title: Carotenoid radical cations as a probe for the molecular mechanism of nonphotochemical quenching in oxygenic photosynthesis.
abstract: Nonphotochemical quenching (NPQ) is a fundamental mechanism in photosynthesis which protects plants against excess excitation energy and is of crucial importance for their survival and fitness. Recently, carotenoid radical cation (Car*+) formation has been discovered to be a key step for the feedback deexcitation quenching mechanism (qE), a component of NPQ, of which the molecular mechanism and location is still unknown. We have generated and characterized carotenoid radical cations by means of resonant two color, two photon ionization (R2C2PI) spectroscopy. The Car*+ bands have maxima located at 830 nm (violaxanthin), 880 nm (lutein), 900 nm (zeaxanthin), and 920 nm (beta-carotene). The positions of these maxima depend strongly on solution conditions, the number of conjugated C=C bonds, and molecular structure. Furthermore, R2C2PI measurements on the light-harvesting complex of photosystem II (LHC II) samples with or without zeaxanthin (Zea) reveal the violaxanthin (Vio) radical cation (Vio*+) band at 909 nm and the Zea*+ band at 983 nm. The replacement of Vio by Zea in the light-harvesting complex II (LHC II) has no influence on the Chl excitation lifetime, and by exciting the Chls lowest excited state, no additional rise and decay corresponding to the Car*+ signal observed previously during qE was detected in the spectral range investigated (800-1050 nm). On the basis of our findings, the mechanism of qE involving the simple replacement of Vio with Zea in LHC II needs to be reconsidered.
authors: Institute for Physical and Theoretical Chemistry, Johann Wolfgang Goethe-University-Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main, Germany.
authors: Sergiu
authors: S
authors: Amarie
authors: Jörg
authors: J
authors: Standfuss
authors: Tiago
authors: T
authors: Barros
authors: Werner
authors: W
authors: Kühlbrandt
authors: Andreas
authors: A
authors: Dreuw
authors: Josef
authors: J
authors: Wachtveitl
mesh_terms: D002412:Cations; D005609:Free Radicals; D014975:Lutein / Q000737:chemistry*; D010084:Oxidation-Reduction; D018532:Pisum sativum / Q000737:chemistry; D010788:Photosynthesis; D045332:Photosystem II Protein Complex / Q000737:chemistry; D018515:Plant Leaves / Q000737:chemistry; D011789:Quantum Theory; D012996:Solutions; D013057:Spectrum Analysis; D020524:Thylakoids / Q000737:chemistry; D024341:Xanthophylls / Q000737:chemistry*; D065146:Zeaxanthins; D019207:beta Carotene / Q000737:chemistry*
chemical_list: D002412:Cations; D005609:Free Radicals; D045332:Photosystem II Protein Complex; D012996:Solutions; D024341:Xanthophylls; D065146:Zeaxanthins; D019207:beta Carotene; C005613:violaxanthin; D014975:Lutein