Exciton interactions of chlorophyll tetramer in water-soluble chlorophyll-binding protein BoWSCP.

The exciton interaction of four chlorophyll a (Chl a) molecules in a symmetrical tetrameric complex of the water-soluble chlorophyll-binding protein BoWSCP was analyzed in the pH range of 3-11. Exciton splitting ΔE = 232 ± 2 cm-1 of the Qy band of Chl a into two subcomponents with relative intensities of 78.1 ± 0.7 % and 21.9 ± 0.7 % was determined by a joint decomposition of the absorption and circular dichroism spectra into Gaussian functions. The exciton coupling parameters were calculated based on the BoWSCP atomic structure in three approximations: the point dipole model, the distributed atomic monopoles, and direct ab initio calculations in the TDDFT/PCM approximation. The Coulomb interactions of monomers were calculated within the continuum model using three values of optical permittivity. The models based on the properties of free Chl a in solution suffer from significant errors both in estimating the absolute value of the exciton interaction and in the relative intensity of exciton transitions. Calculations within the TDDFT/PCM approximation reproduce the experimentally determined parameters of the exciton splitting and the relative intensities of the exciton bands. The following factors of pigment-protein and pigment-pigment interactions were examined: deviation of the macrocycle geometry from the planar conformation of free Chl; the formation of hydrogen bonds between the macrocycle and water molecules; the overlap of wave functions of monomers at close distances. The most significant factor is the geometrical deformation of the porphyrin macrocycle, which leads to an increase in the dipole moment of Chl monomer from 5.5 to 6.9 D and to a rotation of the dipole moment by 15° towards the cyclopentane ring. The contributions of resonant charge-transfer states to the wave functions of the Chl dimer were determined and the transition dipole moments of the symmetric and antisymmetric charge-transfer states were estimated.

Isomerization of carotenoids in photosynthesis and metabolic adaptation.

In nature, carotenoids are present as trans- and cis-isomers. Various physical and chemical factors like light, heat, acids, catalytic agents, and photosensitizers can contribute to the isomerization of carotenoids. Living organisms in the process of evolution have developed different mechanisms of adaptation to light stress, which can also involve isomeric forms of carotenoids. Particularly, light stress conditions can enhance isomerization processes. The purpose of this work is to review the recent studies on cis/trans isomerization of carotenoids as well as the role of carotenoid isomers for the light capture, energy transfer, photoprotection in light-harvesting complexes, and reaction centers of the photosynthetic apparatus of plants and other photosynthetic organisms. The review also presents recent studies of carotenoid isomers for the biomedical aspects, showing cis- and trans-isomers differ in bioavailability, antioxidant activity and biological activity, which can be used for therapeutic and prophylactic purposes.