Influence of Extreme Thermodynamic Conditions and Pyrite Surfaces on Peptide Synthesis in Aqueous Media
journal contributionposted on 05.03.2008, 00:00 by Eduard Schreiner, Nisanth N. Nair, Dominik Marx
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 α-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.
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Extreme temperaturepeptidizationfluctuationPyrite SurfacesAqueous MediaFree energy landscapesdiglycinepreformationreaction mechanismspyrite surfaceExtreme Thermodynamic Conditionscarbonyl sulfidefavorsynthesisacid activationisocyanateLeuchPeptide Synthesisformationreaction barrierscomputationallyscaffoldingambient bulk water environmentcyclicInfluencepathwaypressure conditionsFeSNCAanhydride