0000000000194217
AUTHOR
Paavo H. Hynninen
Molecular structures of chlorophyll a aggregates: spectroscopic and molecular modeling study
Molecular structures of chlorophyll a aggregates have been studied. Spectroscopic properties of these aggregates have been studied by absorption and fluorescence spectroscopy in hydrocarbon solution at various temperatures. Observed spectroscopic shifts were interpreted in terms of simple exciton theory. Exciton splittings were estimated from computer optimized models of previously suggested Chl a aggregate structures.
Investigations of Chl a aggregates cross-linked by dioxane in 3-methylpentane
In this work, dioxane-bound aggregates of chlorophyll a are prepared in 3-methylpentane. The properties of the aggregates are studied by using steady-state and time-resolved spectroscopies. The Q -region absorption spectrum of the y chlorophyll a-dioxane aggregate shows four clearly resolvable narrow bands with comparable intensities. The band maxima are located at 683, 689, 698 and 702 nm. The emission spectrum consists of two emission bands centred at 699 and 702 nm suggesting the presence of two types of aggregates. High degree of fluorescence polarization is detected yielding the angles between the absorption transition moments with respect to the 702 nm emission transition moment. The …
Horseradish peroxidase-catalyzed oxidation of chlorophyll a with hydrogen peroxide
Horseradish peroxidase was verified to catalyze, without any phenol, the hydrogen peroxide oxidation of chlorophyll a (Chl a), solubilized with Triton X-100. The 13(2)(S) and 13(2)(R) diastereomers of 13(2)-hydroxyChl a were characterized as major oxidation products (ca. 60%) by TLC on sucrose, UV-vis, (1)H, and (13)C NMR spectra, as well as fast-atom bombardment MS. A minor amount of the 15(2)-methyl, 17(3)-phytyl ester of Mg-unstable chlorin was identified on the basis of its UV-vis spectrum and reactivity with diazomethane, which converted it to the 13(1),15(2)-dimethyl, 17(3)-phytyl ester of Mg-purpurin 7. The side products (ca. 10%) were suggested to include the 17(3)-phytyl ester of M…
Characterisation of Chlorophyll a and Chlorophyll b Monomers in Various Solvent Environments with Ultrafast Spectroscopy
In photosynthesis the energy from the sun is captured by light harvesting chlorophyll pigments and converted to stable chemical energy, by the photochemical reaction center. Photosynthetic energy transfer in the antenna systems of green plants has previously been studied by ultrafast time resolved spectroscopy. The characteristics of the chlorophyll pigments itself is important to study in order to understand the dynamics on a femtosecond timescale. One way to study the energy transfer is to use transient absorption spectroscopy and follow the increase or decrease in the transient absorption signal with time (1). Another way to study the energy transfer is to monitor the change in dichroism…
Dynamics of ground and excited state chlorophylla molecules in pyridine solution probed by femtosecond transient absorption spectroscopy
Abstract Femtosecond pump–probe spectroscopy was used to investigate the ground and excited state dynamics of chlorophyll a (Chl a ) in pyridine following excitation by a 100 fs optical pulse. The transient absorption spectrum and kinetics reveal spectral evolution on two ultrafast time scales: ∼100 fs and ∼3 ps. We attribute these dynamics to ground-state transient hole-burning and solvation dynamics. Transient absorption anisotropy at early times (∼500 fs) was measured for Chl a in pyridine and shows a pronounced wavelength dependence, where anisotropy varies between 0 and 0.5. Strong contribution from excited state absorption is the origin of the variation.
Horseradish peroxidase-catalyzed oxidation of chlorophyll a with hydrogen peroxide Characterization of the products and mechanism of the reaction
AbstractHorseradish peroxidase was verified to catalyze, without any phenol, the hydrogen peroxide oxidation of chlorophyll a (Chl a), solubilized with Triton X-100. The 132(S) and 132(R) diastereomers of 132-hydroxyChl a were characterized as major oxidation products (ca. 60%) by TLC on sucrose, UV–vis, 1H, and 13C NMR spectra, as well as fast-atom bombardment MS. A minor amount of the 152-methyl, 173-phytyl ester of Mg-unstable chlorin was identified on the basis of its UV–vis spectrum and reactivity with diazomethane, which converted it to the 131,152-dimethyl, 173-phytyl ester of Mg-purpurin 7. The side products (ca. 10%) were suggested to include the 173-phytyl ester of Mg-purpurin 18,…