Origins of Life and Evolution of Biospheres

, Volume 39, Issue 6, pp 495–515

Simple Formation of an Abiotic Porphyrinogen in Aqueous Solution

  • Jonathan S. Lindsey
  • Marcin Ptaszek
  • Masahiko Taniguchi
Prebiotic Chemistry

DOI: 10.1007/s11084-009-9168-3

Cite this article as:
Lindsey, J.S., Ptaszek, M. & Taniguchi, M. Orig Life Evol Biosph (2009) 39: 495. doi:10.1007/s11084-009-9168-3

Abstract

Porphyrins have long been proposed as key ingredients in the emergence of life yet plausible routes for forming their essential pyrrole precursor have heretofore not been identified. Here we show that the anaerobic reaction of δ-aminolevulinic acid (ALA, 1–5 mM) with the β-ketoester methyl 4-methoxyacetoacetate (2–40 mM) in water (pH 5–7) at 70–100°C for >6 h affords the porphyrinogen, which upon chemical oxidation gives the corresponding porphyrin in overall yield of up to 10%. The key intermediate is the α-methoxymethyl-substituted pyrrole, which undergoes tetramerization and macrocycle formation under kinetic control. The resulting type-I porphyrin bears four propionic acid and four carbomethoxy groups, is distinct from porphyrins (e.g., uroporphyrin or coproporphyrin) derivable from ALA alone via the extant universal biosynthetic path to tetrapyrroles, and is photoactive upon assembly into cationic micelles in aqueous solution. The simple self-organization of eight acyclic molecules into a tetrapyrrole macrocycle, from which a porphyrin is derived that is photoactive in lipid assemblies, augurs well for the spontaneous origin of catalysts and pigments essential for prebiotic metabolism and proto-photosynthesis.

Keywords

PrebioticPyrrolePorphyrinogenPorphyrinSelf-assemblyMicellePhotosynthesis

Supplementary material

11084_2009_9168_MOESM1_ESM.pdf (752 kb)
ESM 1ESI-MS spectra; 1H NMR spectra; discussion concerning expected spectra for distinct porphyrin regioisomers; and full experimental procedures for anaerobic reactions as well as the preparation and isolation of porphyrin 4. (PDF 751 kb)

Copyright information

© Springer Science+Business Media B.V. 2009

Authors and Affiliations

  • Jonathan S. Lindsey
    • 1
  • Marcin Ptaszek
    • 1
  • Masahiko Taniguchi
    • 1
  1. 1.Department of ChemistryNorth Carolina State UniversityRaleighUSA