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 Q(y)-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 (A(L) - A(R)) 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 flow of paraffin oil, The isotropic absorption maximum peaks at 742 nm in paraffin oil, whereas the maximum of the LD signal is at 743 nm. The LD signal is positive over the whole water-adduct absorption band indicating that the transition dipole of the 742 nm transition is preferentially oriented along the long axis of the aggregate. The structure of the Chl b-water adduct is less well defined, The preparations of the Chl b-water adduct are unstable, The Chl b-water adduct absorption band maximum is at 683 nm. The CD signal of the Chl a-water adduct is about 200-fold the CD of the Chl b-water adduct, We could not orient the Chl b-water adducts by flow, which suggests that the adducts are small or disordered.