Search Results (61)

Alkaline lakes are thought to have facilitated prebiotic synthesis reactions on the early Earth because their modern analogs accumulate vital chemical feedstocks such as phosphate through the evaporation of dilute groundwaters. Yet, the conditions required for some building block synthesis reactions are distinct from others, and these conditions are generally incompatible with those permissible for nascent cellular function. However, because current scenarios for prebiotic synthesis have not taken account of the physical processes that drive the chemical evolution of alkaline lakes, the potential for the co-occurrence of both prebiotic synthesis and the origins and early evolution of life in prebiotic alkaline lake environments remains poorly constrained. Here, we investigate the dynamics of active, prebiotically relevant alkaline lakes using near-surface geophysics, aqueous geochemistry, and hydrogeologic modeling. Due to their small size, representative range of chemistry, and contrasting evaporation behavior, the investigated, neighboring Last Chance and Goodenough Lakes in British Columbia, Canada offer a uniquely tractable environment for investigating the dynamics of alkaline lake behavior. The results show that the required, extreme phosphate enrichments in alkaline lake waters demand geomorphologically-driven vulnerability to evaporation, while the resultant contrast between evaporated brines and inflowing groundwaters yields Rayleigh–Taylor instabilities and vigorous surface–subsurface cycling and mixing of lake and groundwaters. These results provide a quantitative basis to reconcile conflicting prebiotic requirements of UV light, salinity, metal concentration, and pH in alkaline lake environments. The complex physical and chemical processing inherent to prebiotic alkaline lake environments thus may have not only facilitated prebiotic reaction networks, but also provided habitable environments for the earliest evolution of life. Full article

Prebiotic pre-Darwinian reactions continued throughout biochemical or Darwinian evolution. Early chemical processes could have occurred on Earth between 4.5 and 3.6 billion years ago when cellular life was about to come into being. Pre-Darwinian evolution assumes the development of hereditary elements but does not regard them as self-organizing processes. The presence of biochemical self-organization after the pre-Darwinian evolution did not justify distinguishing between different types of evolution. From the many possible solutions, evolution selected from among those stable reactions that led to catalytic networks, and under gradually changing external conditions produced a reproducible, yet constantly evolving and adaptable, living system. Major abiotic factors included sunlight, precipitation, air, minerals, soil and the Earth’s atmosphere, hydrosphere and lithosphere. Abiotic sources of chemicals contributed to the formation of prebiotic RNA, the development of genetic RNA, the RNA World and the initial life forms on Earth and the transition of genRNA to the DNA Empire, and eventually to the multitude of life forms today. The transition from the RNA World to the DNA Empire generated new processes such as oxygenic photosynthesis and the hierarchical arrangement of processes involved in the transfer of genetic information. The objective of this work is to unite earlier work dealing with the formose, the origin and synthesis of ribose and RNA reactions that were published as a series of independent reactions. These reactions are now regarded as the first metabolic pathway. Full article

Homochirality is an obvious feature of life on Earth. On the other hand, extraterrestrial samples contain largely racemic compounds. The same is true for any common organic synthesis. Therefore, it has been a perplexing puzzle for decades how these racemates could have formed enantiomerically enriched fractions as a basis for the origin of homochiral life forms. Numerous hypotheses have been put forward as to how preferentially homochiral molecules could have formed and accumulated on Earth. In this article, it is shown that homochirality of the abiotic organic pool at the time of formation of the first self-replicating molecules is not necessary and not even probable. It is proposed to abandon the notion of a molecular ensemble and to focus on the level of individual molecules. Although the formation of the first self-replicating, most likely homochiral molecule, is a seemingly improbable event, on a closer look, it is almost inevitable that some homochiral molecules have formed simply on a statistical basis. In this case, the non-selective leap to homochirality would be one of the first steps in chemical evolution directly out of a racemic “ocean”. Moreover, most studies focus on the chirality of the primordial monomers with respect to an asymmetric carbon atom. However, any polymer with a minimal size that allows folding to a secondary structure would spontaneously lead to asymmetric higher structures (conformations). Most of the functions of these polymers would be influenced by this inherently asymmetric folding. Furthermore, a concept of physical compartmentalization based on rock nanopores in analogy to nanocavities of digital immunoassays is introduced to suggest that complex cell walls or membranes were also not required for the first steps of chemical evolution. To summarize, simple and universal mechanisms may have led to homochiral self-replicating systems in the context of chemical evolution. A homochiral monomer pool is deemed unnecessary and probably never existed on primordial Earth. Full article

Most contemporary theories for the chemical origins of life include the prebiotic synthesis of informational polymers, including strong interpretations of the RNA World hypothesis. Existing challenges to the prebiotic emergence of RNA have encouraged exploration of the possibility that RNA was preceded by an ancestral informational polymer, or proto-RNA, that formed more easily on the early Earth. We have proposed that the proto-nucleobases of proto-RNA would have readily formed glycosides with ribose and that these proto-nucleosides would have formed base pairs as monomers in aqueous solution, two properties not exhibited by the extant nucleosides or nucleotides. Here we demonstrate that putative proto-nucleotides of the model proto-nucleobases barbituric acid and melamine can be formed in the same one-pot reaction with ribose-5-phosphate. Additionally, the proto-nucleotides formed in these reactions spontaneously form assemblies that are consistent with the presence of Watson–Crick-like base pairs. Together, these results provide further support for the possibility that heterocycles closely related to the extant bases of RNA facilitated the prebiotic emergence of RNA-like molecules, which were eventually replaced by RNA over the course of chemical and biological evolution. Full article

The chemical evolution of biomolecules was clearly affected by the overall extreme environmental conditions found on Early Earth. Periodic temperature changes inside the Earth’s crust may have played a role in the emergence and survival of functional peptides embedded in vesicular compartments. In this study, all-atom molecular dynamic (MD) simulations were used to elucidate the effect of temperature on the properties of functionalized vesicle membranes. A plausible prebiotic system was selected, constituted by a model membrane bilayer from an equimolar mixture of long-chain fatty acids and fatty amines, and an octapeptide, KSPFPFAA, previously identified as an optimized functional peptide in an evolution experiment. This peptide tends to form the largest spontaneous aggregates at higher temperatures, thereby enhancing the pore-formation process and the eventual transfer of essential molecules in a prebiotic scenario. The analyses also suggest that peptide–amphiphile interactions affect the structural properties of the membrane, with a significant increase in the degree of interdigitation at the lowest temperatures under study. Full article

The Braess paradox (discovered in 1968 by the German mathematician Dietrich Braess) describes how a possible relief of a system, by introducing new possibilities to distribute load or local density in flows inside the system, can actually increase stress on the system. It is most often researched in a world of rational decision-makers, who are assumed to cause the worsening situation due to rational optimization of individual interests. In strongly complex networks, the exploitation of new possibilities most probably needs rational decision-makers who can see the use of new possibilities for them. Interestingly, a mechanical analogy of the situation also exists, where new possibilities—in this case for forces in a system to attack—lead to a loss of stability inside the system. In this example, a string that was introduced to relieve the load on two springs leads to counter-intuitive overloading. With the perspective that the evolution of information processing systems is already beginning in a physical and chemical pre-biotic world, this is an interesting case that might give further insight into how and when choices between many possibilities could threaten the function of a system rather than making it more durable and adaptable. The example is discussed based on a review of literature from the humanities as well as the natural sciences. Full article

The formose reaction is a plausible prebiotic chemistry, famed for its production of sugars. In this work, we demonstrate that the Cannizzaro process is the dominant process in the formose reaction under many different conditions, thus necessitating a catalyst for the formose reaction under various environmental circumstances. The investigated formose reactions produce primarily organic acids associated with metabolism, a protometabolic system, and yield very little sugar left over. This is due to many of the acids forming from the degradation and Cannizaro reactions of many of the sugars produced during the formose reaction. We also show the heterogeneous Lewis-acid-based catalysis of the formose reaction by mineral systems associated with serpentinization. The minerals that showed catalytic activity include olivine, serpentinite, and calcium, and magnesium minerals including dolomite, calcite, and our Ca/Mg-chemical gardens. In addition, computational studies were performed for the first step of the formose reaction to investigate the reaction of formaldehyde, to either form methanol and formic acid under a Cannizzaro reaction or to react to form glycolaldehyde. Here, we postulate that serpentinization is therefore the startup process necessary to kick off a simple proto metabolic system—the formose protometabolic system. Full article

The origin of life possibly required processes in confined systems that facilitated simple chemical reactions and other more complex reactions impossible to achieve under the condition of infinite dilution. In this context, the self-assembly of micelles or vesicles derived from prebiotic amphiphilic molecules is a cornerstone in the chemical evolution pathway. A prime example of these building blocks is decanoic acid, a short-chain fatty acid capable of self-assembling under ambient conditions. This study explored a simplified system made of decanoic acids under temperatures ranging from 0 °C to 110 °C to replicate prebiotic conditions. The study revealed the first point of aggregation of decanoic acid into vesicles and examined the insertion of a prebiotic-like peptide in a primitive bilayer. The information gathered from this research provides critical insights into molecule interactions with primitive membranes, allowing us to understand the first nanometric compartments needed to trigger further reactions that were essential for the origin of life. Full article

This review points out that three of the essential features of natural selection—competition for a finite resource, variation, and transmission of memory—occur in an extremely simple, thermalized molecular population, one of colliding “billiard balls” subject to an anisotropy, a directional flux of energetic molecules. The emergence of scaling behavior, scale invariance, in such systems is considered in the context of the emergence of complexity driven by Gibbs free energy, the origins of life, and known chemistries in planetary and astrophysical conditions. It is suggested that the thermodynamic formalism of statistical multifractality offers a parallel between the microscopic and macroscopic views of non-equilibrium systems and their evolution, different from, empirically determinable, and therefore complementing traditional definitions of entropy and its production in living systems. Further, the approach supports the existence of a bridge between microscopic and macroscopic scales, the missing mesoscopic scale. It is argued that natural selection consequently operates on all scales—whether or not life results will depend on both the initial and the evolving boundary conditions. That life alters the boundary conditions ensures nonlinearity and scale invariance. Evolution by natural selection will have taken place in Earth’s fluid envelope; both air and water display scale invariance and are far from chemical equilibrium, a complex condition driven by the Gibbs free energy arising from the entropy difference between the incoming solar beam and the outgoing infrared radiation to the cold sink of space acting on the initial conditions within evolving boundary conditions. Symmetry breaking’s role in the atmospheric state is discussed, particularly in regard to aerosol fission in the context of airborne bacteria and viruses in both current and prebiotic times. Over 4.4 billion years, the factors operating to support natural selection will have evolved along with the entire system from relative simplicity to the current complexity. Full article

The role of minerals in the origin of life and prebiotic evolution remains unknown and controversial. Mineral surfaces have the potential to facilitate prebiotic polymerization due to their ability to adsorb and concentrate biomolecules that subsequently can catalyse reactions; however, the precise nature of the interaction between the mineral host and the guest biomolecule still needs to be understood. In this context, we spectroscopically characterized, using infrared, X-ray photoemission spectroscopy (XPS) and X-ray diffraction (XRD) techniques, the interaction between L-proline and montmorillonite, olivine, iron disulphide, and haematite (minerals of prebiotic interest), by evaluating their interaction from a liquid medium. This work provides insight into the chemical processes occurring between proline, the only cyclic amino acid, and this selection of minerals, each of them bearing a particular chemical and crystal structures. Proline was successfully adsorbed on montmorillonite, haematite, olivine, and iron disulphide in anionic and zwitterionic chemical forms, being the predominant form directly related to the mineral structure and composition. Silicates (montmorillonite) dominate adsorption, whereas iron oxides (haematite) show the lowest molecular affinity. This approach will help to understand structure-affinity relationship between the mineral surfaces and proline, one of the nine amino acids generated in the Miller-Urey experiment. Full article

The standard approach to exploring prebiotic chemistry is to use a small number of highly purified reactants and to attempt to optimize the conditions required to produce a particular end product. However, purified reactants do not exist in nature. We have previously proposed that what drives prebiotic evolution are complex chemical ecologies. Therefore, we have begun to explore what happens if one substitutes “sea water”, with its complex mix of minerals and salts, for distilled water in the classic Miller experiment. We have also adapted the apparatus to permit it to be regassed at regular intervals so as to maintain a relatively constant supply of methane, hydrogen, and ammonia. The “sea water” used in the experiments was created from Mediterranean Sea salt with the addition of calcium phosphate and magnesium sulfate. Tests included several types of mass spectrometry, an ATP-monitoring device capable of measuring femtomoles of ATP, and a high-sensitivity cAMP enzyme-linked immunoadsorption assay. As expected, amino acids appeared within a few days of the start of the experiment and accumulated thereafter. Sugars, including glucose and ribose, followed as did long-chain fatty acids (up to C₂₀). At three-to-five weeks after starting the experiment, ATP was repeatedly detected. Thus, we have shown that it is possible to produce a “one-pot synthesis” of most of the key chemical prerequisites for living systems within weeks by mimicking more closely the complexity of real-world chemical ecologies. Full article

It is generally recognized that the evolution of the early Earth was affected by an external energy source: radiation from the early Sun. The hypothesis about the important role of natural radioactivity, as a source of internal energy in the evolution of the early Earth, is considered and substantiated in this work. The decay of the long-lived isotopes ²³²Th, ²³⁸U, ²³⁵U, and ⁴⁰K in the Global Ocean initiated the oxygenation of the hydro- and atmosphere, and the abiogenesis. The content of isotopes in the ocean and the kinetics of their decay, the values of the absorbed dose and dose rate, and the efficiency of sea water radiolysis, as a function of time, were calculated. The ocean served as both a “reservoir” that collected components of the early atmosphere and products of their transformations, and a “converter” in which further chemical reactions of these compounds took place. Radical mechanisms were proposed for the formation of simple amino acids, sugars, and nitrogen bases, i.e., the key structures of all living things, and also for the formation of oxygen. The calculation results confirm the possible important role of natural radioactivity in the evolution of terrestrial matter, and the emergence of life. Full article

The abundance and biological role of potassium suggest that its unstable nuclide was present in all stages of terrestrial biogenesis. With its enhanced isotopic ratio in the Archean eon, ${}^{40}$K may have contributed to the special, perhaps unique, biogenetic conditions that were present in the primitive Earth. Compared to the U and Th radionuclides, ${}^{40}$K has a less disruptive radiochemical impact, which may drive a moderate, but persistent evolution of the structural and functional properties of proto-biological molecules. In the main $\beta$-decay route of ${}^{40}$K, the radiation dose generated by an Archean solution with potassium ions can be larger than the present background radiation on Earth by one to two orders of magnitude. Estimates of the rates of organic molecules indirectly affected by $\beta$ decays are provided for two schematic models of the propagation of secondary events in the solvent of prebiotic solutions. The left-handed ${\beta }^{-}$ particles emitted by ${}^{40}$K are the best candidates to trigger an enantiomeric excess of L-type amino acids via weak nuclear forces in the primitive Earth. The concentration-dependent radiation dose of ${}^{40}$K fits well in dry–wet scenarios of life’s origins and should be considered in realistic simulations of prebiotic chemical pathways. Full article

Origins-of-life chemical experiments usually aim to produce specific chemical end-products such as amino acids, nucleic acids or sugars. The resulting chemical systems do not evolve or adapt because they lack natural selection processes. We have modified Miller origins-of-life apparatuses to incorporate several natural, prebiotic physicochemical selection factors that can be tested individually or in tandem: freezing-thawing cycles; drying-wetting cycles; ultraviolet light-dark cycles; and catalytic surfaces such as clays or minerals. Each process is already known to drive important origins-of-life chemical reactions such as the production of peptides and synthesis of nucleic acid bases and each can also destroy various reactants and products, resulting selection within the chemical system. No previous apparatus has permitted all of these selection processes to work together. Continuous synthesis and selection of products can be carried out over many months because the apparatuses can be re-gassed. Thus, long-term chemical evolution of chemical ecosystems under various combinations of natural selection may be explored for the first time. We argue that it is time to begin experimenting with the long-term effects of such prebiotic natural selection processes because they may have aided biotic life to emerge by taming the combinatorial chemical explosion that results from unbounded chemical syntheses. Full article

One of the problems that make it difficult to solve the mystery of the origin of life is determining how life emerged in chemically complex messy environments on primitive Earth. In this article, the “chemically complex messy environments” that are focused on are a mixed state of various organic compounds produced via prebiotic means and accumulated on primitive earth. The five factors described below are thought to have contributed to opening the way for the emergence of life: (1) A characteristic inherent in [GADV]-amino acids, which are easily produced via prebiotic means. [GADV] stands for four amino acids, Gly [G], Ala [A], Asp [D] and Val [V], which are indicated by a one-letter symbol. (2) The protein 0th-order structure or a [GADV]-amino acid composition generating water-soluble globular protein with some flexibility, which can be produced even by the random joining of [GADV]-amino acids. (3) The formation of versatile [GADV]-microspheres, which can grow, divide and proliferate even without a genetic system, was the emergence of proto-life. (4) The [GADV]-microspheres with a higher proliferation ability than others were able to be selected. Proto-Darwin evolution made it possible to proceed forward to the creation of a core life system composed of the (GNC)_n gene, anticodon stem-loop tRNA or AntiC-SL tRNA (GNC genetic code), and [GADV]-protein. (5) Eventually, the first genuine life with a core life system emerged. Thus, the formation processes of [GADV]-protein and the (GNC)_n gene in chemically complex messy environments were the steps to the emergence of genuine life. Full article