Artículo
Abstract:
The excited states of the double hydrogen bond in the adenine-thymine nucleotide base pair has been investigated in the semiempirical CNDO/S-CI approximation. Double-minimum potential curves are obtained for several nuclear configurations characterizing simultaneous tautomeric rearrangements of the NH⋯N and O⋯HN bonds. The energy profiles for the coupled movement of the hydrogen bonding show that the Watson-Crick configuration of the adenine-thymine base pair is the most stable for all of the excited states studied. Estimates are made within the WKB approximation of the tunneling rate and tunneling probability. The results indicate that increasing the energy of the excited states would increase the probability of double protonic transfer by tunnel effect and thus for irreversible mutation. A comparison of the composition of the potentials for the single movement of the protons with the double-minimum potential of the concerted movement shows that the potential is nonseparable. The shortcomings that follow from the WKB approximation as applied to the present problem are discussed. © 1981 American Chemical Society.
Registro:
| Documento: | Artículo |
| Título: | Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and tautomeric equilibrium of the NH⋯N and O⋯HN bonds in the adenine-thymine base pair |
| Autor: | Grinberg, H.; Capparelli, A.L.; Spina, A.; Marañon, J.; Sorarrain, O.M. |
| Filiación: | Departmento de Quimica Organica, Facultad de Farmacia y Bioquimica, Universidad de Buenos Aires, Buenos Aires, Argentina Instituto de Investigaciones Fisico-Quimicas Teoricas y Aplicadas (INIFTA), La Plata, Argentina Laboratorio de Fisica Teorica, Departamento de Fisica, Universidad Nacional de La Plata, 1900 La Plata, Argentina Departamento do Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Buenos Aires, Argentina MCIC CONICET CONICET MCIC CIC, Provincia de Buenos Aires, Argentina |
| Año: | 1981 |
| Volumen: | 85 |
| Número: | 19 |
| Página de inicio: | 2751 |
| Página de fin: | 2759 |
| Título revista: | Journal of Physical Chemistry |
| ISSN: | 00223654 |
| PDF: | https://bibliotecadigital.exactas.uba.ar/download/paper/paper_00223654_v85_n19_p2751_Grinberg.pdf |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223654_v85_n19_p2751_Grinberg |
Citas:
---------- APA ----------
Grinberg, H., Capparelli, A.L., Spina, A., Marañon, J. & Sorarrain, O.M. (1981) . Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and tautomeric equilibrium of the NH⋯N and O⋯HN bonds in the adenine-thymine base pair. Journal of Physical Chemistry, 85(19), 2751-2759.Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223654_v85_n19_p2751_Grinberg [ ]
---------- CHICAGO ----------
Grinberg, H., Capparelli, A.L., Spina, A., Marañon, J., Sorarrain, O.M. "Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and tautomeric equilibrium of the NH⋯N and O⋯HN bonds in the adenine-thymine base pair" . Journal of Physical Chemistry 85, no. 19 (1981) : 2751-2759.Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223654_v85_n19_p2751_Grinberg [ ]
---------- MLA ----------
Grinberg, H., Capparelli, A.L., Spina, A., Marañon, J., Sorarrain, O.M. "Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and tautomeric equilibrium of the NH⋯N and O⋯HN bonds in the adenine-thymine base pair" . Journal of Physical Chemistry, vol. 85, no. 19, 1981, pp. 2751-2759.Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223654_v85_n19_p2751_Grinberg [ ]
---------- VANCOUVER ----------
Grinberg, H., Capparelli, A.L., Spina, A., Marañon, J., Sorarrain, O.M. Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and tautomeric equilibrium of the NH⋯N and O⋯HN bonds in the adenine-thymine base pair. 1981;85(19):2751-2759.Available from: https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223654_v85_n19_p2751_Grinberg [ ]
