title: Single and multi-exciton dynamics in aqueous protochlorophyllide aggregates.
abstract: In plants, the oxidoreductase enzyme POR reduces protochlorophyllide (Pchlide) into chlorophyllide (Chlide), using NADPH as a cofactor. The reduction involves the transfer of two electrons and two protons to the C17═C18 double bond of Pchlide, and the reaction is initiated by the absorption of light by Pchlide itself. In this work we have studied the excited state dynamics of Pchlide dissolved in water, where it forms excitonically coupled aggregates, by ultrafast time-resolved transient absorption and fluorescence experiments performed in the 480-720 nm visible region and in the 1780-1590 cm(-1) mid-IR region. The ground state visible absorption spectrum of aqueous Pchlide red shifts and broadens in comparison to the spectrum of monomeric Pchlide in organic solvents. The population of the one-exciton state occurs at low excitation densities, of <1 photon per aggregate. We characterized the multiexciton manifolds spectra by measuring the absorption difference spectra at increasingly higher photon densities. The multiexciton states are characterized by blue-shifted stimulated emission and red-shifted excited state absorption in comparison to those of the one-exciton manifold. The relaxation dynamics of the multiexciton manifolds into the one-exciton manifold is found to occur in ∼10 ps. This surprisingly slow rate we suggest is due to the intrinsic charge transfer character of the PChlide excited state that leads to solvation, stabilizing the CT state, and subsequent charge recombination, which limits the exciton relaxation.
authors.affiliation: Department of Physics and Astronomy, Faculty of Sciences, Vrije Universiteit, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands.
authors.forename: Olga A
authors.initials: OA
authors.lastname: Sytina
authors.forename: Ivo H M
authors.initials: IH
authors.lastname: van Stokkum
authors.forename: Rienk
authors.initials: R
authors.lastname: van Grondelle
authors.forename: Marie Louise
authors.initials: ML
authors.lastname: Groot
mesh_terms: D002735:Chlorophyllides / Q000737:chemistry* / Q000302:isolation & purification / Q000378:metabolism; D009249:NADP / Q000737:chemistry / Q000378:metabolism; D044925:Oxidoreductases Acting on CH-CH Group Donors / Q000737:chemistry / Q000378:metabolism; D011789:Quantum Theory; D016354:Rhodobacter capsulatus / Q000737:chemistry; D014867:Water / Q000737:chemistry
chemical_list: D002735:Chlorophyllides; D014867:Water; D009249:NADP; D044925:Oxidoreductases Acting on CH-CH Group Donors; C023886:protochlorophyllide reductase