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Initial excited-state relaxation of the bilin chromophores of phytochromes: a computational study
Linköping University, Department of Physics, Chemistry and Biology, Computational Physics . Linköping University, The Institute of Technology.
Linköping University, Department of Physics, Chemistry and Biology, Computational Physics . Linköping University, The Institute of Technology.
2011 (English)In: PHOTOCHEMICAL and PHOTOBIOLOGICAL SCIENCES, ISSN 1474-905X, Vol. 10, no 4, 569-579 p.Article in journal (Refereed) Published
Abstract [en]

The geometric relaxation following light absorption of the biliverdin, phycocyanobilin and phytochromobilin tetrapyrrole chromophores of bacterial, cyanobacterial and plant phytochromes has been investigated using density functional theory methods. Considering stereoisomers relevant for both red-absorbing Pr and far-red-absorbing Pfr forms of the photoreceptor, it is found that the initial excited-state evolution is dominated by torsional motion at the C10-C11 bond. This holds true for all three chromophores and irrespective of which configuration the chromophores adopt. This finding suggests that the photochromic cycling of phytochromes between their Pr and Pfr forms, which is known to be governed by Z/E photoisomerizations at the C15-C16 bond, relies on interactions between the chromophore and the protein to prevent photoisomerizations at C10-C11. Further, it is found that the uneven distribution of positive charge between the pyrrole rings is a major factor for the photochemical reactivity of the C10-C11 bond.

Place, publisher, year, edition, pages
Royal Society of Chemistry , 2011. Vol. 10, no 4, 569-579 p.
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Engineering and Technology
Identifiers
URN: urn:nbn:se:liu:diva-67548DOI: 10.1039/c0pp00307gISI: 000288964800016OAI: oai:DiVA.org:liu-67548DiVA: diva2:411258
Note
Original Publication: Angela Strambi and Bo Durbeej, Initial excited-state relaxation of the bilin chromophores of phytochromes: a computational study, 2011, PHOTOCHEMICAL and PHOTOBIOLOGICAL SCIENCES, (10), 4, 569-579. http://dx.doi.org/10.1039/c0pp00307g Copyright: Royal Society of Chemistry http://www.rsc.org/ Available from: 2011-04-18 Created: 2011-04-18 Last updated: 2011-05-04

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