its short-term disappearance. This may result in considerable climatic changes and an increased frequency of mutations caused by the solar wind and cosmic radiation. This review analyses data on the influence of the GMF on different aspects of life and it also presents current knowledge in the area. In conclusion, the GMF has a positive impact on living organisms, whereas a diminishing or disappearing GMF negatively affects living organisms. The influence of the GMF may also be an important factor determining both survival of terrestrial organisms outside Earth and the emergence of life on other planets.

How life arose on the primitive Earth is one of the biggest questions in science. Biomolecular emergence scenarios have proliferated in the literature but accounting for the ubiquity of oxidized (+ 5) phosphate (PO43−) in extant biochemistries has been challenging due to the dearth of phosphate and molecular oxygen on the primordial Earth. A compelling body of work suggests that exogenous schreibersite ((Fe,Ni)3P) was delivered to Earth via meteorite impacts during the Heavy Bombardment (ca. 4.1–3.8 Gya) and there converted to reduced P oxyanions (e.g., phosphite (HPO32−) and hypophosphite (H2PO2−)) and phosphonates. Inspired by this idea, we review the relevant literature to deduce a plausible reduced phospholipid analog of modern phosphatidylcholines that could have emerged in a primordial hydrothermal setting. A shallow alkaline lacustrine basin underlain by active hydrothermal fissures and meteoritic schreibersite-, clay-, and metal-enriched sediments is envisioned. The water column is laden with known and putative primordial hydrothermal reagents. Small system dimensions and thermal- and UV-driven evaporation further concentrate chemical precursors. We hypothesize that a reduced phospholipid arises from Fischer–Tropsch-type (FTT) production of a C8 alkanoic acid, which condenses with an organophosphinate (derived from schreibersite corrosion to hypophosphite with subsequent methylation/oxidation), to yield a reduced protophospholipid. This then condenses with an α-amino nitrile (derived from Strecker-type reactions) to form the polar head. Preliminary modeling results indicate that reduced phospholipids do not aggregate rapidly; however, single layer micelles are stable up to aggregates with approximately 100 molecules.

It has been proposed that clays could have served as key factors in promoting the increase in complexity of organic matter in primitive terrestrial and extraterrestrial environments. The aim of this work is to study the adsorption–desorption of two dicarboxylic acids, fumaric and succinic acids, onto clay minerals (sodium and iron montmorillonite). These two acids may have played a role in prebiotic chemistry, and in extant biochemistry, they constitute an important redox couple (e.g. in Krebs cycle) in extant biochemistry. Smectite clays might have played a key role in the origins of life. The effect of pH on sorption has been tested; the analysis was performed by UV–vis and FTIR-ATR spectroscopy, X-ray diffraction and X-ray fluorescence. The results show that chemisorption is the main responsible of the adsorption processes among the dicarboxylic acids and clays. The role of the ion, present in the clay, is fundamental in the adsorption processes of dicarboxylic acids. These ions (sodium and iron) were selected due to their relevance on the geochemical environments that possibly existed into the primitive Earth. Different mechanisms are proposed to explain the sorption of dicarboxylic acids in the clay. In this work, we propose the formation of complexes among metal cations in the clays and dicarboxylic acids. The organic complexes were probably formed in the prebiotic environments enabling chemical processes, prior to the appearance of life. Thus, the data presented here are relevant to the origin of life studies.

Chiral symmetry breaking in far from equilibrium systems with large number of amino acids and peptides, like a prebiotic Earth, was considered. It was shown that if organic catalysts were abundant, then effective averaging of enantioselectivity would prohibit any symmetry breaking in such systems. It was further argued that non-linear (catalytic) reactions must be very scarce (called the abundance parameter) and catalysts should work on small groups of similar reactions (called the similarity parameter) in order to chiral symmetry breaking have a chance to occur. Models with 20 amino acids and peptide lengths up to three were considered. It was shown that there are preferred ranges of abundance and similarity parameters where the symmetry breaking can occur in the models with catalytic synthesis / catalytic destruction / both catalytic synthesis and catalytic destruction. It was further shown that models with catalytic synthesis and catalytic destruction statistically result in a substantially higher percentage of the models where the symmetry breaking can occur in comparison to the models with just catalytic synthesis or catalytic destruction. It was also shown that when chiral symmetry breaking occurs, then concentrations of some amino acids, which collectively have some mutually beneficial properties, go up, whereas the concentrations of the ones, which don’t have such properties, go down. An open source code of the whole system was provided to ensure that the results can be checked, repeated, and extended further if needed.

Pyrite and organic matter closely coexist in some hydrothermally-altered gabbroic xenoliths from the Hyblean Plateau, Sicily. The representative sample consists of plagioclase, Fe-oxides, clinopyroxene, pyrite and minor amounts of many other minerals. Plagioclase displays incipient albitization, clinopyroxene is deeply corroded. Pyrite grains are widely replaced by spongy-textured magnetite, which locally hosts Ca-(and Fe-)sulfate micrograins and blebs of condensed organic matter. Whole-rock trace element distribution evidences that incompatible elements, particularly the fluid-mobile Ba, U and Pb, are significantly enriched with respect to N-MORB values. The mineralogical and geochemical characteristics of the sample, and its U-Pb zircon age of 216.9 ± 6.7 MA, conform to the xenolith-based viewpoint that the unexposed Hyblean basement is a relict of the Ionian Tethys lithospheric domain, mostly consisting of abyssal-type serpentinized peridotites with small gabbroic intrusions. Circulating hydrothermal fluids there favored the formation of hydrocarbons trough Fischer-Tropsch-type organic synthesis, giving also rise to sulfidization episodes. Subsequent variations in temperature and redox conditions of the system induced partial de-sulfidization, Fe-oxides precipitation and sulfate-forming reactions, also promoting poly-condensation and aromatization of the already-formed hydrocarbons. Here we show organic matter adhering to a crystal face of a microscopic pyrite grain. Pyrite surfaces, as abiotic analogues of enzymes, can adsorb and concentrate organic molecules, also acting as catalysts for a broad range of proto-biochemical reactions. The present data therefore may support established abiogenesis models suggesting that pyrite surfaces carried out primitive metabolic cycles in suitable environments of the early Earth, such as endolithic recesses in mafic rocks permeated by hydrothermal fluids.

Prebiotic processes required a reliable source of free energy and complex chemical mixtures that may have included sugars. The formose reaction is a potential source of those sugars. At moderate to elevated temperature and pH ranges, these sugars rapidly decay. Here it is shown that CaCO3-based chemical gardens catalyze the formose reaction to produce glucose, ribose, and other monosaccharides. These thin inorganic membranes are explored as analogs of hydrothermal vent materials-a possible place for the origin of life-and similarly exposed to very steep pH gradients. Supported by simulations of a simple reaction-diffusion model, this study shows that such gradients allow for the dynamic accumulation of sugars in specific layers of the thin membrane, effectively protecting formose sugar yields. Therefore, the formose reaction may be a plausible prebiotic reaction in alkaline hydrothermal vent environments, possibly setting the stage for an RNA world.

The origin of translation is critical for understanding the evolution of life, including the origins of life. The canonical genetic code is one of the most dominant aspects of life on this planet, while the origin of heredity is one of the key evolutionary transitions in living world. Why the translation apparatus evolved is one of the enduring mysteries of molecular biology. Assuming the hypothesis, that during the emergence of life evolution had to first involve autocatalytic systems which only subsequently acquired the capacity of genetic heredity, we propose and discuss possible mechanisms, basic aspects of the emergence and subsequent molecular evolution of translation and ribosomes, as well as enzymes as we know them today. It is possible, in this sense, to view the ribosome as a digital-to-analogue information converter. The proposed mechanism is based on the abilities and tendencies of short RNA and polypeptides to fold and to catalyse biochemical reactions. The proposed mechanism is in concordance with the hypothesis of a possible chemical co-evolution of RNA and proteins in the origin of the genetic code or even more generally at the early evolution of life on Earth. The possible abundance and availability of monomers at prebiotic conditions are considered in the mechanism. The hypothesis that early polypeptides were folding on the RNA scaffold is also considered and mutualism in molecular evolutionary development of RNA and peptides is favoured.

Laboratory studies provide a fundamental understanding of photochemical processes in planetary atmospheres. Photochemical reactions taking place on giant planets like Jupiter and possibly comets and the interstellar medium are the subject of this research. Reaction pathways are proposed for the coupled photochemistry of NH3 (ammonia) and C2H2 (acetylene) within the context Jupiter’s atmosphere. We then extend the discussion to the Great Red Spot, Extra-Solar Giant Planets, Comets and Interstellar Organic Synthesis. Reaction rates in the form of quantum yields were measured for the decomposition of reactants and the formation of products and stable intermediates: HCN (hydrogen cyanide), CH3CN (acetonitrile), CH3CH = N-N = CHCH3 (acetaldazine), CH3CH = N-NH2 (acetaldehyde hydrazone), C2H5NH2 (ethylamine), CH3NH2 (methylamine) and C2H4 (ethene) in the photolysis of NH3/C2H2 mixtures. Some of these compounds, formed in our investigation of pathways for HCN synthesis, were not encountered previously in observational, theoretical or laboratory photochemical studies. The quantum yields obtained allowed for the formulation of a reaction mechanism that attempts to explain the observed results under varying experimental conditions. In general, the results of this work are consistent with the initial observations of Ferris and Ishikawa (1988). However, their proposed reaction pathway which centers on the photolysis of CH3CH = N-N = CHCH3 does not explain all of the results obtained in this study. The formation of CH3CH = N-N = CHCH3 by a radical combination reaction of CH3CH = N• was shown in this work to be inconsistent with other experiments where the CH3CH = N• radical is thought to form but where no CH3CH = N-N = CHCH3 was detected. The importance of the role of H atom abstraction reactions was demonstrated and an alternative pathway for CH3CH = N-N = CHCH3 formation involving nucleophilic reaction between N2H4 and CH3CH = NH is advanced.

This study explores the collaborative nature and interdisciplinarity of the origin(s) of life (OoL) research community. Although OoL research is one of the oldest topics in philosophy, religion, and science; to date there has been no review of the field utilizing bibliometric measures. A dataset of 5647 publications that are tagged as OoL, astrobiology, exobiology, and prebiotic chemistry is analyzed. The most prolific authors (Raulin, Ehrenfreund, McKay, Cleaves, Cockell, Lazcano, etc.), most cited scholars and their articles (Miller 1953, Gilbert 1986, Chyba & Sagan 1992, Wȁchtershȁuser 1988, etc.), and popular journals (Origins of Life and Evolution of Biospheres and Astrobiology) for OoL research are identified. Moreover, interdisciplinary research conducted through research networks, institutions (NASA, Caltech, University of Arizona, University of Washington, CNRS, etc.), and keywords & concepts (astrobiology, life, Mars, amino acid, prebiotic chemistry, evolution, RNA) are explored.

The biogenic elements, H, C, N, O, P and S, have a long cosmic history, whose evolution can still be observed in diverse locales of the known universe, from interstellar clouds of gas and dust, to pre-stellar cores, nebulas, protoplanetary discs, planets and planetesimals. The best analytical window into this cosmochemical evolution as it neared Earth has been provided so far by the small bodies of the Solar System, some of which were not significantly altered by the high gravitational pressures and temperatures that accompanied the formation of larger planets and may carry a pristine record of early nebular chemistry. Asteroids have delivered such records, as their fragments reach the Earth frequently and become available for laboratory analyses. The Carbonaceous Chondrite meteorites (CC) are a group of such fragments with the further distinction of containing abundant organic materials with structures as diverse as kerogen-like macromolecules and simpler compounds with identical counterparts in Earth's biosphere. All have revealed a lineage to cosmochemical synthetic regimes. Several CC show that asteroids underwent aqueous alteration of their minerals or rock metamorphism but may yet yield clues to the reactivity of organic compounds during parent-body processes, on asteroids as well as larger ocean worlds and planets. Whether the exogenous delivery by meteorites held an advantage in Earth's molecular evolution remains an open question as many others regarding the origins of life are. Nonetheless, the natural samples of meteorites allow exploring the physical and chemical processes that might have led to a selected chemical pool amenable to the onset of life. Graphical Abstract ᅟ.

Submarine hydrothermal vents are generally considered as the likely habitats for the origin and evolution of early life on Earth. In recent years, a novel hydrothermal system in Archean subseafloor has been proposed. In this model, highly alkaline and high temperature hydrothermal fluids were generated in basalt-hosted hydrothermal vents, where H2 and CO2 could be abundantly provided. These extreme conditions could have played an irreplaceable role in the early evolution of life. Nevertheless, sufficient information has not yet been obtained for the abiotic synthesis of amino acids, which are indispensable components of life, at high temperature and alkaline condition. This study aims to propose a new method for the synthesis of glycine in simulated Archean submarine alkaline vent systems. We investigated the formation of glycine from ethanolamine under conditions of high temperature (80–160 °C) and highly alkaline solutions (pH = 9.70). Experiments were performed in an anaerobic environment under mild pressure (0.1–8.0 MPa) at the same time. The results suggested that the formation of glycine from ethanolamine occurred rapidly and efficiently in the presence of metal powders, and was favored by high temperatures and high pressures. The experiment provides a new pathway for prebiotic glycine formation and points out the phenomenal influence of high-temperature alkaline hydrothermal vents in origin of life in the early ocean.

Polymerization of amino acids is a fundamentally important step for the chemical evolution of life. Nevertheless, its response to changing environmental conditions has not yet been well understood because of the lack of reliable quantitative information. For thermodynamics, detailed prediction over diverse combinations of temperature and pH has been made only for a few amino acid–peptide systems. This study used recently reported thermodynamic dataset for the polymerization of the simplest amino acid “glycine (Gly)” to its short peptides (di-glycine and tri-glycine) to examine chemical and structural characteristics of amino acids and peptides that control the temperature and pH dependence of polymerization. Results showed that the dependency is strongly controlled by the intramolecular distance between the amino and carboxyl groups in an amino acid structure, although the side-chain group role is minor. The polymerization behavior of Gly reported earlier in the literature is therefore expected to be a typical feature for those of α-amino acids. Equilibrium calculations were conducted to examine effects of dissolved metals as a function of pH on the monomer–polymer equilibria of Gly. Results showed that metals shift the equilibria toward the monomer side, particularly at neutral and alkaline pH. Metals that form weak interaction with Gly (e.g., Mg2+) have no noticeable influence on the polymerization, although strong interaction engenders significant decrease of the equilibrium concentrations of Gly peptides. Considering chemical and structural characteristics of Gly and Gly peptides that control their interactions with metals, it can be expected that similar responses to the addition of metals are applicable in the polymerization of neutral α-amino acids. Neutral and alkaline aqueous environments with dissolved metals having high affinity with neutral α-amino acids (e.g., Cu2+) are therefore not beneficial places for peptide bond formation on the primitive Earth.

International audience; In a famous experiment Stanley Miller showed that a large number of organic substances can emerge from sparking a mixture of methane, ammonia and hydrogen in the presence of water (Miller, Science 117: 528-529, 1953). Among these substances Miller identified different amino acids, and he concluded that prebiotic events may well have produced many of Life's molecular building blocks. There have been many variants of the original experiment since, including different gas mixtures (Miller, J Am Chem Soc 77: 2351-2361, 1955; Oro, Nature 197: 862-867, 1963; Schlesinger and Miller, J Mol Evol 19: 376-382, 1983; Miyakawa et al., Proc Natl Acad Sci 99:14,628-14,631, 2002). Recently some of Miller's remaining original samples were analyzed with modern equipment (Johnson et al. Science 322:404-404, 2008; Parker et al. Proc Natl Acad Sci 108: 5526-5531, 2011) and a total of 23 racemic amino acids were identified. To give an overview of the chemical variety of a possible prebiotic broth, here we analyze a ``Miller type'' experiment using state of the art mass spectrometry and NMR spectroscopy. We identify substances of a wide range of saturation, which can be hydrophilic, hydrophobic or amphiphilic in nature. Often the molecules contain heteroatoms, with amines and amides being prominent classes of molecule. In some samples we detect ethylene glycol based polymers. Their formation in water requires the presence of a catalyst. Contrary to expectations, we cannot identify any preferred reaction product. The capacity to spontaneously produce this extremely high degree of molecular variety in a very simple experiment is a remarkable feature of organic chemistry and possibly prerequisite for Life to emerge. It remains a future task to uncover how dedicated, organized chemical reaction pathways may have arisen from this degree of complexity.

The composition of organic matter and fluctuations of thermodynamic parameters were investigated in the hydrothermal systems of the Kamchatka peninsula in the context of the origin of life. Organics were analyzed by gas-chromatography/mass spectrometry, and 111 organic compounds belonging to 14 homologous series (aromatic hydrocarbons, alkanes and isoalkanes, halogenated aromatic hydrocarbons, carboxylic acids, esters, etc.) were found in hot springs inhabited by Archaeal and Bacterial thermophiles. The organics detected in the sterile condensate of water-steam mixture taken from deep boreholes (temperature 108-175 °C) consisted of 69 compounds of 11 homologous series, with aromatic hydrocarbons and alkanes being prevalent. The organic material included important prebiotic components such as nitrogen-containing compounds and lipid precursors. A separate organic phase (oil) was discovered in the Uzon Caldera. A biogenic origin is supported by the presence of sterane and hopane biomarkers and the δ(13)C value of the bulk oil; its age determined by (14)C measurements was 1030 ± 40 years. Multilevel fluctuations of thermodynamic parameters proposed to be required for the origin of life were determined in the Mutnovsky and Pauzhetsky hydrothermal systems. The low-frequency component of the hydrothermal fluid pressure varied by up to 2 bars over periods of hours to days, while mid-frequency variations had regular micro-oscillations with periods of about 20 min; the high-frequency component displayed sharp changes of pressure and microfluctuations with periods less than 5 min. The correlation coefficient between pressure and temperature ranges from 0.89 to 0.99 (average 0.96). The natural regimes of pressure and temperature fluctuations in Kamchatka hydrothermal systems can guide future experiments on prebiotic chemistry under oscillating conditions.

Alkaline hydrothermal systems have received considerable attention as candidates for the origin and evolution of life on the primitive Earth. Nevertheless, sufficient information has not yet been obtained for the thermodynamic properties of amino acids, which are necessary components for life, at high temperatures and alkaline pH. These properties were estimated using experimental high-temperature volume and heat capacity data reported in the literature for several amino acids, together with correlation algorithms and the revised Helgeson-Kirkham-Flowers (HKF) equations of state. This approach enabled determination of a complete set of the standard molal thermodynamic data and the revised HKF parameters for the 20 protein amino acids in their zwitterionic and ionization states. The obtained dataset was then used to evaluate the energetics of amino acid syntheses from simple inorganic precursors (CO2, H2, NH3 and H2S) in a simulated alkaline hydrothermal system on the Hadean Earth. Results show that mixing between CO2-rich seawater and the H2-rich hydrothermal fluid can produce energetically favorable conditions for amino acid syntheses, particularly in the lower-temperature region of such systems. Together with data related to the pH and temperature dependences of the energetics of amino acid polymerizations presented in earlier reports, these results suggest the following. Hadean alkaline hydrothermal settings, where steep pH and temperature gradients may have existed between cool, slightly acidic Hadean ocean water and hot, alkaline hydrothermal fluids at the vent-ocean interface, may be energetically the most suitable environment for the synthesis and polymerization of amino acids.

In the context of the origin of life, rocks are considered mainly for catalysis and adsorption-desorption processes. Here it is shown how some rocks evolve in energy and might induce synthesis of molecules of biological interest. Radioactive rocks are a source of thermal energy and water radiolysis producing molecular hydrogen, H2. Mafic and ultramafic rocks evolve in water and dissolved carbon dioxide releasing thermal energy and H2. Peridotites and basalts contain ferromagnesian minerals which transform through exothermic reactions with the generation of heat. These reactions might be triggered by any heating process such as radioactive decay, hydrothermal and subduction zones or post-shock of meteorite impacts. H2 might then be generated from endothermic hydrolyses of the ferromagnesian minerals olivine and pyroxene. In both cases of mafic and radioactive rocks, production of CO might occur through high temperature hydrogenation of CO2. CO, instead of CO2, was proven to be necessary in experiments synthesizing biological-type macromolecules with a gaseous mixture of CO, N2 and H2O. In the geological context, N2 is present in the environment, and the activation source might arise from cosmic radiation and/or radionuclides. Ferromagnesian and radioactive rocks might consequently be a starting point of an hydrothermal chemical evolution towards the abiotic formation of biological molecules. The two usually separate worlds of rocks and life are shown to be connected through molecular and thermodynamic chemical evolution. This concept has been proposed earlier by the author (Bassez J Phys: Condens Matter 15:L353-L361, 2003, 2008a, 2008b; Bassez Orig Life Evol Biosph 39(3-4):223-225, 2009; Bassez et al. 2011; Bassez et al. Orig Life Evol Biosph 42(4):307-316, 2012, Bassez 2013) without thermodynamic details. This concept leads to signatures of prebiotic chemistry such as radionuclides and also iron and magnesium carbonates associated with serpentine and/or talc, which were discussed at the 2014 European Astrobiology Network Association conference on Signatures of Life.

The ubiquity of phosphorus (P) in modern biochemistry suggests that P may have participated in prebiotic chemistry prior to the emergence of life. Of the major biogenic elements, phosphorus alone lacks a substantial volatile phase and its ultimate source therefore had to have been a mineral. However, as most native P minerals are chemically un-reactive within the temperature-pressure-pH regimes of contemporary life, it begs the question as to whether the most primitive early living systems on earth had access to a more chemically reactive P-mineral inventory. The meteoritic mineral schreibersite has been proposed as an important source of reactive P on the early earth. The chemistry of schreibersite as a P source is summarized and reviewed here. Recent work has also shown that reduced oxidation state P compounds were present on the early earth; these compounds lend credence to the relevance of schreibersite as a prebiotic mineral. Ultimately, schreibersite will oxidize to phosphate, but several high-energy P intermediates may have provided the reactive material necessary for incorporating P into prebiotic molecules.

Two of the most fundamental questions concerning the origin of life, how biologically important molecules (RNA, proteins) find their unique spatial configuration, and how coding sequences can evolve beyond a certain critical length, are discussed. It is shown that both of these problems have not been solved. Experiments that could clarify the mechanisms of interaction between biologically important molecules in the simplest cells are discussed.

The RNA World scenario of prebiotic chemical evolution is among the most plausible conceptual framework available today for modelling the origin of life. RNA offers genetic and catalytic (metabolic) functionality embodied in a single chemical entity, and a metabolically cooperating community of RNA molecules would constitute a viable infrabiological subsystem with a potential to evolve into proto-cellular life. Our Metabolically Coupled Replicator System (MCRS) model is a spatially explicit computer simulation implementation of the RNA-World scenario, in which replicable ribozymes cooperate in supplying each other with monomers for their own replication. MCRS has been repeatedly demonstrated to be viable and evolvable, with different versions of the model improved in depth (chemical detail of metabolism) or in extension (additional functions of RNA molecules). One of the dynamically relevant extensions of the MCRS approach to prebiotic RNA evolution is the explicit inclusion of template replication into its assumptions, which we have studied in the present version. We found that this modification has not changed the behaviour of the system in the qualitative sense, just the range of the parameter space which is optimal for the coexistence of metabolically cooperating replicators has shifted in terms of metabolite mobility. The system also remains resistant and tolerant to parasitic replicators.

The autocatalytic self-reproduction of micelles and vesicles has been studied for several decades. These systems are vital components of certain protocell models and some models for how life may have begun from mixtures of simple chemicals. Here we discuss our recently described autocatalytic systems where self-reproducing micelles are driven by bond-forming reactions. These systems generate increased complexity on both the molecular level, through covalent bond formation, and the supramolecular level, through spontaneous self-assembly into functional aggregates. This provides the conceptual basis for novel studies of the potential roles of self-reproducing lipid aggregates in the prebiotic world.

Self-replicating molecules, in particular RNA, have long been assumed as key to origins of life on Earth. This notion, however, is not very secure since the reduction of life's complexity to self-replication alone relies on thermodynamically untenable assumptions. Alternative, earlier hypotheses about peptide-dominated colloid self-assembly should be revived. Such macromolecular conglomerates presumably existed in a dynamic equilibrium between confluent growth in sessile films and microspheres detached in turbulent suspension. The first organic syntheses may have been driven by mineral-assisted photoactivation at terrestrial geothermal fields, allowing photo-dependent heterotrophic origins of life. Inherently endowed with rudimentary catalyst activities, mineral-associated organic microstructures can have evolved adaptively toward cooperative 'protolife' communities, in which 'protoplasmic continuity' was maintained throughout a graded series of 'proto-biofilms', 'protoorganisms' and 'protocells' toward modern life. The proneness of organic microspheres to merge back into the bulk of sessile films by spontaneous fusion can have made large populations promiscuous from the beginning, which was important for the speed of collective evolution early on. In this protein-centered scenario, the emergent coevolution of uncoded peptides, metabolic cofactors and oligoribonucleotides was primarily optimized for system-supporting catalytic capabilities arising from nonribosomal peptide synthesis and nonreplicative ribonucleotide polymerization, which in turn incorporated other reactive micromolecular organics as vitamins and cofactors into composite macromolecular colloid films and microspheres. Template-dependent replication and gene-encoded protein synthesis emerged as secondary means for further optimization of overall efficieny later on. Eventually, Darwinian speciation of cell-like lineages commenced after minimal gene sets had been bundled in transmissible genomes from multigenomic protoorganisms.

Terrestrial biosystems depend on macromolecules, and this feature is often considered as a likely universal aspect of life. While opinions differ regarding the importance of small-molecule systems in abiogenesis, escalating biological functional demands are linked with increasing complexity in key molecules participating in biosystem operations, and many such requirements cannot be efficiently mediated by relatively small compounds. It has long been recognized that known life is associated with the evolution of two distinct molecular alphabets (nucleic acid and protein), specific sequence combinations of which serve as informational and functional polymers. In contrast, much less detailed focus has been directed towards the potential universal need for molecular alphabets in constituting complex chemically-based life, and the implications of such a requirement. To analyze this, emphasis here is placed on the generalizable replicative and functional characteristics of molecular alphabets and their concatenates. A primary replicative alphabet based on the simplest possible molecular complementarity can potentially enable evolutionary processes to occur, including the encoding of secondarily functional alphabets. Very large uniquely specified ('non-alphabetic') molecules cannot feasibly underlie systems capable of the replicative and evolutionary properties which characterize complex biosystems. Transitions in the molecular evolution of alphabets can be related to progressive bridging of barriers which enable higher levels of biosystem organization. It is thus highly probable that molecular alphabets are an obligatory requirement for complex chemically-based life anywhere in the universe. In turn, reference to molecular alphabets should be usefully applied in current definitions of life.

Oligoribonucleotides are potentially capable of Darwinian evolution – they may replicate and can express an independent chemical phenotype, as embodied in modern enzymatic cofactors. Using quantitative chemical kinetics on a sporadically fed ribonucleotide pool, unreliable supplies of unstable activated ribonucleotides A and B at low concentrations recurrently yield a replicating AB polymer with a potential chemical phenotype. Self-complementary replication in the pool occurs during a minority (here ≈ 35 %) of synthetic episodes that exploit coincidental overlaps between 4, 5 or 6 spikes of arbitrarily arriving substrates. Such uniquely productive synthetic episodes, in which near-ideal reaction sequences recur at random, account for most AB oligonucleotide synthesis, and therefore underlie the emergence of net replication under realistic primordial conditions. Because overlapping substrate spikes are unexpectedly frequent, and in addition, complex spike sequences appear disproportionately, a sporadically fed pool can host unexpectedly complex syntheses. Thus, primordial substrate fluctuations are not necessarily a barrier to Darwinism, but instead can facilitate early evolution.

This model proposes that the origin of life on Earth occurred as a result of a process of alteration of the chemical composition of prebiotic macromolecules. The stability of organic compounds assembled into polymers generally exceeded the stability of the same compounds as free monomers. This difference in stability stimulated accumulation of prebiotic macromolecules. The prebiotic circulation of matter included constant formation and decomposition of polymers. Spontaneous chemical reactions between macromolecules with phosphodiester backbones resulted in a non-Darwinian selection for chemical stability, while formation of strong structures provided an advantage in the struggle for stability. Intermolecular structures between nucleotide-containing polymers were further stabilized by occasional acquisition of complementary nucleotides. Less stable macromolecules provided the source of nucleotides. This process resulted first in the enrichment of nucleotide content in prebiotic polymers, and subsequently in the accumulation of complementary oligonucleotides. Finally, the role of complementary copy molecules changed from the stabilization of the original templates to the de novo production of template-like molecules. I associate this stage with the origin of life in the form of cell-free molecular colonies. Original life acquired ready-to-use substrates from constantly forming prebiotic polymers. Metabolism started to develop when life began to consume more substrates than the prebiotic cycling produced. The developing utilization of non-polymeric compounds stimulated the formation of the first membrane-enveloped cells that held small soluble molecules. Cells "digested" the nucleotide-containing prebiotic macromolecules to nucleotide monomers and switched the mode of replication to the polymerization of nucleotide triphosphates.

We have recently reconstructed the 'hatcheries' of the first cells by combining geochemical analysis with phylogenomic scrutiny of the inorganic ion requirements of universal components of modern cells (Mulkidjanian et al. Proc Natl Acad Sci U S A 109:E821-830, 2012). These ubiquitous, and by inference primordial, proteins and functional systems show affinity to and functional requirement for K⁺, Zn²⁺, Mn²⁺, and phosphate. Thus, protocells must have evolved in habitats with a high K⁺/Na⁺ ratio and relatively high concentrations of Zn, Mn and phosphorous compounds. Geochemical reconstruction shows that the ionic composition conducive to the origin of cells could not have existed in marine settings but is compatible with emissions of vapor-dominated zones of inland geothermal systems. Under an anoxic, CO₂-dominated atmosphere, the ionic composition of pools of cool, condensed vapor at anoxic geothermal fields would resemble the internal milieu of modern cells. Such pools would be lined with porous silicate minerals mixed with metal sulfides and enriched in K⁺ ions and phosphorous compounds. Here we address some questions that have appeared in print after the publication of our anoxic geothermal field scenario. We argue that anoxic geothermal fields, which were identified as likely cradles of life by using a top-down approach and phylogenomics analysis, could provide geochemical conditions similar to those which were suggested as most conducive for the emergence of life by the chemists who pursuit the complementary bottom-up strategy.

There are strong reasons to believe that the laws, principles and constraints of physics and chemistry are universal. It is much less clear how this universality translates into our understanding of the origins of life. Conventionally, discussions of this topic focus on chemistry that must be sufficiently rich to seed life. Although this is clearly a prerequisite for the emergence of living systems, I propose to focus instead on self-organization of matter into functional structures capable of reproduction, evolution and responding to environmental changes. In biology, most essential functions are largely mediated by noncovalent interactions (interactions that do not involve making or breaking chemical bonds). Forming chemical bonds is only a small part of what living systems do. There are specific implications of this point of view for universality. I will concentrate on one of these implications. Strength of non-covalent interactions must be properly tuned. If they were too weak, the system would exhibit undesired, uncontrolled response to natural fluctuations of physical and chemical parameters. If they were too strong kinetics of biological processes would be slow and energetics costly. This balance, however, is not a natural property of complex chemical systems. Instead, it has to be achieved with the aid of an appropriate solvent for life. In particular, potential solvents for life must be characterized by a high dielectric constant to ensure solubility of polar species and sufficient flexibility of biological structures stabilized by electrostatic interactions. Among these solvents, water exhibits a remarkable trait that it also promotes solvophobic (hydrophobic) interactions between non-polar species, typically manifested by a tendency of these species to aggregate and minimize their contacts with the aqueous solvent. Hydrophobic interactions are responsible, at least in part, for many self-organization phenomena in biological systems, such as the formation of cellular boundary structures or protein folding. Strengths of electrostatic and hydrophobic interactions are similar and can be balanced over a wide range of temperatures, which considerably increases the repertoire of interactions that can be used to modulate biological functions. Some properties of water, e.g. its chemical activity against polymerization reactions, are considered as unfavorable to life. In actuality, this might be a favorable trait because life requires a balance between constructive and destructive processes. For example, molecules synthesized in response to specific conditions must be degraded once these conditions change. Otherwise regulation of biological processes would be virtually impossible. Water might not be the only liquid with favorable properties for supporting life. It has been proposed that formamide, which might be present elsewhere in the universe in sufficient quantities to warrant interest, could be a potential alternative to water for the origin of life. However, this will remain highly hypothetical until it is demonstrated in further studies on its physical, chemical and biological properties it is capable of mediating self-organization of matter and providing proper balance between different types of non-covalent interactions.

Keywords Originoflife.Autopoiesis.Prebioticecology.RNAworldcritique.LipidworldThe existence of many “worlds” in origin-of-life literature; such as the “lipid world” (Segre etal.2001),the“iron-sulfur world ”(Wachtershauser1992),the“aromaticworld”(Ehrenfreundetal. 2006) and others, leads to the impression that there are many competing hypothesis for theorigin of life. However, if one postulates that a concrete theory for the origin of life shouldprovide a plausible pathway from the stage of prebiotic soup to the stage of life in a series oflogical steps, then none of the above mentioned “worlds” comply with this requirement. Mostsimply provide us with new or alternative ways of making components of the prebiotic soup,whether monomeric or polymeric.There is only one origin-of-life theory which complies with the above stated requirement:the so called “RNA world” theory (Gilbert 1986). A brief, modern recapitulation of theRNA-world theory goes something like this: On an early Earth there was a prebiotic soupstage in which, in some aqueous environment, there was an abundance of various organicmolecules, including nucleotide components. The complex interactions of these molecules,at some point, allowed for the emergence of RNA chains and later on a self-replicating RNAmolecule. Once such a molecule was present it made many copies of itself. Due to non-perfect replication, some of the molecules were different and thus behaved differently in theenvironment (for example they were better replicators), thus paving the way for hereditaryfeatures, environmental selection and therefore evolution. Some of these RNAs (namelyribozymes) possessed catalytic activities. RNA molecules which were encapsulated insidelipid vesicles were advantaged over those that were not, principally thanks to protectionfrom the outside environment. Later on those that were able to catalyse synthesis of theirown lipid vesicles prevailed over those that could not. At this stage the macromolecularconglomerate started resembling modern cells and the RNA in these “cells” performed bothgenetic and enzymatic functions. At some point, the RNA protocell “invented” DNA for

In addressing the question of the origins of the relationship between metabolism and genetic replication, we consider the implications of a prebiotic, fission-fusion, ecology of composomes. We emphasise the importance of structures and non-specific catalysis on interfaces created by structures. From the assumption that the bells of the metabolism-replication wedding still echo in modern cells, we argue that the functional assemblies of macromolecules that constitute hyperstructures in modern bacteria are the descendants of composomes and that interactions at the hyperstructure level control the cell cycle. A better understanding of the cell cycle should help understand the original metabolism-replication marriage. This understanding requires new concepts such as metabolic signalling, metabolic sensing and Dualism, which entails the cells in a population varying the ratios of equilibrium to non-equilibrium hyperstructures so as to maximise the chances of both survival and growth. A deeper understanding of the coupling between metabolism and replication may also require a new view of cell cycle functions in creating a coherent diversity of phenotypes and in narrowing the combinatorial catalytic space. To take these ideas into account, we propose the Accordion model in which a dynamic interface between lipid domains catalysed monomer to polymer reactions and became decorated with peptides and nucleotides that favoured their own catalysis. In this model, metabolism, replication, differentiation and division all began together at the interface between extended equilibrium structures within protocells or composomes.

We discuss the origin of life in terms of an RNA World scenario in which the creation of autocatalytic sequences is the key step. Our computational models illustrate that life arises by a rare stochastic event that occurs due to spatially localized concentration fluctuations. This allows the chemical system to jump from a non-living state with very low ribozyme concentration to a living state that is controlled by ribozymes. Once the living state is established locally, it can spread deterministically through the rest of the system. These are generic features also possessed by more complex models with a greater degree of chemical realism.

The essence of the inversion concept of the origin of life can be narrowed down to the following theses: 1) thermodynamic inversion is the key transformation of prebiotic microsystems leading to their transition into primary forms of life; 2) this transformation might occur only in the microsystems oscillating around the bifurcation point under far-from-equilibrium conditions. The transformation consists in the inversion of the balance "free energy contribution / entropy contribution", from negative to positive values. At the inversion moment the microsystem radically reorganizes in accordance with the new negentropy (i.e. biological) way of organization. According to this approach, the origin-of-life process on the early Earth took place in the fluctuating hydrothermal medium. The process occurred in two successive stages: a) spontaneous self-assembly of initial three-dimensional prebiotic microsystems composed mainly of hydrocarbons, lipids and simple amino acids, or their precursors, within the temperature interval of 100-300°C (prebiotic stage); b) non-spontaneous synthesis of sugars, ATP and nucleic acids started at the inversion moment under the temperature 70-100°C (biotic stage). Macro- and microfluctuations of thermodynamic and physico-chemical parameters able to sustain this way of chemical conversion have been detected in several contemporary hydrothermal systems. A minimal self-sufficient unit of life on the early Earth was a community of simplest microorganisms (not a separate microorganism).

To understand how life could have originated on early Earth, it is essential to know what biomolecules and metabolic pathways are shared by extant organisms and what organic compounds and their chemical reaction channels were likely to have been primordially available during the initial phase of the formation of prebiotic metabolism. In a previous study, we demonstrated for the first time the reversible amination of α-oxo acids on the surface of photo-illuminated ZnS. The sulfide mineral is a typical component at the periphery of submarine hydrothermal vents which has been frequently argued as a very attractive venue for the origin of life. In this work, in order to simulate more closely the precipitation environments of ZnS in the vent systems, we treated newly-precipitated ZnS with hydrothermal conditions and found that its photocatalytic power was significantly enhanced because the relative crystallinity of the treated sample was markedly increased with increasing temperature. Since the reported experimental conditions are believed to have been prevalent in shallow-water hydrothermal vents of early Earth and the reversible amination of α-oxo acids is a key metabolic pathway in all extant life forms, the results of this work provide a prototypical model of the prebiotic amino acid redox metabolism. The amino acid dehydrogenase-like chemistry on photo-irradiated ZnS surfaces may advance our understanding of the establishment of archaic non-enzymatic metabolic systems.

We examine the stability of three key components needed to establish an RNA World under a range of potential conditions present on the early earth. The stability of ribose, cytosine, and the phosphodiester bond are estimated at different pH values and temperatures by extrapolating available experimental data. The conditions we have chosen range from highly acidic or alkaline hydrothermal vents, to the milder conditions in a primordial ocean at a range of atmospheric CO(2) partial pressures.

We critically examine the proposal by Wächtershäuser (Prokaryotes 1:275-283, 2006a, Philos Trans R Soc Lond B Biol Sci 361: 787-1808, 2006b) that putative transition metal binding sites in protein components of the translation machinery of hyperthermophiles provide evidence of a direct relationship with the FeS clusters of pyrite and thus indicate an autotrophic origin of life in volcanic environments. Analysis of completely sequenced cellular genomes of Bacteria, Archaea and Eucarya does not support the suggestion by Wächtershäuser (Prokaryotes 1:275-283, 2006a, Philos Trans R Soc Lond B Biol Sci 361: 787-1808, 2006b) that aminoacyl-tRNA synthetases and ribosomal proteins bear sequence signatures typical of strong covalent metal bonding whose absence in mesophilic species reveals a process of adaptation towards less extreme environments.

Only random processes should occur on the primitive Earth. In contrast, many ordered sequences are synthesized according to genetic information on the present Earth. In this communication, I have proposed an idea that protein 0(th)-order structures or specific amino acid compositions would mediate the transfer from random process to formation of ordered sequences, after formation of double-stranded genes.

The paper presents a model of coevolution of short peptides (P) and short oligonucleotides (N) at an early stage of chemical evolution leading to the origin of life. The model describes polymerization of both P and N types of molecules on mineral surfaces in aqueous solution at moderate temperatures. It is assumed that amino acid and nucleotide monomers were available in a prebiotic milieu, that periodic variation in environmental conditions between dry/warm and wet/cool took place and that energy sources were available for the polymerization. An artificial chemistry approach in combination with agent-based modeling was used to explore chemical evolution from an initially random mixture of monomers. It was assumed that the oligonucleotides could serve as templates for self-replication and for translation of peptide compositional sequences, and that certain peptides could serve as weak catalysts. Important features of the model are the short lengths of the peptide and oligonucleotide molecules that prevent an error catastrophe caused by copying errors and a finite diffusion rate of the molecules on a mineral surface that prevents excessive development of parasitism. The result of the simulation was the emergence of self-replicating molecular systems consisting of peptide catalysts and oligonucleotide templates. In addition, a smaller but significant number of molecules with alternative compositions also survived due to imprecise reproduction and translation of templates providing variability for further evolution. In a more general context, the model describes not only peptide-oligonucleotide molecular systems, but any molecular system containing two types of polymer molecules: one of which serves as templates and the other as catalysts.The presented coevolutionary system suggests a possible direction towards finding the origin of molecular functionality in a prebiotic environment.

According to Wachtershauser’s “Iron-Sulfur-World” one major requirement for the development of life on the prebiotic Earth is compartmentalization. Vesicles spontaneously formed from amphiphilic components containing a specific set of molecules including sulfide minerals may have lead to the first autotrophic prebiotic units. The iron sulfide minerals may have been formed by geological conversions in the environment of deep-sea volcanos (black smokers), which can be observed even today. Wachtershauser postulated the evolution of chemical pathways as fundamentals of the origin of life on earth. In contrast to the classical Miller-Urey experiment, depending on external energy sources, the “Iron-Sulfur-World” is based on the catalytic and energy reproducing redox system $$ FeS + {H_2}S \to FeS{}_2 + {H_2} $$ . The energy release out of this redox reaction (∆RG° = −38 kJ/mol, pH 0) could be the cause for the subsequent synthesis of complex organic molecules and the precondition for the development of more complex units similar to cells known today. Here we show the possibility for precipitating iron sulfide inside vesicles composed of amphiphilic block-copolymers as a model system for a first prebiotic unit. Our findings could be an indication for a chemoautotrophic FeS based origin of life.

A main unsolved problem in the RNA world scenario for the origin of life is how a template-dependent RNA polymerase ribozyme emerged from short RNA oligomers generated by random polymerization of ribonucleotides (Joyce and Orgel 2006). Current estimates establish a minimum size about 165 nt long for such a ribozyme (Johnston et al. 2001), a length three to four times that of the longest RNA oligomers obtained by random polymerization on clay mineral surfaces (Huang and Ferris 2003, 2006). To overcome this gap, we have developed a stepwise model of ligation-based, modular evolution of RNA (Briones et al. 2009) whose main conceptual steps are summarized in Figure 1. This scenario has two main advantages with respect to previous hypotheses put forward for the origin of the RNA world: i) short RNA....

It is commonly accepted among origin-of-life scientists that the emergence of life was an evolutionary process involving at one stage or other the working of natural selection. Researchers disagree, however, on the nature of the chemical infrastructure that could have formed prebiotically, enabling the evolutionary process. The division of the origin-of-life research community into 'geneticists' and 'metabolists' usually revolves around the issue whether the first to arise prebiotically was a genetic polymer or a primitive metabolic system. In this paper I offer an alternative classification based on the attitude to the onset of natural selection. From this perspective I add to the conventional division between gene-first and metabolism-first groups a position I call "preparatory metabolism". By this line of thought, an RNA or an RNA-like polymer could not have emerged prebiotically. Nevertheless, the onset of natural selection had to wait until such a polymer had arised. This paper examines the RNA-first, RNA-later, metabolism-first and preparatory-metabolism scenarios, assessing the weaknesses and strengths of each. I conclude that despite the recent theoretical advances in all these lines of research, and despite experimental breakthroughs, especially in overcoming several RNA-first hurdles, none of the examined paradigms has yet attained decisive experimental support. Demonstrating the evolvability of a potentially prebiotic infrastructure, whether genetic or metabolic, is a most serious challenge. So is the experimental demonstration of the emergence of such an infrastructure under prebiotic conditions. The current agenda before origin-of-life researchers of all stripes and colors is the search for the experimental means to tackle all these difficulties.

Strong arguments can be found in the literature addressed to the question of the origin of homochirality in life, supporting the hypothesis that primordial life could have evolved in both homochiral forms and that early on when life was still rarely found, random events led to the survival of only one of these living mirror images. This proposal is an alternative to the generally accepted view that small enantiomeric excesses of biologically important molecules were amplified to homochirality prior to life's origin. Acceptance of the possibility of "two equal runners" leads to the importance of research investigations on routes to formation of ensembles of racemic mixtures of isotactic biologically interesting polymers, supramolecular entities and aggregates.

The research on the origin of life, as such, seems to have reached an impasse as a clear and universal scientific definition of life is probably impossible. On the contrary, the research on the origin of evolution may provide a clue. But it is necessary to identify the minimum requirements that allowed evolution to emerge on early Earth. The classical approach, the 'RNA world hypothesis' is one way, but an alternative based on nonlinear dynamics dealing with far-from-equilibrium self-organization and dissipative structures can also be proposed. The conditions on early Earth, near deep-sea hydrothermal sites, were favorable to the emergence of dissipative structures such as vesicles with bilayer membranes composed of a mixture of amphiphilic and hydrophobic molecules. Experimentally these vesicles are able to self-reproduce but not to evolve. A plausible scenario for the emergence of a positive feedback process giving them the capability of evolving on early Earth is suggested. The possibilities offered by such a process are described in regard to specific characteristics of extant biological organisms and leads for future research in the field are suggested.

The idea is advanced that under the extreme earth conditions for ~3.9 billions years ago, protein-based beta-sheet molecular structures were the first self-propagating and information-processing biomolecules that evolved. The amyloid structure of these aggregates provided an effective protection against the harsh conditions known to decompose both polyribonucleotides and natively folded polypeptides. In the prebiotic amyloid world, both the replicative and informational functions were carried out by structurally stable beta-sheet protein aggregates in a prion-like mode involving templated self-propagation and storage of information in the beta-sheet conformation. In this amyloid (protein)-first, hybrid replication-metabolism view, the synthesis of RNA, and the evolvement of an RNA-protein world, were later, but necessary events for further biomolecular evolution to occur. I further argue that in our contemporary DNA--RNA--protein world, the primordial beta-conformation-based information system is preserved in the form of a cytoplasmic epigenetic memory.

The aim of this article is to discuss four topics: First, the origin of molecular reproduction. Second, the origin of agency - the capacity of a system to act on its own behalf. Agency is a stunning feature of human and some wider range of life. Third, to discuss a still poorly articulated feature of life noticed by the philosopher Immanuel Kant over 200 years ago: A self propagating organization of process. We have no theory for this aspect of life, yet it is central to life. Fourth, I will discuss constraints, as in Schroedinger's aperiodic crystal (Schroedinger E, What is life? The physical aspect of the living cell, 1944), as information, part of the total non-equilibrium union of matter, energy, work, work cycles, constraints, and information that appear to comprise the living state.

Here, the undisputed steps in the beginning of life on earth are compiled, before a retrograde approach is presented outlining a possible minimal set of components required for protein synthesis, based on our knowledge of modern translational apparatus of Escherichia coli.

The possibilities of pseudo peptide DNA mimics like PNA (peptide nucleic acid) having a role for the prebiotic origin of life prior to an RNA world is discussed. In particular a scenario is proposed in which protocells with an achiral genetic material through several generations stepwise is converted into a chiral genetic material, e.g., by incorporation of RNA units. Provided that a sufficiently large sequence space is occupied, a selection process based on catalytic function in which a single cell (first common ancestor) has a definite evolutionary advantage, selection of this cell would by contingency also lock it into homochirality.

Some experimental aspects concerning either the enantio-enrichment of alpha-amino acids starting from non-racemic mixtures or the formation of homochiral oligopeptides and oligonucleotides starting from racemic precursors are described. In principle, it is possible that more than one of these processes had played a role in chirobiogenesis.

The discovery of catalytic RNA has revolutionised modern molecular biology and bears important implications for the origin of Life research. Catalytic RNA, in particular self-replicating RNA, prompted the hypothesis of an early "RNA world" where RNA molecules played all major roles such information storage and catalysis. The actual role of RNA as primary actor in the origin of life has been under debate for a long time, with a particular emphasis on possible pathways to the prebiotic synthesis of mononucleotides; their polymerization and the possibility of spontaneous emergence of catalytic RNAs synthesised under plausible prebiotic conditions. However, little emphasis has been put on the chemical reality of an RNA world; in particular concerning the chemical constrains that such scenario should have met to be feasible. This paper intends to address those concerns with regard to the achievement of high local RNA molecules concentration and the aetiology of unique sequence under plausible prebiotic conditions.

In the answer to major questions of astrobiology and chirality, the panspermia-hypothesis is often discussed as the only proposal of transportation of life to the Earth. On the basis of the known presence of ionizing radiation in the space, assumed on the level calculated by Clark (Orig Life Evol Biosph 31:185-197, 2001), the hypothesis is rejected as the explanation of origins of life on Earth. In fact, comparatively low doses of radiation sterilize irreversibly all biological material. Sufficiently long sojourn in space of objects containing prebiotic chemical blocks also does not contribute to the origins of life on Earth, because of elimination of homochirality, if any, and of radiation induced reactions of dehydrogenation, decarboxylation and deamination of chemical compounds closing with complete decomposition of organics, leaving elementary nano-carbon and/or minerals like calcium carbonate.

At some point in life's development, membranes formed, providing barriers between the environment and the interior of the 'cell.' This paper evaluates the research to date on the prebiotic origin of cell membranes and highlights possible areas of continuing study. A careful review of the literature uncovered unexpected factors that influence membrane evolution. The major stages in primitive membrane formation and the transition to contemporary cell membranes appear to require an exacting relationship between environmental conditions and amphiphile composition and phase behavior. Also, environmental and compositional requirements for individual stages are in some instances incompatible with one another, potentially stultifying the pathway to contemporary membranes. Previous studies in membrane evolution have noted the effects composition and environment have on membrane formation but the crucial dependence and interdependence on these two factors has not been emphasized. This review makes clear the need to focus future investigations away from proof-of-principle studies towards developing a better understanding of the roles that environmental factors and lipid composition and polymorphic phase behavior played in the origin and evolution of cell membranes.