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Relative Ground and Excited-State pKa Values of Phytochromobilin in the Photoactivation of Phytochrome: A Computational StudyRelative Ground and Excited-State pKa Values of Phytochromobilin in the Photoactivation of Phytochrome: A Computational Study
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kvantkemi.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kvantkemi.
2007 (engelsk)Inngår i: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 111, nr 39, s. 11554-11565Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

The conversion of the plant photoreceptor phytochrome from an inactive (Pr) to an active form (Pfr) is accomplished by a red-light induced Z→ E photoisomerization of its phytochromobilin chromophore. In recent years, the question whether the photoactivation involves a change in chromophore protonation state has been the subject of many experimental studies. Here, we have used quantum chemical methods to calculate relative ground and excited-state pKa values of the different pyrrole moieties of phytochromobilin in a protein-like environment. Assuming (based on experimental data) a Pr ZaZsZa chromophore and considering isomerizations at C15 and C5, it is found that moieties B and C are the strongest acids both in the ground state and in the bright first singlet excited state, which is rationalized in simple geometric and electronic terms. It is also shown that neither light absorption nor isomerization increases the acidity of phytochromobilin relative to the reference Pr state with all pyrrolenic nitrogens protonated. Hence, provided that the subset of chromophore geometries under investigation is biologically relevant, there appears to be no intrinsic driving force for a proton-transfer event. In a series of benchmark calculations, the performance of ab initio and time-dependent density functional theory methods for excited-state studies of phytochromobilin is evaluated in light of available experimental data.

sted, utgiver, år, opplag, sider
2007. Vol. 111, nr 39, s. 11554-11565
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Identifikatorer
URN: urn:nbn:se:uu:diva-96764DOI: 10.1021/jp0727953ISI: 000249838600031OAI: oai:DiVA.org:uu-96764DiVA, id: diva2:171445
Tilgjengelig fra: 2008-02-26 Laget: 2008-02-26 Sist oppdatert: 2017-12-14bibliografisk kontrollert
Inngår i avhandling
1. Theoretical Photochemistry: Halogenated Arenes, Phytochromobilin, Ru(II)polypyridyl complexes and 6-4 photoadducts
Åpne denne publikasjonen i ny fane eller vindu >>Theoretical Photochemistry: Halogenated Arenes, Phytochromobilin, Ru(II)polypyridyl complexes and 6-4 photoadducts
2008 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
Abstract [en]

This thesis presents Quantum Chemical calculations on the Photochemistry of Halogenated benzenes, Phytochromobilin, Ruthenium Polypyridyl complexes and 6-4 photoadducts in DNA. The work is focused on improving the understanding of a number of experimentally observed photochemical processes in these systems. New results regarding the mechanism of photodissociation of halogenated arenes, photointerconversion of phytochromobilin are presented, as well as of the photoprocesses of Ruthenium Polypyridyl complexes and new mechanistic insights in the repair of 6-4 photoadducts in DNA.

sted, utgiver, år, opplag, sider
Uppsala: Acta Universitatis Upsaliensis, 2008. s. 61
Serie
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 394
Emneord
Quantum chemistry, Quantum Chemistry, Halogenated Arenes, Phytochromobilin, Phytochrome, Ruthenium, 6-4 photoadducts, Photochemistry, Kvantkemi
HSV kategori
Identifikatorer
urn:nbn:se:uu:diva-8469 (URN)978-91-554-7096-8 (ISBN)
Disputas
2008-03-19, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 10:15 (engelsk)
Opponent
Veileder
Tilgjengelig fra: 2008-02-26 Laget: 2008-02-26 Sist oppdatert: 2011-03-14bibliografisk kontrollert

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