0000000001059416

AUTHOR

P. H. Hynninen

Circular and linear dichroism of aggregates of chlorophyll a and chlorophyll b in 3-methylpentane and paraffin oil.

A circular (CD) and linear dichroism (LD) study of the water adducts of the green plant chlorophylls a (Chl a) and b (Chl b) in hydrocarbon solvents 3-methylpentane and paraffin oil is presented. A strong red shift of the Qy-absorption band from 663 to 746 nm (1678 cm−1) is observed as the water adduct of Chl a is formed. The Chl a-water adduct shows a strong, nonconservative CD signal, which is characterized by a positive peak at 748 nm and two negative peaks at 720 and 771 nm. The maximum CD (AL - AR) is only one order of magnitude smaller than the isotropic absorption maximum. We propose that this exceptionally strong signal is the so-called psi-type CD. The LD spectrum was measured in a…

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CHLOROPHYLL a AGGREGATES IN HYDROCARBON SOLUTION, A PICOSECOND SPECTROSCOPY AND MOLECULAR MODELING STUDY

Chlorophyll a aggregates in 3-methylpentane solution have been studied by using picosecond absorption and fluorescence spectroscopy and molecular modeling. Chlorophyll a aggregates give rise to reversible temperature changes in the absorption and fluorescence spectra. Time-dependent anisotropies were used to estimate rotational correlation times of the aggregates. These were indicative of the sizes of the aggregates. The rotational diffusion of the monomer and the two identified aggregates was hydrodynamic over the viscosity range studied (0.29–1.8 cP). Molecular mechanics calculations were used to predict the minimum energy structures of several chlorophyll a dimers suggested earlier in th…

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