title: Cooperativity in the Self-Assembly of the Guanine Nucleobase into Quartet and Ribbon Structures on Surfaces.
abstract: The guanine nucleobase can self-assemble into tetrameric or ribbon structures on surfaces or in solution. The origin for the occurrence of different aggregation patterns has not yet been investigated. Herein, a quantum chemical study on the different self-assembled structures of guanine and xanthine by using dispersion-corrected DFT is presented. Theoretical investigations can be used to explain, from an electronic point of view, the differences between the experimental findings. With quantitative Kohn-Sham molecular orbital theory and the accompanying energy decomposition analysis, the hydrogen-bonding mechanism within the guanine ribbons can be disclosed and the preferred self-assembled structures under different experimental conditions can be explained. An important role of the σ-electronic system in the guanine self-assembled structures is revealed as the main factor for the switch between different arrangements on surfaces and in crystals.
authors.affiliation: Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.|MTA-SZTE, Supramolecular and Nanostructured Materials Research Group, Dóm tér 8, Szeged, Hungary.
authors.forename: Gábor
authors.identifier: http://orcid.org/0000-0001-5408-1748
authors.initials: G
authors.lastname: Paragi
authors.affiliation: Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
authors.forename: Célia
authors.identifier: http://orcid.org/0000-0002-2973-5321
authors.initials: C
authors.lastname: Fonseca Guerra
mesh_terms: D054856:G-Quadruplexes; D006147:Guanine / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D049329:Nanostructures / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D006147:Guanine
keywords: G-quadruplexes; cooperative effects; hydrogen bonds; nanostructures; self-assembly