Porphyrin in prebiotic catalysis: Ascertaining a route for the emergence of early metalloporphyrins

Abstract

Metal ions are known to catalyze certain prebiotic reactions. However, the transition from metal ions to extant metalloenzymes remains unclear. Porphyrins are found ubiquitously in the catalytic core of many ancient metalloenzymes. In this study, we evaluated the influence of porphyrin-based organic scaffold, on the catalysis, emergence and putative molecular evolution of prebiotic metalloporphyrins. We studied the effect of porphyrins on the transition metal ion-mediated oxidation of hydroquinone (HQ). We report a change in the catalytic activity of the metal ions in the presence of porphyrin. This was observed to be facilitated by the coordination between metal ions and porphyrins or by formation of non-coordinated complexes. The metal-porphyrin complexes also oxidized NADH, underscoring its versatility at oxidizing more than one substrate. Our study highlights the selective advantage that some of the metal ions would have had in the presence of porphyrin, underscoring their role in shaping the evolution of protometalloenzymes.

Ferric hemebin aqueous micellar and vesicular systems: state-of-the-art and challenges

“…In numerous examples it has been clearly showcased that different types of heme and their organic precursors can be synthesized under prebiotically plausible conditions. These conditions include (i) different Miller–Urey type experimental settings (Szutka, 1964; Hodgson and Baker, 1967; Hodgson and Ponnamperuma, 1968; Simionescu et al ., 1978; Meierhenrich et al ., 2005; Lindsey et al ., 2009); (ii) conditions that mimic primordial volcanic islands (Fox and Strasdeit, 2013) or hydrothermal vents (Seitz et al ., 2021); and (iii) other conditions as well (Soares et al ., 2013; Alexy et al ., 2015; Deans et al ., 2016; Taniguchi et al ., 2016; Pleyer et al ., 2018; Dagar et al ., 2022).…”

“…As a reaction product, a mixture of different porphyrins is obtained. Metalation of the porphyrins occurs in a third step (Pleyer et al ., 2018; Dagar et al ., 2022) or alternatively, metal salts are present during the synthesis with the metal ion coordinating to the forming porphyrins. In the latter case, it has been shown that the presence of metal ions significantly increased the yield of pyrroles (Seitz et al ., 2021) and porphyrins (Simionescu et al ., 1978) as compared to metal-free reactions.…”