Physiological Significance of the Heterogeneous Distribution of Zeaxanthin and Lutein in the Retina of the Human Eye.

Zeaxanthin and lutein are xanthophyll pigments present in the human retina and particularly concentrated in its center referred to as the yellow spot (macula lutea). The fact that zeaxanthin, including its isomer meso-zeaxanthin, is concentrated in the central part of the retina, in contrast to lutein also present in the peripheral regions, raises questions about the possible physiological significance of such a heterogeneous distribution of macular xanthophylls. Here, we attempt to address this problem using resonance Raman spectroscopy and confocal imaging, with different laser lines selected to effectively distinguish the spectral contribution of lutein and zeaxanthin. Additionally, fluorescence lifetime imaging microscopy (FLIM) is used to solve the problem of xanthophyll localization in the axon membranes. The obtained results allow us to conclude that one of the key advantages of a particularly high concentration of zeaxanthin in the central part of the retina is the high efficiency of this pigment in the dynamic filtration of light with excessive intensity, potentially harmful for the photoreceptors.

Benzophosphol-3-yl Triflates as Precursors of 1,3-Diarylbenzophosphole Oxides.

A simple method for the synthesis of 3-arylbenzophosphole oxides under Suzuki-Miyaura coupling conditions has been presented. It employs benzophosphol-3-yl triflate starting materials which, prior to our work, had not been used for the synthesis of 3-arylbenzophosphole oxides. The reactions proceed over 24 h and provide a library of 3-arylbenzophosphole oxides. The synthetic access to the benzophosphol-3-yl triflates has been improved. The preliminary photophysical properties of some 3-arylbenzophosphole oxides have been investigated by absorption and emission measurements. The theoretical calculations were performed to establish structure-property relationships.

The photoprotective dilemma of a chloroplast: to avoid high light or to quench the fire?

The safe and smooth functioning of photosynthesis in plants is ensured by the operation of numerous regulatory mechanisms that adjust the density of excitation resulting from photon absorption to the capabilities of the photosynthetic apparatus. Such mechanisms include the movement of chloroplasts inside cells and the quenching of electronic excitations in the pigment-protein complexes. Here, we address the problem of a possible cause-and-effect relationship between these two mechanisms. Both the light-induced chloroplast movements and quenching of chlorophyll excitations were analyzed simultaneously with the application of fluorescence lifetime imaging microscopy of Arabidopsis thaliana leaves, wild-type and impaired in chloroplast movements or photoprotective excitation quenching. The results show that both regulatory mechanisms operate over a relatively wide range of light intensities. By contrast, impaired chloroplast translocations have no effect on photoprotection at the molecular level, indicating the direction of information flow in the coupling of these two regulatory mechanisms: from the photosynthetic apparatus to the cellular level. The results show also that the presence of the xanthophyll zeaxanthin is necessary and sufficient for the full development of photoprotective quenching of excessive chlorophyll excitations in plants.

Mechanisms shaping the synergism of zeaxanthin and PsbS in photoprotective energy dissipation in the photosynthetic apparatus of plants.

Safe operation of photosynthesis is vital to plants and is ensured by the activity of processes protecting chloroplasts against photo-damage. The harmless dissipation of excess excitation energy is considered to be the primary photoprotective mechanism and is most effective in the combined presence of PsbS protein and zeaxanthin, a xanthophyll accumulated in strong light as a result of the xanthophyll cycle. Here we address the problem of specific molecular mechanisms underlying the synergistic effect of zeaxanthin and PsbS. The experiments were conducted with Arabidopsis thaliana, using wild-type plants, mutants lacking PsbS (npq4), and mutants affected in the xanthophyll cycle (npq1), with the application of molecular spectroscopy and imaging techniques. The results lead to the conclusion that PsbS interferes with the formation of densely packed aggregates of thylakoid membrane proteins, thus allowing easy exchange and incorporation of xanthophyll cycle pigments into such structures. It was found that xanthophylls trapped within supramolecular structures, most likely in the interfacial protein region, determine their photophysical properties. The structures formed in the presence of violaxanthin are characterized by minimized dissipation of excitation energy. In contrast, the structures formed in the presence of zeaxanthin show enhanced excitation quenching, thus protecting the system against photo-damage.