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Hole-Burning Spectroscopy on Excitonically Coupled Pigments in Proteins: Theory Meets Experiment.

ABSTRACT: A theory for the calculation of resonant and nonresonant hole-burning (HB) spectra of pigment-protein complexes is presented and applied to the water-soluble chlorophyll-binding protein (WSCP) from cauliflower. The theory is based on a non-Markovian line shape theory ( Renger and Marcus J. Chem. Phys. 2002 , 116 , 9997 ) and includes exciton delocalization, vibrational sidebands, and lifetime broadening. An earlier approach by Reppert ( J. Phys. Chem. Lett. 2011 , 2 , 2716 ) is found to describe nonresonant HB spectra only. Here we present a theory that can be used for a quantitative description of HB data for both nonresonant and resonant burning conditions. We find that it is important to take into account the excess energy of the excitation in the HB process. Whereas excitation of the zero-phonon transition of the lowest exciton state, that is, resonant burning allows the protein to access only its conformational substates in the neighborhood of the preburn state, any higher excitation gives the protein full access to all conformations present in the original inhomogeneous ensemble. Application of the theory to recombinant WSCP from cauliflower, reconstituted with chlorophyll a or chlorophyll b, gives excellent agreement with experimental data by Pieper et al. ( J. Phys. Chem. B 2011 , 115 , 4053 ) and allows us to obtain an upper bound of the lifetime of the upper exciton state directly from the HB experiments in agreement with lifetimes measured recently in time domain 2D experiments by Alster et al. ( J. Phys. Chem. B 2014 , 118 , 3524 ).

SUBMITTER: Adolphs J

PROVIDER: S-EPMC4786881 | biostudies-literature | 2016 Mar

REPOSITORIES: biostudies-literature

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Hole-Burning Spectroscopy on Excitonically Coupled Pigments in Proteins: Theory Meets Experiment.

Adolphs Julian J Berrer Manuel M Renger Thomas T

Journal of the American Chemical Society 20160225 9

A theory for the calculation of resonant and nonresonant hole-burning (HB) spectra of pigment-protein complexes is presented and applied to the water-soluble chlorophyll-binding protein (WSCP) from cauliflower. The theory is based on a non-Markovian line shape theory ( Renger and Marcus J. Chem. Phys. 2002 , 116 , 9997 ) and includes exciton delocalization, vibrational sidebands, and lifetime broadening. An earlier approach by Reppert ( J. Phys. Chem. Lett. 2011 , 2 , 2716 ) is found to describe ...[more]

PMID: 26811003

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Project description:The optical spectra of photosynthetic pigment-protein complexes usually show broad absorption bands, often consisting of a number of overlapping, "hidden" bands belonging to different species. Spectral hole burning is an ideal technique to unravel the optical and dynamic properties of such hidden species. Here, the principles of spectral hole burning (HB) and the experimental set-up used in its continuous wave (CW) and time-resolved versions are described. Examples from photosynthesis studied with hole burning, obtained in our laboratory, are then presented. These examples have been classified into three groups according to the parameters that were measured: (1) hole widths as a function of temperature, (2) hole widths as a function of delay time and (3) hole depths as a function of wavelength. Two examples from light-harvesting (LH) 2 complexes of purple bacteria are given within the first group: (a) the determination of energy-transfer times from the chromophores in the B800 ring to the B850 ring, and (b) optical dephasing in the B850 absorption band. One example from photosystem II (PSII) sub-core complexes of higher plants is given within the second group: it shows that the size of the complex determines the amount of spectral diffusion measured. Within the third group, two examples from (green) plants and purple bacteria have been chosen for: (a) the identification of "traps" for energy transfer in PSII sub-core complexes of green plants, and (b) the uncovering of the lowest k = 0 exciton-state distribution within the B850 band of LH2 complexes of purple bacteria. The results prove the potential of spectral hole burning measurements for getting quantitative insight into dynamic processes in photosynthetic systems at low temperature, in particular, when individual bands are hidden within broad absorption bands. Because of its high-resolution wavelength selectivity, HB is a technique that is complementary to ultrafast pump-probe methods. In this review, we have provided an extensive bibliography for the benefit of scientists who plan to make use of this valuable technique in their future research.

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Hole-Burning Spectroscopy on Excitonically Coupled Pigments in Proteins: Theory Meets Experiment.

Publications

Hole-Burning Spectroscopy on Excitonically Coupled Pigments in Proteins: Theory Meets Experiment.

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