Origin of Life

Theories and evidence for chemical biopoieses

Iron-sulfur world

Wächtershäuser, in the iron-sulfur world theory, postulates that an early form of metabolism predated genetics. By metabolism, Wächtershäuser refered to a cycle of chemical reactions that produce energy in a form that can be harnessed by other processes. Wächtershäuser's idea was that a primitive metabolic cycle could produce increasingly complex compounds.

A key concept within the iron-sulfur theory was that this early chemistry of life occurred on mineral surfaces, such as iron pyrites, near deep submarine hydrothermal vents. This was an anerobic, hyperthermic (near 100oC), high pressure environment. Acetic acid plays a special role in Wächtershäuser's theory because acetic acid is part of the citric acid cycle that is fundamental to cellular metabolism.

Discussing the origin of life. [Science. 2002] PMID: 12400544
Origin of life. Some like it hot, but not the first biomolecules. [Science. 2002] PMID: 12065824
Origin of life. II. From prebiotic replicators to protocells. [Arch Sci Compte Rendu Seances Soc. 1999] PMID: 14677551
The role of accuracy for early stages of the origin of life. [Orig Life Evol Biosph. 1995] PMID: 11536674
Electroweak enantioselection and the origin of life. [Orig Life Evol Biosph. 1995] PMID: 11536670
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Critique of the hypothesis: Two-dimensional life? [Proc Natl Acad Sci U S A. 1991]
A model [Wachtershauser, G. (1988) Microbiol. Rev. 52, 452-484], according to which life started in the form of a monomolecular layer of interacting anionic metabolites electrostatically bound to a positively charged surface, is examined critically. The model raises a number of thermodynamic and kinetic difficulties.
de Duve C, Miller SL. Two-Dimensional Life? (Free Full Text pdf) Proc Natl Acad Sci U S A. 1991 Nov;88:10014-7.

Polymerization on the rocks: theoretical introduction. [Orig Life Evol Biosph. 1998] PMID: 9611763
The reactions of methanimine and cyanogen with carbon monoxide in prebiotic molecular evolution on earth. [Orig Life Evol Biosph. 2001] PMID: 11770257
Gunter Wachtershauser profile. Between a rock and a hard place. [Science. 2002] PMID: 11896256
The REH theory of protein and nucleic acid divergence: a retrospective update. [J Mol Evol. 1978] PMID: 722809
Reaction sequence of iron sulfide minerals in bacteria and their use as biomarkers
Primordial carbonylated iron-sulfur compounds and the synthesis of pyruvate. [Science. 2000] PMID: 10958777
A sulfurous start for protein synthesis? [Science. 1998] PMID: 9714669
Prebiotic chemistry. Where smokers rule. [Science. 1997] PMID: 9132945
See
Structure of subtilosin A, a cyclic antimicrobial peptide from Bacillus subtilis with unusual sulfur to alpha-carbon cross-links: formation and reduction of alpha-thio-alpha-amino acid derivatives. [Biochemistry. 2004] PMID: 15035610
The emergence of life from iron monosulphide bubbles at a submarine hydrothermal redox and pH front. [J Geol Soc London. 1997] PMID: 11541234
Ammonia formation by the reduction of nitrite/nitrate by FeS: ammonia formation under acidic conditions. [Orig Life Evol Biosph. 2005] PMID: 16228644
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Peptides by activation of amino acids with CO on (Ni,Fe)S surfaces: implications for the origin of life. [Science. 1998] PMID: 9685253
Activated acetic acid by carbon fixation on (Fe,Ni)S under primordial conditions. [Science. 1997] : modified: "In experiments modeling the reactions of the reductive acetyl-coenzyme A pathway at hydrothermal temperatures, it was found that an aqueous slurry of coprecipitated NiS and FeS converted CO and CH3SH into the activated thioester CH3-CO-SCH3, which hydrolyzed to acetic acid. In the presence of aniline, acetanilide was formed. When NiS-FeS was modified with catalytic amounts of selenium, acetic acid and CH3SH were formed from CO and H2S alone. The reaction can be considered as the primordial initiation reaction for a chemoautotrophic origin of life."
Huber C, Wachtershauser G. Activated acetic acid by carbon fixation on (Fe,Ni)S under primordial conditions. Science. 1997 Apr 11;276(5310):245-7. Comment in: Science. 1997 Apr 11;276(5310):222..

More from Wächtershäuser:
Review : Before enzymes and templates: theory of surface metabolism. Microbiol Rev. 1988 Dec;52(4):452-84.

A possible primordial peptide cycle. [Science. 2003] PMID: 12920291
A sulfurous start for protein synthesis? [Science. 1998] PMID: 9714669
Origin of life. Life as we don't know it. [Science. 2000] PMID: 10979855
Organic sulfur compounds resulting from the interaction of iron sulfide, hydrogen sulfide and carbon dioxide in an anaerobic aqueous environment. [Orig Life Evol Biosph. 1996] PMID: 11536750
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Historical perspective: the problem of the origin of life in the context of developments in biology. [Orig Life Evol Biosph. 1988] PMID: 3285284
Evolution of the first metabolic cycles. [Proc Natl Acad Sci U S A. 1990] PMID: 2296579
Life in a ligand sphere. [Proc Natl Acad Sci U S A. 1994] PMID: 8183902
Between history and physics. [J Mol Evol. 1982] PMID: 6178836
Obcells as proto-organisms: membrane heredity, lithophosphorylation, and the origins of the genetic code, the first cells, and photosynthesis. [J Mol Evol. 2001] PMID: 11675615
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Investigation of the prebiotic synthesis of amino acids and RNA bases from CO2 using FeS/H2S as a reducing agent. [Proc Natl Acad Sci U S A. 1995] PMID: 8524872
[FeS/FeS2], a redox system for the origin of life (some experiments on the pyrite-hypothesis). [Orig Life Evol Biosph. 1994] PMID: 11536658
Energetics and kinetics of the prebiotic synthesis of simple organic acids and amino acids with the FeS-H2S/FeS2 redox couple as reductant. [Orig Life Evol Biosph. 1999] PMID: 10077866
Activated acetic acid by carbon fixation on (Fe,Ni)S under primordial conditions. [Science. 1997] PMID: 9092471
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The origin of life and its methodological challenge. [J Theor Biol. 1997] PMID: 9299293
Evolution of the first metabolic cycles. [Proc Natl Acad Sci U S A. 1990] PMID: 2296579
A model for the origin of life. [J Mol Evol. 1982] PMID: 7120429
On the origin of metabolic pathways. [J Mol Evol. 1999] PMID: 10486000
Noisy clues to the origin of life. [Proc Biol Sci. 2002] PMID: 12495484
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The iron-sulphur proteins: evolution of a ubiquitous protein from model systems to higher organisms. [Orig Life. 1974] PMID: 4416334
Chemical evolution. [Nature. 1971] PMID: 4923113
Chemical evolution. [Am Sci. 1975] PMID: 1115436
Ambiguity in the interpretation of abiotic syntheses. [Orig Life. 1975] PMID: 1153186
Life's beginnings--origin

Photoelectrochemical power, chemical energy and catalytic activity for organic evolution on natural pyrite interfaces. [Orig Life Evol Biosph. 2003] PMID: 12967264
Reaction sequence of iron sulfide minerals in bacteria and their use as biomarkers. [Science. 1998] PMID: 9572727
Asymmetric adsorption by quartz: a model for the prebiotic origin of optical activity. [Orig Life. 1975] PMID: 171608
No soup for starters? Autotrophy and the origins of metabolism. [Trends Biochem Sci. 1995] PMID: 7482696
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A theoretical approach to the link between oxidoreductions and pyrite formation in the early stage of evolution. [Biochim Biophys Acta. 2002] PMID: 11997130
The origin of intermediary metabolism. [Proc Natl Acad Sci U S A. 2000] PMID: 10859347
The origin of life and its methodological challenge. [J Theor Biol. 1997] PMID: 9299293
Formation of amide bonds without a condensation agent and implications for origin of life. [Nature. 1994] PMID: 8159243
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The chemical basis of membrane bioenergetics.
All organisms rely on chemiosmotic membrane systems for energy transduction; the great variety of participating proteins and pathways can be reduced to a few universal principles of operation. This chemical basis of bioenergetics is reviewed with respect to the origin and early evolution of life. For several of the cofactors which play important roles in bioenergetic reactions, plausible prebiotic sources have been proposed, and it seems likely that these cofactors were present before elaborate protein structures. In particular, the hydrophobic quinones require only a membrane-enclosed compartment to yield a minimum chemiosmotic system, since they can couple electron transport and proton translocation in a simple way. It is argued that the central features of modern bioenergetics, such as the coupling of redox reactions and ion translocation at the cytoplasmic membrane, probably are ancient features which arose early during the process of biogenesis. The notion of a thermophile root of the universal phylogenetic tree has been discussed controversially, nevertheless, thermophiles are interesting model organisms for reconstructing the origin of chemiosmotic systems, since they are often acidophiles and anaerobic respirers exploiting iron-sulfur chemistry. This perspective can help to explain the prominent role of iron-sulfur proteins in extant biochemistry as well as the origin of both respiration and proton extrusion within the context of a possible origin of life in the vicinity of hot vents.
Berry S. The chemical basis of membrane bioenergetics. J Mol Evol. 2002 May;54(5):595-613.

More abstracts on membrane bioenergetics on PubMed:
Evolution of membrane bioenergetics. [J Supramol Struct. 1980] PMID: 6453255
Chemiosmotic systems in bioenergetics: H(+)-cycles and Na(+)-cycles. [Biosci Rep. 1991] PMID: 1668527
Bioenergetics of the Archaea. [Microbiol Mol Biol Rev. 1999] PMID: 10477309
Obcells as proto-organisms: membrane heredity, lithophosphorylation, and the origins of the genetic code, the first cells, and photosynthesis. [J Mol Evol. 2001] PMID: 11675615
The first cellular bioenergetic process: primitive generation of a proton-motive force. [J Mol Evol. 1991] PMID: 1663558

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