title: The molecular second hyperpolarizability of the light-harvesting chlorophyll a/b pigment-protein complex of photosystem II.
abstract: Photosynthetic structures when imaged with nonlinear optical microscopy give rise to high third harmonic generation (THG) signal intensity due to the presence of chlorophylls and xanthophylls which have large second hyperpolarizabilitiy (γ) values. The γ value of trimers of the light-harvesting chlorophyll a/b pigment-protein complex of photosystem II (LHCII) isolated from pea (Pisum sativum) plants was investigated by the THG ratio technique at 1028 nm wavelength and found to have the value (-1600 ± 400) × 10(-41) m(2) V(-2). The large negative γ value of trimeric LHCII is due to the presence of chlorophyll a and chlorophyll b which have large negative γ values, while positive γ values of xanthophylls reduce the magnitude of the THG signal. Variation was observed between the measured γ value of LHCII and the approximated γ value of LHCII obtained by adding individual γ values of chlorophylls and xanthophylls. This difference can be attributed to the differing inter-pigment interactions of oriented chlorophylls and xanthophylls in the pigment-protein complex compared to randomly oriented non-interacting pigments in solution, as well as a differing dielectric environment of the pigments within LHCII versus the surrounding organic solvent.
authors.affiliation: Department of Chemical and Physical Sciences, University of Toronto Mississauga , 3359 Mississauga Road North, Mississauga, ON, Canada L5L 1C6.
authors.forename: Danielle
authors.initials: D
authors.lastname: Tokarz
authors.forename: Richard
authors.initials: R
authors.lastname: Cisek
authors.forename: Ulrich
authors.initials: U
authors.lastname: Fekl
authors.forename: Virginijus
authors.initials: V
authors.lastname: Barzda
mesh_terms: D002734:Chlorophyll / Q000737:chemistry* / Q000378:metabolism; D000077194:Chlorophyll A; D017830:Octoxynol / Q000737:chemistry; D018532:Pisum sativum / Q000378:metabolism; D045332:Photosystem II Protein Complex / Q000737:chemistry* / Q000378:metabolism; D010940:Plant Proteins / Q000737:chemistry* / Q000378:metabolism; D011485:Protein Binding; D013053:Spectrophotometry
chemical_list: D045332:Photosystem II Protein Complex; D010940:Plant Proteins; D002734:Chlorophyll; C037184:chlorophyll b; D017830:Octoxynol; D000077194:Chlorophyll A