Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy

Enriquez, Miriam M.; Zhang, Cheng; Tan, Howe-Siang; Akhtar, Parveen; Garab, Győző

doi:10.1063/1.4919239

Title: Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy

Full Record
Other Related Research

Abstract

The pathways and dynamics of excitation energy transfer between the chlorophyll (Chl) domains in solubilized trimeric and aggregated light-harvesting complex II (LHCII) are examined using two-dimensional electronic spectroscopy (2DES). The LHCII trimers and aggregates exhibit the unquenched and quenched excitonic states of Chl a, respectively. 2DES allows direct correlation of excitation and emission energies of coupled states over population time delays, hence enabling mapping of the energy flow between Chls. By the excitation of the entire Chl b Q{sub y} band, energy transfer from Chl b to Chl a states is monitored in the LHCII trimers and aggregates. Global analysis of the two-dimensional (2D) spectra reveals that energy transfer from Chl b to Chl a occurs on fast and slow time scales of 240–270 fs and 2.8 ps for both forms of LHCII. 2D decay-associated spectra resulting from the global analysis identify the correlation between Chl states involved in the energy transfer and decay at a given lifetime. The contribution of singlet–singlet annihilation on the kinetics of Chl energy transfer and decay is also modelled and discussed. The results show a marked change in the energy transfer kinetics in the time range of a few picoseconds. Owing to slow energymore »« less

Authors:

Enriquez, Miriam M.; Zhang, Cheng; Tan, Howe-Siang ^[1]; Akhtar, Parveen; Garab, Győző

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore)

Publication Date:: Sun Jun 07 00:00:00 EDT 2015

OSTI Identifier:: 22415905

Resource Type:: Journal Article

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 142; Journal Issue: 21; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606

Country of Publication:: United States

Language:: English

Subject:: 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANNIHILATION; CHLOROPHYLL; COMPLEXES; CORRELATIONS; ELECTRON SPECTROSCOPY; ENERGY TRANSFER; EXCITATION; EXCITED STATES; EXCITONS; LIFETIME; PROBES; TIME DELAY; TWO-DIMENSIONAL CALCULATIONS; TWO-DIMENSIONAL SYSTEMS; VISIBLE RADIATION

Citation Formats


                    Enriquez, Miriam M., Zhang, Cheng, Tan, Howe-Siang, Akhtar, Parveen, Garab, Győző, and Lambrev, Petar H., E-mail: lambrev@brc.hu. Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy.  United States: N. p., 2015. 
        Web.  doi:10.1063/1.4919239.

Copy to clipboard


                    Enriquez, Miriam M., Zhang, Cheng, Tan, Howe-Siang, Akhtar, Parveen, Garab, Győző, & Lambrev, Petar H., E-mail: lambrev@brc.hu. Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy.  United States.  https://doi.org/10.1063/1.4919239

Copy to clipboard


                    Enriquez, Miriam M., Zhang, Cheng, Tan, Howe-Siang, Akhtar, Parveen, Garab, Győző, and Lambrev, Petar H., E-mail: lambrev@brc.hu. 2015.  
        "Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy".  United States.  https://doi.org/10.1063/1.4919239.

Copy to clipboard


                    
@article{osti_22415905,

  title        = {Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy},

  author       = {Enriquez, Miriam M. and Zhang, Cheng and Tan, Howe-Siang and Akhtar, Parveen and Garab, Győző and Lambrev, Petar H., E-mail: lambrev@brc.hu},

  abstractNote = {The pathways and dynamics of excitation energy transfer between the chlorophyll (Chl) domains in solubilized trimeric and aggregated light-harvesting complex II (LHCII) are examined using two-dimensional electronic spectroscopy (2DES). The LHCII trimers and aggregates exhibit the unquenched and quenched excitonic states of Chl a, respectively. 2DES allows direct correlation of excitation and emission energies of coupled states over population time delays, hence enabling mapping of the energy flow between Chls. By the excitation of the entire Chl b Q{sub y} band, energy transfer from Chl b to Chl a states is monitored in the LHCII trimers and aggregates. Global analysis of the two-dimensional (2D) spectra reveals that energy transfer from Chl b to Chl a occurs on fast and slow time scales of 240–270 fs and 2.8 ps for both forms of LHCII. 2D decay-associated spectra resulting from the global analysis identify the correlation between Chl states involved in the energy transfer and decay at a given lifetime. The contribution of singlet–singlet annihilation on the kinetics of Chl energy transfer and decay is also modelled and discussed. The results show a marked change in the energy transfer kinetics in the time range of a few picoseconds. Owing to slow energy equilibration processes, long-lived intermediate Chl a states are present in solubilized trimers, while in aggregates, the population decay of these excited states is significantly accelerated, suggesting that, overall, the energy transfer within the LHCII complexes is faster in the aggregated state.},

  doi          = {10.1063/1.4919239},

  url          = {https://www.osti.gov/biblio/22415905},
  journal      = {Journal of Chemical Physics},

  issn         = {0021-9606},

  number       = 21,

  volume       = 142,

  place        = {United States},

  year         = {Sun Jun 07 00:00:00 EDT 2015},

  month        = {Sun Jun 07 00:00:00 EDT 2015}

}

Copy to clipboard

Journal Article:

https://doi.org/10.1063/1.4919239

Other availability

Find in Google Scholar

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

Ultrafast spectroscopy of trimeric light-harvesting complex II from higher plants

Journal Article Connelly, J; Mueller, G; Hucke, M; ... - Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical

Time-resolved femtosecond transient absorption measurements have been carried out at room temperature on light-harvesting chlorophyll a/b protein complex of photosystem II (LHC II) trimers prepared from spinach. Exciting in the chlorophyll (Chl) b region at 650 nm with very low intensity, virtually annihilation-free two-color transient absorption measurement of the kinetics over 100 ps, between 645 and 690 nm, yield global lifetimes of 175 fs, 625 fs, and 5 ps and a long component (>=790 ps) where the three fastest lifetimes reflect Chl b to Chl a energy transfer. On the basis of these results and recent electron diffraction structural data,more »« less
https://doi.org/10.1021/jp9619651
Correlated fluorescence quenching and topographic mapping of Light-Harvesting Complex II within surface-assembled aggregates and lipid bilayers

Journal Article Adams, Peter; Vasilev, Cvetelin; Hunter, C.; ... - Biochimica et Biophysica Acta - Bioenergetics

Light-Harvesting Complex II (LHCII) is a chlorophyll-protein antenna complex that efficiently absorbs solar energy and transfers electronic excited states to photosystems I and II. Under excess light intensity LHCII can adopt a photoprotective state in which excitation energy is safely dissipated as heat, a process known as Non-Photochemical Quenching (NPQ). In vivo NPQ is triggered by combinatorial factors including transmembrane ΔpH, PsbS protein and LHCII-bound zeaxanthin, leading to dramatically shortened LHCII fluorescence lifetimes. In vitro, LHCII in detergent solution or in proteoliposomes can reversibly adopt an NPQ-like state, via manipulation of detergent/protein ratio, lipid/protein ratio, pH or pressure. Previous spectroscopicmore »« less
Cited by 17
https://doi.org/10.1016/j.bbabio.2018.06.011
Can H-aggregates serve as light-harvesting antennae? Triplet-triplet energy transfer between excited aggregates and monomer thionine in aerosol-OT solutions

Journal Article Das, S; Kamat, P - Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical

The cationic dye thionine undergoes slow dissolution in aerosol-OT (AOT) containing solutions of heptane and toluene. By controlling the ratio of [dye]/[AOT], it is possible to obtain varying amounts of monomer, dimer, and higher order aggregates (trimer) in dilute dye solutions. The thionine aggregates exhibit characteristic absorption maxima at 565 and 530 nm for the dimer and trimer forms, respectively. The singlet excited states of these dye aggregates are short-lived ({tau} = 40--63 ps) as they undergo efficient intersystem crossing to generate the triplet excited states. Triplet energy transfer from the excited dye aggregates to monomeric thionine molecules was observedmore »« less
https://doi.org/10.1021/jp983816j
Picosecond spectroscopic study of chlorophyll-based models for the primary photochemistry of photosynthesis. [Dimers and trimers of chlorophyllide derivatives]

Journal Article Bucks, R; Netzel, T; Fujita, I; ... - J. Phys. Chem.; (United States)

A series of covalently linked dimers and trimers of chlorophyllide derivatives was investigated by time-resolved absorption and fluorescence spectroscopy (3 to 10/sup 4/ ps). For these compounds, the free energy difference between the singlet excited state of the electron donor and the anticipated cation-anion photoproduct (..delta..G/sub ET/) is estimated to range from +200 to -400 MeV. For the dimers studied, the singlet-excited-state lifetimes range from 1 to 7 ns and depend inversely on the solvent's static dielectric constant. Since no decrease in lifetime or fluorescence quantum yield was found as ..delta..G/sub ET/ became more negative, this effect is unlikely tomore »« less
https://doi.org/10.1021/j100208a009
Two mechanisms for dissipation of excess light in monomeric and trimeric light-harvesting complexes

Journal Article Dall'Osto, Luca; Cazzaniga, Stefano; Bressan, Mauro; ... - Nature Plants

Oxygenic photoautotrophs require mechanisms for rapidly matching the level of chlorophyll excited states from light harvesting with the rate of electron transport from water to carbon dioxide. These photoprotective reactions prevent formation of reactive excited states and photoinhibition. The fastest response to excess illumination is the so-called non-photochemical quenching which, in higher plants, requires the luminal pH sensor PsbS and other yet unidentified components of the photosystem II antenna. Both trimeric light-harvesting complex II (LHCII) and monomeric LHC proteins have been indicated as site(s) of the heat-dissipative reactions. Different mechanisms have been proposed: Energy transfer to a lutein quencher inmore »« less
https://doi.org/10.1038/nplants.2017.33

Similar Records