title: The Influence of Mineral Matrices on the Thermal Behavior of Glycine.
abstract: On the Hadean-Early Archean Earth, the first islands must have provided hot and dry environments for abiotically formed organic molecules. The heat sources, mainly volcanism and meteorite impacts, were also available on Mars during the Noachian period. In recent work simulating this scenario, we have shown that neat glycine forms a black, sparingly water-soluble polymer ("thermomelanoid") when dry-heated at 200 °C under pure nitrogen. The present study explores whether relevant minerals and mineral mixtures can change this thermal behavior. Most experiments were conducted at 200 or 250 °C for 2 or 7 days. The mineral matrices used were phyllosilicates (Ca-montmorillonites SAz-1 and STx-1, Na-montmorillonite SAz-1-Na, nontronite NAu-1, kaolinite KGa-1), salts (NaCl, NaCl-KCl, CaCl2, artificial sea salt, gypsum, magnesite), picritic basalt, and three Martian regolith simulants (P-MRS, S-MRS, JSC Mars-1A). The main analytical method employed was high-performance liquid chromatography (HPLC). Glycine intercalated in SAz-1 and SAz-1-Na was well protected against thermomelanoid formation and sublimation at 200 °C: after 2 days, 95 and 79 %, respectively, had either survived unaltered or been transformed into the cyclic dipeptide (DKP) and linear peptides up to Gly6. The glycine survival rate followed the order SAz-1 > SAz-1-Na > STx-1 ≈ NAu-1 > KGa-1. Very good protection was also provided by artificial sea salt (84 % unaltered glycine after 200 °C for 7 days). P-MRS promoted the condensation up to Gly6, consistent with its high phyllosilicate content. The remaining matrices were less effective in preserving glycine as such or as peptides.
authors.affiliation: Department of Bioinorganic Chemistry, Institute of Chemistry, University of Hohenheim, Garbenstr. 30, 70599, Stuttgart, Germany.
authors.forename: Punam
authors.initials: P
authors.lastname: Dalai
authors.affiliation: Department of Bioinorganic Chemistry, Institute of Chemistry, University of Hohenheim, Garbenstr. 30, 70599, Stuttgart, Germany.
authors.forename: Hannes Lukas
authors.initials: HL
authors.lastname: Pleyer
authors.affiliation: Department of Bioinorganic Chemistry, Institute of Chemistry, University of Hohenheim, Garbenstr. 30, 70599, Stuttgart, Germany. henry.strasdeit@uni-hohenheim.de.
authors.forename: Henry
authors.initials: H
authors.lastname: Strasdeit
authors.affiliation: Department of Bioinorganic Chemistry, Institute of Chemistry, University of Hohenheim, Garbenstr. 30, 70599, Stuttgart, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Fox
mesh_terms: D019418:Evolution, Chemical; D005998:Glycine / Q000737:chemistry*; D008903:Minerals / Q000737:chemistry*
chemical_list: D008903:Minerals; D005998:Glycine
keywords: Clay minerals; Dry heating; Early Earth and Mars; Evaporites; Glycine homopeptides; Martian regolith simulants