title: Catalyzed Synthesis of Zinc Clays by Prebiotic Central Metabolites.
abstract: How primordial metabolic networks such as the reverse tricarboxylic acid (rTCA) cycle and clay mineral catalysts coevolved remains a mystery in the puzzle to understand the origin of life. While prebiotic reactions from the rTCA cycle were accomplished via photochemistry on semiconductor minerals, the synthesis of clays was demonstrated at low temperature and ambient pressure catalyzed by oxalate. Herein, the crystallization of clay minerals is catalyzed by succinate, an example of a photoproduced intermediate from central metabolism. The experiments connect the synthesis of sauconite, a model for clay minerals, to prebiotic photochemistry. We report the temperature, pH, and concentration dependence on succinate for the synthesis of sauconite identifying new mechanisms of clay formation in surface environments of rocky planets. The work demonstrates that seeding induces nucleation at low temperatures accelerating the crystallization process. Cryogenic and conventional transmission electron microscopies, X-ray diffraction, diffuse reflectance Fourier transformed infrared spectroscopy, and measurements of total surface area are used to build a three-dimensional representation of the clay. These results suggest the coevolution of clay minerals and early metabolites in our planet could have been facilitated by sunlight photochemistry, which played a significant role in the complex interplay between rocks and life over geological time.
authors.affiliation: Department of Chemistry, University of Kentucky, Lexington, KY, 40506, USA.
authors.forename: Ruixin
authors.initials: R
authors.lastname: Zhou
authors.affiliation: Facility for Electron Microscopy Research, McGill University, 3640 University Street, Montreal, Quebec, H3A 0C7, Canada.
authors.forename: Kaustuv
authors.initials: K
authors.lastname: Basu
authors.affiliation: Earth, Atmosphere, and Planetary Science Department, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA.
authors.forename: Hyman
authors.initials: H
authors.lastname: Hartman
authors.affiliation: Department of Plant and Soil Sciences, University of Kentucky, Lexington, KY, 40546, USA.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Matocha
authors.affiliation: Facility for Electron Microscopy Research, McGill University, 3640 University Street, Montreal, Quebec, H3A 0C7, Canada.
authors.forename: S Kelly
authors.initials: SK
authors.lastname: Sears
authors.affiliation: Facility for Electron Microscopy Research, McGill University, 3640 University Street, Montreal, Quebec, H3A 0C7, Canada.|Department of Anatomy & Cell Biology, 3640 University Street, Montreal, H3A 0C7, Canada.
authors.forename: Hojatollah
authors.initials: H
authors.lastname: Vali
authors.affiliation: Department of Chemistry, University of Kentucky, Lexington, KY, 40506, USA. marcelo.guzman@uky.edu.
authors.forename: Marcelo I
authors.initials: MI
authors.lastname: Guzman