title: Does silica surface catalyse peptide bond formation? New insights from first-principles calculations.
abstract: The role that silica surface could have played in prebiotic chemistry as a catalyst for peptide bond formation has been addressed at the B3LYP/6-31+G(d,p) level for a model reaction involving glycine and ammonia on a silica cluster mimicking an isolated terminal silanol group present at the silica surface. Hydrogen-bond complexation between glycine and the silanol is followed by the formation of the mixed surface anhydride Si(surf)-O-C(=O)-R, which has been suggested in the literature to activate the C=O bond towards nucleophilic attack by a second glycine molecule, here simulated by the simpler NH3 molecule. However, B3LYP/6-31+G(d,p) calculations show that formation of the surface mixed anhydride Si(surf)-O-C(=O)-R is disfavoured (delta(r)G298 approximately 6 kcal mol(-1)), and that the surface bond only moderately lowers the free-energy barrier of the nucleophilic attack responsible for peptide bond formation (deltaG298(double dagger) approximately 48 kcal mol(-1)) in comparison with the uncatalysed reaction (deltaG298(double dagger) approximately 52 kcal mol(-1)). A further decrease of the free-energy barrier of peptide bond formation (deltaG298(double dagger) approximately 41 kcal mol(-1)) is achieved by a single water molecule close to the reaction centre acting as a proton-transfer helper in the activated complex. A possible role of strained silica surface defects on the formation of the surface mixed anhydride Si(surf)-O-C(=O)-R has also been addressed.
authors.affiliation: Departament de Química, Universitat Autònoma de Barcelona, Bellaterra 08193, Spain.
authors.forename: Albert
authors.initials: A
authors.lastname: Rimola
authors.forename: Sergio
authors.initials: S
authors.lastname: Tosoni
authors.forename: Mariona
authors.initials: M
authors.lastname: Sodupe
authors.forename: Piero
authors.initials: P
authors.lastname: Ugliengo
mesh_terms: D002384:Catalysis; D008958:Models, Molecular; D010455:Peptides / Q000737:chemistry*; D012822:Silicon Dioxide / Q000737:chemistry*; D012984:Software; D013816:Thermodynamics
chemical_list: D010455:Peptides; D012822:Silicon Dioxide