Did Cyclic Metaphosphates Have a Role in the Origin of Life?

Abstract

How life began still eludes science life, the initial progenote in the context presented herein, being a chemical aggregate of primordial inorganic and organic molecules capable of self-replication and evolution into ever increasingly complex forms and functions.Presented is a hypothesis that a mineral scaffold generated by geological processes and containing polymerized phosphate units was present in primordial seas that provided the initiating factor responsible for the sequestration and organization of primordial life’s constituents. Unlike previous hypotheses proposing phosphates as the essential initiating factor, the key phosphate described here is not a polynucleotide or just any condensed phosphate but a large (in the range of at least 1 kilo-phosphate subunits), water soluble, cyclic metaphosphate, which is a closed loop chain of polymerized inorganic phosphate residues containing only phosphate middle groups. The chain forms an intrinsic 4-phosphate helix analogous to its structure in Na Kurrol’s salt, and as with DNA, very large metaphosphates may fold into hairpin structures. Using a Holliday-junction-like scrambling mechanism, also analogous to DNA, rings may be manipulated (increased, decreased, exchanged) easily with little to no need for additional energy, the reaction being essentially an isomerization.A literature review is presented describing findings that support the above hypothesis. Reviewed is condensed phosphate inorganic chemistry including its geological origins, biological occurrence, enzymes and their genetics through eukaryotes, polyphosphate functions, circular polynucleotides and the role of the Holliday junction, previous biogenesis hypotheses, and an Eoarchean Era timeline.

Ionically conducting inorganic binders: a paradigm shift in electrochemical energy storage

“…Also, the blue shift of O-P-O (enhanced bond length) and redshift of P-O-P (shortened bond length) stretching frequencies indicate a geometrical change in the PO 3 group. Besides, chain phosphates hydrolyze readily in water, unlike cyclic phosphates 28 . SHMP, SPP, and STMP were dissolved in water, dried, and heated at various temperatures to validate this postulate.…”

“…Besides, chain phosphates hydrolyze readily in water, unlike cyclic phosphates. 28 SHMP, SPP, and STMP were dissolved in water, dried, and heated at various temperatures to validate this postulate. STMP showed a crystalline XRD pattern that typically matches that of pristine STMP (Fig.…”

Prebiotic Chemistry: The Role of Trimetaphosphate in Prebiotic Chemical Evolution

“…All of the above evidences infer the existence of polyphosphates before the existence of living matter, and promotes the occurrence of chemical reactions and the evolution of life. Furthermore, numerous investigations into the phosphorylation and polymerization of biomolecules and polyphosphates have been conducted in this area ( Ponnamperuma et al, 1963b ; Schwartz and Fox, 1964 ; Ponnamperuma and Mack, 1965 ; Ferris, 1968 ; Fox and Waehneldt, 1968 ; Lohrmann and Orgel, 1968 ; Rabinowitz et al, 1968 ; Schwartz and Ponnamperuma, 1968 ; Rabinowitz et al, 1969 ; Rabinowitz, 1970 ; Lohrmann and Orgel, 1971 ; Handschuh et al, 1973 ; Lohrmann, 1975 ; Hulshof and Ponnamperuma, 1976 ; Schoffstall, 1976 ; Yamagata et al, 1979 ; Yamanaka et al, 1988 ; Schwartz, 2006 ; Holm and Baltscheffsky, 2011 ; Kee and Monnard, 2017 ; Christ et al, 2020 ; Serov et al, 2020 ; Brunk and Marshall, 2021 ; Glonek, 2021 ; Ying et al, 2021 ).…”

Lost in Condensation: Poly-, Cyclo-, and Ultraphosphates

“…21−23 A ring containing 12 phosphorus atoms has been described and was structurally characterized as its guanidinium salt, 24 but beyond that lies uncharted territory. 25 The analogy to (cyclo)alkanes helps us to grasp the structural richness that could potentially be generated within the family of condensed phosphates, let alone the fact that also metal coordination to deprotonated OH groups will create further diversity. 22 Given the many opportunities, our groups have embarked on a synthesis program that is aiming toward further exploring the condensed phosphates and their potential application to (modified) metabolite synthesis and inorganic and analytical biochemistry.…”

“…Despite the many hundreds of condensed phosphate structures for molecules containing from only 1 to 12 phosphorus atoms (cyclic, linear, branched in different ways, admixtures of rings and chains, fused rings, and stereoisomers), the number of crystallographically characterized polyphosphate structures is barely in double digits. − A ring containing 12 phosphorus atoms has been described and was structurally characterized as its guanidinium salt, but beyond that lies uncharted territory …”