Groundworks for an evolutionary biochemistry: The iron-sulphur world

Crystalline surfaces of common rock-forming minerals are likely to have played several important roles in life’s geochemical origins. Transition metal sulfides and oxides promote a variety of organic reactions, including nitrogen reduction, hydroformylation, amination, and Fischer-Tropsch-type synthesis. Fine-grained clay minerals and hydroxides facilitate lipid self-organization and condensation polymerization reactions, notably of RNA monomers. Surfaces of common rock-forming oxides, silicates, and carbonates select and concentrate specific amino acids, sugars, and other molecular species, while potentially enhancing their thermal stabilities. Chiral surfaces of these minerals also have been shown to separate left- and right-handed molecules. Thus, mineral surfaces may have contributed centrally to the linked prebiotic problems of containment and organization by promoting the transition from a dilute prebiotic “soup” to highly ordered local domains of key biomolecules.

/pdf/mineral-surfaces-geochemical-complexities-and-the-origins-of-56mu84fw11.pdf

Mineral Surfaces, Geochemical Complexities, and the Origins of Life

Publisher Summary Over the past two decades there has been a phenomenal increase in the study of the chemistry of transition metal complexes containing sulfur ligands. There are a number of reasons for this, the major one being the revitalization of the chemistry of the unsaturated sulphur donor chelates. These were used as early as the 1930s as analytical reagents for various metals. The interest in complexes of these ligand systems now embraces areas ranging from purely academic syntheses to large-scale industrial production. Almost every available physical technique has been utilized for the elucidation of the molecular and electronic structures and the kinetics manifested in these systems. The spiraling interest in the complexes of sulfur donor ligands has prompted number of excellent and frequently exhaustive reviews. Other reasons for the expansion of the field of dithiochelate chemistry have undoubtedly included the correlations of model complexes with biological systems.

1,2-Dithiolene Complexes of Transition Metals

▪ Abstract The history of the theory and experimental evidence that the natural catalytic and reactive qualities of transition metal sulfides are linked to primitive metabolism is reviewed. In the late 1980s, a hypothesis arose that proposed that transition metal sulfides (in particular pyrrhotite and pyrite) might play a significant role promoting abiotic organic chemistry. As an outgrowth of this hypothesis, elaborate theories were presented, including proposals for earliest life being structurally distinct from extant prokaryotic life. During the 1990s and into the twenty-first century, experimental evidence has emerged that supports certain aspects of these theories; in other cases, the experiments reveal chemistry that diverges significantly from that which was proposed theoretically. In either case, however, there is clear evidence that transition metal sulfide minerals exhibit catalytic qualities for the promotion of reactions that have obvious metabolic utility and, therefore, could have provided ...

Transition metal sulfides and the origins of metabolism

https://hazen.carnegiescience.edu/sites/default/files/167-Cody-2001GCA.pdf

Geochemical roots of autotrophic carbon fixation: Hydrothermal experiments in the system citric acid, H 2 O-(FeS)-(NiS)

IN bacterial photosynthesis, reductive CO2 fixation was thought to proceed through activation of carboxylic acid by coenzyme A followed by the reductive incorporation of CO2 in the presence of reduced ferredoxin (a kind of non-haem iron–sulphur protein) and an enzyme, pyruvate synthase, as shown in equation (1). The reaction takes place in vitro in the same way using CoA, reduced ferredoxin and pyruvate synthase1.

Y. Yabushita

Papers

Amino acid synthesis through biogenetic-type CO2 fixation.