Influence of extreme thermodynamic conditions and pyrite surfaces on peptide synthesis in aqueous media.

Free energy landscapes and reaction mechanisms underlying the synthesis of diglycine in water were studied computationally. It was found that amino acid activation by carbonyl sulfide, leading to the formation of a cyclic alpha-amino acid N-carboxyanhydride (NCA, or Leuchs anhydride), preferentially follows an indirect pathway that involves an isocyanate intermediate. Extreme temperature and pressure conditions accelerate peptidization greatly compared to the ambient bulk water environment and are shown to favor, in general, concerted versus stepwise mechanisms. Finally, a pyrite surface, FeS2 (001), is found to lower reaction barriers further by decreasing fluctuations and by assisting the preformation of the cyclic five-membered NCA ring due to scaffolding.

[1]  H. Weingärtner,et al.  Supercritical water as a solvent. , 2005, Angewandte Chemie.

[2]  M. Sprik.  Computation of the pK of liquid water using coordination constraints , 2000 .

[3]  E. Baerends,et al.  Chemical Involvement of Solvent Water Molecules in Elementary Steps of the Fenton Oxidation Reaction. , 2001, Angewandte Chemie.

[4]  L. Cattolico,et al.  Genome Sequence of a Polydnavirus: Insights into Symbiotic Virus Evolution , 2004, Science.

[5]  D. Marx,et al.  Glycine on a wet pyrite surface at extreme conditions. , 2003, Journal of the American Chemical Society.

[6]  D. Marx,et al.  AB INITIO Simulations of Desorption and Reactivity of Glycine at a Water-Pyrite Interface at “Iron-Sulfur World” Prebiotic Conditions , 2006, Origins of Life and Evolution of Biospheres.

[7]  Bernd Ensing,et al.  Perspective on the reactions between F- and CH3CH2F: the free energy landscape of the E2 and SN2 reaction channels. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[8]  Preston Moore,et al.  Metadynamics as a tool for exploring free energy landscapes of chemical reactions. , 2006, Accounts of chemical research.

[9]  Alessandro Laio,et al.  Efficient exploration of reactive potential energy surfaces using Car-Parrinello molecular dynamics. , 2003, Physical review letters.

[10]  Ab initio molecular dynamics study of the reaction of water with formaldehyde in sulfuric acid solution. , 1998 .

[11]  Alessandro Curioni,et al.  DENSITY FUNCTIONAL THEORY-BASED MOLECULAR DYNAMICS SIMULATION OF ACID-CATALYZED CHEMICAL REACTIONS IN LIQUID TRIOXANE , 1997 .

[12]  J. Hough,et al.  Circular polarization in star-formation regions: implications for biomolecular homochirality. , 1998, Science.

[13]  H. Kricheldorf.  Polypeptides and 100 years of chemistry of α-amino acid N-carboxyanhydrides , 2006 .

[14]  G. Wächtershäuser,et al.  Peptides by activation of amino acids with CO on (Ni,Fe)S surfaces: implications for the origin of life. , 1998, Science.

[15]  G. Wächtershäuser,et al.  From volcanic origins of chemoautotrophic life to Bacteria, Archaea and Eukarya , 2006, Philosophical Transactions of the Royal Society B: Biological Sciences.

[16]  A. Laio,et al.  Escaping free-energy minima , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[17]  M. Parrinello,et al.  Hydrogen bond driven chemical reactions: Beckmann rearrangement of cyclohexanone oxime into epsilon-caprolactam in supercritical water. , 2004, Journal of the American Chemical Society.

[18]  L. Orgel,et al.  Carbonyl Sulfide-Mediated Prebiotic Formation of Peptides , 2004, Science.

[19]  E. Meijer,et al.  Realistic modeling of ruthenium-catalyzed transfer hydrogenation. , 2007, Journal of the American Chemical Society.

[20]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[21]  John M. Stubbs,et al.  Glycosidic bond formation in aqueous solution: on the oxocarbenium intermediate. , 2003, Journal of the American Chemical Society.