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

---

Enhancing d/p‐2π* Orbitals Hybridization via Strain Engineering for Efficient Photoreduction CO2

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(49)

Published: Aug. 13, 2024

Abstract The photoconversion of CO 2 into valuable chemical products using solar energy is a promising strategy to address both and environmental challenges. However, the strongly adsorbed frequently impedes seamless advancement subsequent reaction by significantly increasing activation energy. Here, we present BiFeO 3 material with lattice strain that collaboratively regulates d/p‐2π* orbitals hybridization between metal sites *CO as well *COOH intermediates achieve rapid conversion solidly critical intermediates, accelerating overall reduction kinetics. Quasi in situ X‐ray photoelectron spectroscopy Fourier Transform infrared combined theoretical calculation reveals optimized Fe enhance adsorption effect , continuous internal electrons are rapidly transferred injected surface under condition illumination, which promotes formation stability *COOH. Certainly, performance photoreduction improved 12.81‐fold compared base material. This work offers new perspective for process .

Language: Английский

---

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

---

Quantifying Catalysis at the Origin of Life**

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(53)

Published: Aug. 14, 2023

Abstract The construction of hypothetical environments to produce organic molecules such as metabolic intermediates or amino acids is the subject ongoing research into emergence life. Experiments specifically focused on an anabolic approach typically rely a mineral catalyst facilitate supply organics that may have produced prebiotic building blocks for Alternatively true catalytic system, could be sacrificially oxidized in production organics, necessitating emergent ‘life’ turn virgin materials each iteration processes. aim this perspective view current ‘metabolism‐first’ literature through lens chemistry evaluate need higher activity and analyses. While many elegant studies detailed chemical under geologically plausible biologically relevant conditions, few appear do so with sub‐stoichiometric amounts metals minerals. Moving toward rigorous analyses necessary demonstrate viability elusive cornerstone hypotheses: catalysis. We emphasize future work should decreased loading, increased productivity, and/or evidence

Language: Английский

---

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

---

Prebiotic Synthesis of Aspartate Using Life’s Metabolism as a Guide

Life, Journal Year: 2023, Volume and Issue: 13(5), P. 1177 - 1177

Published: May 12, 2023

A protometabolic approach to the origins of life assumes that conserved biochemistry metabolism has direct continuity with prebiotic chemistry. One most important amino acids in modern biology is aspartic acid, serving as a nodal metabolite for synthesis many other essential biomolecules. Aspartate’s complicated by instability its precursor, oxaloacetate. In this paper, we show use biologically relevant cofactor pyridoxamine, supported metal ion catalysis, sufficiently fast offset oxaloacetate’s degradation. Cu2+-catalysed transamination oxaloacetate pyridoxamine achieves around 5% yield within 1 h, and can operate across broad range pH, temperature, pressure. addition, downstream product β-alanine may also take place same reaction system at very low yields, directly mimicking an archaeal route. Amino group transfer pyridoxal shown from aspartate alanine, but reverse (alanine aspartate) shows poor yield. Overall, our results related indeed be synthesised via pathways foreshadow presence simple ions.

Language: Английский

---

Synergistic Effects of Silica‐Supported Iron−Cobalt Catalysts for CO₂ Reduction to Prebiotic Organics

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(11)

Published: Feb. 19, 2024

To test the ability of geochemical surfaces in serpentinizing hydrothermal systems to catalyze reactions from which metabolism arose, we investigated H

Language: Английский

---

Pinpointing Conditions for a Metabolic Origin of Life: Underlying Mechanisms and the Role of Coenzymes

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(20), P. 3032 - 3043

Published: Oct. 5, 2024

ConspectusFamously found written on the blackboard of physicist Richard Feynman after his death was phrase, "What I cannot create, do not understand." From this perspective, recreating origin life in lab is a necessary condition for achieving deep theoretical understanding biology. The "metabolism-first" hypothesis one leading frameworks life. A complex self-organized reaction network thought to have been driven into existence as chemical path least resistance release free energy environment that could otherwise be dissipated, rerouting from planetary processes organic chemistry. To increase complexity, network, initially under catalysis provided by its geochemical environment, must produced catalysts pruned existing flux through or expanded it new directions. This boot-strapping process would gradually lessen dependence initial catalytic and allow persist using own making. Eventually, leads seemingly inseparable interdependence at heart biology between (coenzymes, enzymes, genes) metabolic pathways synthesize them. Experimentally, primary challenge recreate conditions where such emerged. However, near infinite number microenvironments sources available early Earth elsewhere poses an enormous combinatorial challenge. constrain search, our has surveying reactions making up core some most ancient chemolithoautotrophic metabolisms, which consist only small repeating mechanisms, occur nonenzymatically. give fresh viewpoint first part account, we organized results search (along with important other laboratories) mechanism, rather than pathway. We expect identifying common set each type mechanism will help pinpoint emergence resembling metabolism. Many mechanisms were wide variety nonenzymatic conditions. Others, carboxylate phosphorylation C-C bond formation CO

Language: Английский

---

Direct Synthesis of Formamide from CO₂ and H₂O with Nickel–Iron Nitride Heterostructures under Mild Hydrothermal Conditions

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(36), P. 19768 - 19779

Published: Aug. 29, 2023

Formamide can serve as a key building block for the synthesis of organic molecules relevant to premetabolic processes. Natural pathways its from CO2 under early earth conditions are lacking. Here, we report thermocatalytic conversion and H2O formate formamide over Ni-Fe nitride heterostructures in absence synthetic H2 N2 mild hydrothermal conditions. While water act both solvent hydrogen source, metal nitrides nitrogen sources produce temperature range 25-100 °C 5-50 bar. Longer reaction times promote C-C bond coupling formation acetate acetamide additional products. Besides liquid products, methane ethane also produced gas-phase Postreaction characterization particles reveals structural alteration provides insights into potential mechanism. The findings indicate that gaseous carbon source C-N bonds heterostructure simulated vent

Language: Английский

---

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

---