Leszek Fiedor

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In contrast to porphyrins and chlorins, the direct metalation of bacteriochlorins is difficult. Nevertheless, Cu 2+ and Zn 2+ can be introduced into bacteriopheophytin in acetic acid, whereas Cd 2+ can be inserted in dimethylformamide. The former reactions depend on the substituents of the isocyclic ring: they are facilitated if enolization of the-ketoester(More)
Changes in the electronic transition energies and redox potentials because of metal substitution in bacteriochlorophyll a justify the recently suggested correlation between electronegativity M , covalent radius, and an effective charge, Q M , at the metal atom center. A simple electrostatic theory in which Q M modifies the energies of the frontier molecular(More)
Bacteriochlorophyll (BChl) derivatives (with central Mg replaced by metal "M") ([M]-BChl with M = 2H, Mg, Zn, Pd, Cu) have been investigated for their photodynamic capacity and stability toward photodegradation in organic solvents and aqueous micellar solution. A protocol has been developed for screening new sensitizers. BChl and [Zn]-BChl are efficient(More)
Phytol, a C20 alcohol esterifying the C-17(3) propionate, and Mg2+ ion chelated in the central cavity, are conservative structural constituents of chlorophylls. To evaluate their intramolecular structural effects we prepared a series of metal- and phytyl-free derivatives of bacteriochlorophyll a and applied them as model chlorophylls. A detailed(More)
We found that the levels of mRNA of two enzymes involved in chlorophyll catabolism in Arabidopsis (Arabidopsis thaliana), products of two chlorophyllase genes, AtCLH1 and AtCLH2, dramatically increase (by almost 100- and 10-fold, respectively) upon illumination with white light. The measurements of photosystem II quantum efficiency in(More)
A simple reconstitution technique has been developed and then applied to prepare a series of light-harvesting antenna 1 (LH1) complexes with a programmed carotenoid composition, not available from native photosynthetic membranes. The complexes were reconstituted with different C(40) carotenoids, having two structural parameters variable: the functional side(More)
Practical applications of photosynthesis-inspired processes depend on a thorough understanding of the structures and physiochemical features of pigment molecules such as chlorophylls and bacteriochlorophylls. Consequently, the major structural features of these pigments have been systematically examined as to how they influence the S1 state energy,(More)
The axial coordination of central Mg(2+) ion in chlorophylls is of great structural and functional importance for virtually all photosynthetic chlorophyll proteins; however, little thermodynamic data are available on the ligand binding to these pigments. In the present study, spectral deconvolution of the bacteriochlorophyll Q(X) band serves to determine(More)
Chlorophylls, owing to their adjustable pi-electron system and intense, well-separated electronic transitions, can serve as convenient intrinsic spectroscopic probes of ligand-metal center interactions. They are also interesting for their photosensitizing properties. In order to examine the heavy-atom effects on the chlorophyll triplet state, a key(More)
Chlorophyll derivatives are potentially dangerous xenobiotics of dietary origin. The interactions of water-soluble derivatives of chlorophyll a with the animal organism were investigated using chlorophyllide a and its Zn-substituted analogue as model xenobiotics. The chlorophyllides were administered to tumor-bearing mice and their uptake, distribution, and(More)