Energy transfers between the bacteriochlorophyll c and a antennae in light-harvesting chlorosomes from the green bacterium Chloroflexes aurantiacus have been studied in two-color pump-probe experiments with improved sensitivity and wavelength versatility. The BChl c --> BChl a energy transfers are well simulated with biexponential kinetics, with lifetimes of 2-3 and 11 ps. They do not exhibit an appreciable subpicosecond component. In the context of a kinetic model for chlorosomes, these lifetimes suggest that both internal BChl c processes and the BChl c --> BChl a energy-transfer step contribute materially to the empirical rod-to-baseplate energy-transfer kinetics.
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http://dx.doi.org/10.1021/jp953734k | DOI Listing |
Photochem Photobiol Sci
December 2024
Graduate School of Life Sciences, Ritsumeikan University, Kusatsu, Shiga, 525-8577, Japan.
Zinc methyl 13,13-disubstituted 3-hydroxymethyl-pyropheophorbides-a were prepared as models of bacteriochlorophyll-d, which self-aggregated in the main light-harvesting antenna (chlorosome) of photosynthetic green bacteria. The synthetic zinc 3-hydroxy-13-oxo-chlorins possessing methyl and methoxycarbonyl groups at the 13-position could not self-aggregate in an aqueous Triton X-100 solution. However, another model compound bearing an ethane-1,2-diyl group at the 13-position did self-aggregate under the same conditions to give red-shifted and broadened Qy and Soret absorption bands.
View Article and Find Full Text PDFFront Microbiol
July 2024
Archaea Physiology & Biotechnology Group, Department of Functional and Evolutionary Ecology, Universität Wien, Wien, Austria.
Phys Chem Chem Phys
July 2024
Institute of Physical Chemistry (IPC), Karlsruhe Institute of Technology, Kaiserstrasse 12, 76131 Karlsruhe, Germany.
A trajectory surface hopping approach, which uses machine learning to speed up the most time-consuming steps, has been adopted to investigate the exciton transfer in light-harvesting systems. The present neural networks achieve high accuracy in predicting both Coulomb couplings and excitation energies. The latter are predicted taking into account the environment of the pigments.
View Article and Find Full Text PDFPhotochem Photobiol
January 2025
Graduate School of Life Sciences, Ritsumeikan University, Kusatsu, Shiga, Japan.
Zinc methyl 3-hydroxymethyl-pyropheophorbides-a possessing an acylhydrazinylidene group at the 13-position were prepared by chemically modifying chlorophyll-a, which were models of bacteriochlorophyll-d as one of the light-harvesting pigments in photosynthetic green bacteria. Similar to the self-aggregation of natural bacteriochlorophyll-d in the antenna systems called chlorosomes, some of the synthetic models self-aggregated in an aqueous Triton X-100 solution to give red-shifted and broadened visible absorption bands. The newly appeared oligomeric bands were ascribable to the exciton coupling of the chlorin π-systems along the molecular y-axis, leading to intense circular dichroism bands in the red-shifted Qy and Soret regions.
View Article and Find Full Text PDFJ Phys Chem B
April 2024
Zernike Institute for Advanced Materials, University of Groningen, 9747 AG Groningen, The Netherlands.
Observations of low-lying dark states in several photosynthetic complexes challenge our understanding of the mechanisms behind their efficient energy transfer processes. Computational models are necessary for providing novel insights into the nature and function of dark states, especially since these are not directly accessible in spectroscopy experiments. Here, we will focus on signatures of dark-type states in chlorosomes, a light-harvesting complex from green sulfur bacteria well-known for uniting a broad absorption band with very efficient energy transfer.
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