Mackinawite ([Fe>>Ni)S]), greigite (NiS2[Fe4S4]S2Fe) and a tunnel manganite (CaMn4O8) similar in structure to hollandite were minerals that enabled the onset of chemosynthesis and, later, of oxygenic photosynthesis
— the two events to make the greatest impact at the surface of our planet. The inorganic complexes contributing to the growth
of such minerals — ([FeS2Fe]4H2O; [Fe4S4]2+/1+; [Fe3S4]1+/0; NiFe5S8, CaMn4O8 as well as HP2O7
3−) — were later sequestered by small organic molecules (initially polypeptides or carboxylate groups) to become active centres
of the enzyme precursors that initially catalyzed the primary reactions of energy conversion and nutrient cycling. Examples
of such adventitious cooptions were to produce (i) pyrophosphate ‘eggs’ in successive main chain NH peptide nests; (ii) protoferredoxins
as thiolated metal sulfide eggs in peptide nests; (iii) precursors to carbon monoxide dehydrogenase (CODH)/acetyl CoA synthetase
(ACS) as a Nipeptide and a thiolated egg in a peptide nest and (iv) the precursor to the active centre of the OEC by periplasmic
carboxylates and hydroxyls adjacent to RC II in a protocyanobacterium.
Keywords Greigite - hollandite - mackinawite - origin of life - oxygen evolving complex