Understanding chlorophylls: central magnesium ion and phytyl as structural determinants.
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 spectroscopic study on the model pigments reveals meaningful differences in the spectral characteristics of the phytylated and non-phytylated pigments. Their analysis in terms of solvatochromism and axial coordination shows how the central Mg and phytyl residue shape the properties of the pigment. Surprisingly, the presence/absence of the central Mg has no effect on the solvatochromism of (bacterio)chlorophyll pi-electron system and the hydrophobicity of phytyl does not interfere with the first solvation shell of the chromophore. However, both residues significantly influence the conformation of the pigment macrocycle and the removal of either residue increases the macrocycle flexibility. The chelation of Mg has a flattening effect on the macrocycle whereas bulky phytyl residue seems to control the conformation of the chromophore via steric interactions with ring V and its substituents. The analysis of spectroscopic properties of bacteriochlorophyllide (free acid) shows that esterification of the C-17(3) propionate is necessary in chlorophylls because the carboxyl group may act as a strong chelator of the central Mg. These observations imply that the truncated chlorophylls used in theoretical studies are not adequate as models of native chromophores, especially when fine effects are to be modeled.
Faculty of Biochemistry, Biophysics and Biotechnology, Jagiellonian University, Gronostajowa 7, 30-387 Kraków, Poland. lfiedor@mol.uj.edu.pl
Leszek
L
Fiedor
Agnieszka
A
Kania
Beata
B
Myśliwa-Kurdziel
Łukasz
Ł
Orzeł
Grazyna
G
Stochel
D025541:Bacteriochlorophyll A / Q000737:chemistry; D002734:Chlorophyll / Q000737:chemistry*; D000077194:Chlorophyll A; D004734:Energy Metabolism; D004952:Esters; D006874:Hydrostatic Pressure; D007477:Ions; D008274:Magnesium / Q000737:chemistry*; D010836:Phytol / Q000737:chemistry*; D012242:Rhodobacter sphaeroides / Q000737:chemistry; D012995:Solubility; D012997:Solvents; D013057:Spectrum Analysis; D013997:Time Factors
D025541:Bacteriochlorophyll A; D004952:Esters; D007477:Ions; D012997:Solvents; D002734:Chlorophyll; D010836:Phytol; D008274:Magnesium; D000077194:Chlorophyll A