Supramolecular Switches Based on the Guanine–Cytosine (GC) Watson–Crick Pair: Effect of Neutral and Ionic Substituents
| Autor: | Tushar van der Wijst, Célia Fonseca Guerra, F. Matthias Bickelhaupt |
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| Přispěvatelé: | AIMMS, Theoretical Chemistry |
| Rok vydání: | 2006 |
| Předmět: |
Ions
Guanosine substituent effects Stereochemistry Hydrogen bond supramolecular switch Organic Chemistry Substituent Cationic polymerization Supramolecular chemistry Ionic bonding Molecular Structure of Nucleic Acids: A Structure for Deoxyribose Nucleic Acid General Chemistry Catalysis Cytosine chemistry.chemical_compound Crystallography DNA structures chemistry density functional calculations hydrogen bonds Density functional theory A-DNA Base Pairing |
| Zdroj: | Chemistry: A European Journal, 12(11), 3032-3042. Wiley-VCH Verlag Guerra, C F, van der Wijst, T & Bickelhaupt, F M 2006, ' Supramolecular Switches Based on the Guanine–Cytosine (GC) Watson–Crick Pair: Effect of Neutral and Ionic Substituents ', Chemistry: A European Journal, vol. 12, no. 11, pp. 3032-3042 . https://doi.org/10.1002/chem.200501301 |
| ISSN: | 1521-3765 0947-6539 |
| DOI: | 10.1002/chem.200501301 |
| Popis: | We have theoretically analyzed Watson-Crick guanine-cytosine (GC) base pairs in which purine-C8 and/or pyrimidine-C6 positions carry a substituent X = NH(-), NH(2), NH(3) (+) (N series), O(-), OH, or OH(2) (+) (O series), using the generalized gradient approximation (GGA) of density functional theory at the BP86/TZ2P level. The purpose is to study the effects on structure and hydrogen-bond strength if X= H is substituted by an anionic, neutral, or cationic substituent. We found that replacing X = H by a neutral substituent has relatively small effects. Introducing a charged substituent, on the other hand, led to substantial and characteristic changes in hydrogen-bond lengths, strengths, and hydrogen-bonding mechanism. In general, introducing an anionic substituent reduces the hydrogen-bond-donating and increases the hydrogen-bond-accepting capabilities of a DNA base, and vice versa for a cationic substituent. Thus, along both the N and O series of substituents, the geometric shape and bond strength of our DNA base pair can be chemically switched between three states, thus yielding a chemically controlled supramolecular switch. Interestingly, the orbital-interaction component in some of these hydrogen bonds was found to contribute to more than 49 % of the attractive interactions and is thus virtually equal in magnitude to the electrostatic component, which provides the other (somewhat less than) 51 % of the attraction. |
| Databáze: | OpenAIRE |
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