title: The excited-state chemistry of protochlorophyllide a: a time-resolved fluorescence study.
abstract: The excited-state processes of protochlorophyllide a, the precursor of chlorophyll a in chlorophyll biosynthesis, are studied using picosecond time-resolved fluorescence spectroscopy. Following excitation into the Soret band, two distinct fluorescence components, with emission maxima at 640 and 647 nm, are observed. The 640 nm emitting component appears within the time resolution of the experiment and then decays with a time constant of 27 ps. In contrast, the 647 nm emitting component is built up with a 3.5 ps rise time and undergoes a subsequent decay with a time constant of 3.5 ns. The 3.5 ps rise kinetics are attributed to relaxations in the electronically excited state preceding the nanosecond fluorescence, which is ascribed to emission out of the thermally equilibrated S(1) state. The 27 ps fluorescence, which appears within the experimental response of the streak camera, is suggested to originate from a second minimum on the excited-state potential-energy surface. The population of the secondary excited state is suggested to reflect a very fast motion out of the Franck-Condon region along a reaction coordinate different from the one connecting the Franck-Condon region with the S(1) potential-energy minimum. The 27 ps-component is an emissive intermediate on the reactive excited-state pathway, as its decay yields the intermediate photoproduct, which has been identified previously (J. Phys. Chem. B 2006, 110, 4399-4406). No emission of the photoproduct is observed. The results of the time-resolved fluorescence study allow a detailed spectral characterization of the emission of the excited states in protochlorophyllide a, and the refinement of the kinetic model deduced from ultrafast absorption measurements.
authors.affiliation: Institut für Physikalische Chemie, Bayerische Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Dietzek
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Kiefer
authors.forename: Arkady
authors.initials: A
authors.lastname: Yartsev
authors.forename: Villy
authors.initials: V
authors.lastname: Sundström
authors.forename: Peter
authors.initials: P
authors.lastname: Schellenberg
authors.forename: Paulius
authors.initials: P
authors.lastname: Grigaravicius
authors.forename: Gudrun
authors.initials: G
authors.lastname: Hermann
authors.forename: Jürgen
authors.initials: J
authors.lastname: Popp
authors.forename: Michael
authors.initials: M
authors.lastname: Schmitt
mesh_terms: D018554:Avena / Q000378:metabolism; D002627:Chemistry, Physical / Q000379:methods; D002734:Chlorophyll; D005453:Fluorescence; D007700:Kinetics; D008027:Light; D000432:Methanol / Q000737:chemistry; D008956:Models, Chemical; D010777:Photochemistry / Q000379:methods*; D011166:Porphyrins / Q000737:chemistry; D011521:Protochlorophyllide / Q000737:chemistry*; D013050:Spectrometry, Fluorescence / Q000379:methods*; D013053:Spectrophotometry; D013997:Time Factors
chemical_list: D011166:Porphyrins; D002734:Chlorophyll; D011521:Protochlorophyllide; D000432:Methanol