Influence of Composition of Nickel‐Iron Nanoparticles for Abiotic CO₂ Conversion to Early Prebiotic Organics

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(22)

Published: March 23, 2023

Abiotic synthesis of formate and short hydrocarbons takes place in serpentinizing vents where some members vent microbial communities live on abiotic as their main carbon source. To better understand the catalytic properties Ni-Fe minerals that naturally exist hydrothermal vents, we have investigated ability synthetic based nanoparticular solids to catalyze H2 -dependent reduction CO2 , first step required for beginning pre-biotic chemistry. Mono bimetallic nanoparticles with varied Ni-to-Fe ratios transform into intermediates products acetyl-coenzyme A pathway-formate, acetate, pyruvate-in mM range under mild conditions. Furthermore, catalysts converted similar without molecular by using water a hydrogen Both chemisorption analysis post-reaction characterization materials indicate Ni Fe metals play complementary roles fixation.

Language: Английский

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Ferredoxin reduction by hydrogen with iron functions as an evolutionary precursor of flavin-based electron bifurcation

Proceedings of the National Academy of Sciences, Journal Year: 2024, Volume and Issue: 121(13)

Published: March 21, 2024

Autotrophic theories for the origin of metabolism posit that first cells satisfied their carbon needs from CO 2 and were chemolithoautotrophs obtained energy electrons H . The acetyl-CoA pathway fixation is central to view because its antiquity: Among known fixing pathways it only one i) exergonic, ii) occurs in both bacteria archaea, iii) can be functionally replaced full by single transition metal catalysts vitro. In order operate at a pH close 7, however, requires complex multi-enzyme systems capable flavin-based electron bifurcation reduce low potential ferredoxin—the physiological donor pathway—with How primordial if bifurcation? Here, we show native iron (Fe 0 ), but not Ni , Co Mo NiFe, Fe, 3 or Fe O 4 promotes -dependent reduction aqueous Clostridium pasteurianum ferredoxin 8.5 higher within few hours 40 °C, providing function bifurcation, without help enzymes organic redox cofactors. ties early metabolic evolution chemical process Earth’s crust promoted solid-state iron, still deposited serpentinizing hydrothermal vents today.

Language: Английский

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A prebiotic Krebs cycle analog generates amino acids with H2 and NH3 over nickel

Chem, Journal Year: 2024, Volume and Issue: 10(5), P. 1528 - 1540

Published: Feb. 27, 2024

Hydrogen (H2) has powered microbial metabolism for roughly 4 billion years. The recent discovery that it also fuels geochemical analogs of the most ancient biological carbon fixation pathway sheds light on origin metabolism. However, remains unclear whether H2 can sustain more complex nonenzymatic reaction networks. Here, we show drives reductive amination six ketoacids and glyoxylate to give corresponding amino acids in good yields using ammonium concentrations ranging from 6 150 mM. Catalytic amounts nickel or ground meteorites enable these reactions at 22°C pH 8. same conditions promote an H2-dependent ketoacid-forming aldol chemistry co-occurs with amination, producing a continuous network resembling acid synthesis metabolic core microbes. results support hypothesis earliest biochemical networks could have emerged without enzymes RNA.

Language: Английский

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Low-temperature hydrogen production and consumption in partially-hydrated peridotites in Oman: implications for stimulated geological hydrogen production

Frontiers in Geochemistry, Journal Year: 2024, Volume and Issue: 2

Published: March 25, 2024

The Samail Ophiolite in Oman, the largest exposed body of ultramafic rocks at Earth’s surface, produces a continuous flux hydrogen through low-temperature water/rock reactions. In turn, scale subsurface microbial biosphere is sufficient to consume much this hydrogen, except where H 2 delivered surface seeps via faults. By integrating data from recent investigations into alteration history peridotites, groundwater dynamics, and serpentinite-hosted communities, we identify feasible conditions for pilot demonstration stimulated geological production. A simple technoeconomic analysis shows that stimulation methods be used must increase rate net production least 10,000-fold compared estimated natural economically produce engineered reactions peridotite formations. It may possible meet challenge within upper 1–2 km, given projected availability reactive Fe(II)-bearing phases lower drilling costs associated with shallower operations. Achieving ≥10,000-fold increases will require combination stimuli. likely necessary density fracturing reaction volume by two orders magnitude. Then, -production rates also increased another magnitude increasing ratio modifying chemistry injected fluids optimize formation Fe(III)-bearing secondary phases. These fluid modifications designed simultaneously minimize consumption volume. contrast, preserving high potentials biological shallow groundwaters replete oxidants such as nitrate, sulfate dissolved inorganic carbon reduce potential any inadvertent leaks atmosphere, it acts an indirect greenhouse gas.

Language: Английский

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Chemiosmotic ATP synthesis by minimal protocells

Cell Reports Physical Science, Journal Year: 2025, Volume and Issue: 6(3), P. 102461 - 102461

Published: March 1, 2025

Highlights•Fatty acid membranes can maintain sufficient proton gradients•ATP synthase-embedded minimal protocells produce ATP•The protocell have an influence on ATP synthesisSummaryEnergy conservation is crucial to life's origin and evolution. The common ancestor of all cells used synthase convert gradients into ATP. However, pumps generating lipids maintaining are not universally conserved across lineages. A solution this paradox that ancestral could harness naturally formed geochemical ion with simpler environmentally provided precursors preceding both biogenic membranes. This runs counter traditional views phospholipid bilayers required gradients. Here, we show fatty synthesize by under the steep pH temperature observed in hydrothermal vent systems. These findings shed substantial light early membrane bioenergetics, uncovering a functional intermediate evolution chemiosmotic synthesis during protocellular stages postdating synthase's but advent enzymatically synthesized cell membranes.Graphical abstract

Language: Английский

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Serpentinization as the source of energy, electrons, organics, catalysts, nutrients and pH gradients for the origin of LUCA and life

Frontiers in Microbiology, Journal Year: 2023, Volume and Issue: 14

Published: Oct. 2, 2023

Serpentinization in hydrothermal vents is central to some autotrophic theories for the origin of life because it generates compartments, reductants, catalysts and gradients. During process serpentinization, water circulates through systems crust where oxidizes Fe (II) ultramafic minerals generate (III) H 2 . Molecular hydrogen can, turn, serve as a freely diffusible source electrons reduction CO organic compounds, provided that suitable are present. Using naturally synthesized during serpentinization reduces formate, acetate, pyruvate, methane. These compounds represent backbone microbial carbon energy metabolism acetogens methanogens, strictly anaerobic chemolithoautotrophs use acetyl-CoA pathway fixation inhabit serpentinizing environments today. reduced carbon, nitrogen — newer findings suggest phosphorous were likely conducive origins process. In addition, gives rise inorganic microcompartments proton gradients right polarity sufficient magnitude support chemiosmotic ATP synthesis by rotor-stator synthase. This would help explain why principle harnessing more conserved (older) than machinery ion via pumping coupled exergonic chemical reactions, which case methanogens involve -dependent reduction. Serpentinizing exist terrestrial deep ocean environments. On early Earth they probably abundant There evidence once occurred on Mars still occurring Saturn’s icy moon Enceladus, providing perspective disequilibrium other worlds.

Language: Английский

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The Rock-Hosted Biosphere

Annual Review of Earth and Planetary Sciences, Journal Year: 2023, Volume and Issue: 51(1), P. 493 - 519

Published: May 31, 2023

Our understanding of Earth's rock-hosted subsurface biosphere has advanced over the past two decades through collection and analysis fluids rocks from aquifers within continental oceanic crust. Improvements in cell extraction, sorting, DNA sequencing, techniques for detecting distributions activity have revealed how combination lithology, permeability, fluid mixing processes controls diversity heterogeneous distribution microbial communities fractured rock systems. However, functions most organisms, rates their growth, remain largely unknown. To mechanistically understand what physiochemical hydrological factors control biosphere, future studies are needed to characterize physiology microorganisms adapted mineral-associated growth under energy- nutrient-limited conditions. Experiments should be designed detect synergistic interactions between microorganisms, minerals, at highly variable turnover rates.▪The is controlled by variations porosity, chemical disequilibrium.▪Several imaging can sensitively biosphere.▪The poorly known.

Language: Английский

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A non-methanogenic archaeon within the order Methanocellales

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 13, 2024

Abstract Serpentinization, a geochemical process found on modern and ancient Earth, provides an ultra-reducing environment that can support microbial methanogenesis acetogenesis. Several groups of archaea, such as the order Methanocellales , are characterized by their ability to produce methane. Here, we generate metagenomic sequences from serpentinized springs in The Cedars, California, construct circularized metagenome-assembled genome archaeon, termed Met12, lacks essential genes. includes genes for acetyl-CoA pathway, but encoding enzymes methyl-coenzyme M reductase, heterodisulfide reductases hydrogenases. In situ transcriptomic analyses reveal high expression multi-heme c- type cytochrome, heterologous this protein model bacterium demonstrates it is capable accepting electrons. Our results suggest within not methanogen CO 2 -reducing, electron-fueled acetogen without electron bifurcation.

Language: Английский

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A self-sustaining serpentinization mega-engine feeds the fougerite nanoengines implicated in the emergence of guided metabolism

Frontiers in Microbiology, Journal Year: 2023, Volume and Issue: 14

Published: May 15, 2023

The demonstration by Ivan Barnes et al. that the serpentinization of fresh Alpine-type ultramafic rocks results in exhalation hot alkaline fluids is foundational to submarine vent theory (AVT) for life’s emergence its ‘improbable’ thermodynamic state. In AVT, such ≤ 150°C, bearing H 2 > CH 4 HS − —generated and driven convectively a serpentinizing exothermic mega-engine operating crust—exhale into iron-rich, CO NO 3 -bearing Hadean ocean result hydrothermal precipitate mounds comprising macromolecular ferroferric-carbonate oxyhydroxide minor sulfide. As nanocrystalline minerals fougerite/green rust mackinawite (FeS), they compose spontaneously precipitated inorganic membranes keep highly contrasting solutions apart, thereby maintaining redox pH disequilibria. They do so form fine chimneys chemical gardens. same disequilibria drive reduction HCOO or CO, oxidation methyl group—the two products reacting acetate sequence antedating ‘energy-producing’ acetyl coenzyme-A pathway. Fougerite 2D-layered mineral which hydrous interlayers themselves harbor 2D solutions, effect constricted ~ 1D preferentially directed electron hopping/tunneling, proton Gröthuss ‘bucket-brigading’ when subject charge. redox-driven nanoengine peristaltic pump, fougerite forces ordered nitrate ammonium, amination pyruvate oxalate alanine glycine, their condensation short peptides. turn, these peptides have flexibility sequester founding iron oxyhydroxide, sulfide, pyrophosphate clusters, produce metal- phosphate-dosed organic films cells. feed mound fails, only equivalent sustenance on offer first autotrophs still mildly upper crust beneath. While conditions here are very much less bountiful, similar survivors accustomed to. Sometime during this transition, replicating non-ribosomal guidance system discovered provide rules take incrementally changing surroundings. details how apparatuses emerged hard problem, but doing progenote archaea bacteria could begin colonize what would become deep biosphere. Indeed, anaerobic nitrate-respiring methanotrophic deep-branching Acetothermia presently comprise portion microbiome occupying offers circumstantial support notion. However, inescapable, if jarring conclusion drawn that, absent rust, there be no structured channelway life.

Language: Английский

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Chemical Antiquity in Metabolism

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(16), P. 2267 - 2278

Published: July 31, 2024

ConspectusLife is an exergonic chemical reaction. The same was true when the very first cells emerged at life's origin. In order to live, all need a source of carbon, energy, and electrons drive their overall reaction network (metabolism). most cells, these are separate pathways. There only one biochemical pathway that serves three needs simultaneously: acetyl-CoA CO

Language: Английский

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