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Title: Artificial Photosynthetic Reaction Center Exhibiting Acid-Responsive Regulation of Photoinduced Charge Separation

Journal Article · · Journal of Physical Chemistry. B
 [1];  [1];  [2];  [1];  [1];  [1]
  1. Arizona State Univ., Tempe, AZ (United States). School of Molecular Sciences
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry and QB3 Inst.

Charge separation (CS) is the primary light-driven reaction in photosynthesis whereas onphotochemical quenching (NPQ) is a photoprotective regulatory mechanism employed by many photosynthetic organisms to dynamically modulate energy flow within the photosynthetic apparatus in response to fluctuating light conditions. Activated by decreases in lumen pH produced during periods of high photon flux, NPQ induces rapid thermal dissipation of excess excitation energy. As a result, the rate of CS decreases, thereby limiting the accumulation of potentially deleterious reactive intermediates and byproducts. In this article, a molecular triad that functionally mimics the effects of NPQ associated with an artificial photosynthetic reaction center is described. Steady-state absorption and emission, time-resolved fluorescence, and transient absorption spectroscopies have been used to demonstrate a 1 order of magnitude reduction in the CS quantum yield via reversible protonation of an excited-state-quenching molecular switch moiety. As in the natural system, the populations of unquenched and quenched states and therefore the overall yields of CS were found to be dependent on acid concentration.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC03-76F000098; AC02-05CH11231; FG02-03ER15393
OSTI ID:
1378341
Journal Information:
Journal of Physical Chemistry. B, Vol. 120, Issue 40; ISSN 1520-6106
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

References (39)

Regulation of Light Harvesting in Green Plants (Indication by Nonphotochemical Quenching of Chlorophyll Fluorescence) journal October 1994
Molecular Basis of the Vulnerability of Photosystem II to Damage by Light journal January 1995
Photoinhibition and Law of Reciprocity in Photosynthetic Reactions of Synechocystis sp. PCC 6803 journal February 1995
The photoprotective molecular switch in the photosystem II antenna journal January 2012
A quantitative study of the slow decline of chlorophyll a fluorescence in isolated chloroplasts journal October 1979
Excitation-energy quenching in aggregates of the LHC II chlorophyll-protein complex: a time-resolved fluorescence study journal February 1993
Aggregation of Light-Harvesting Complex II leads to formation of efficient excitation energy traps in monomeric and trimeric complexes journal July 2007
The mechanisms of changes in Photosystem II efficiency in spinach thylakoids journal April 1990
Control of the light harvesting function of chloroplast membranes: The LHCII-aggregation model for non-photochemical quenching journal July 2005
Identification of two quenching sites active in the regulation of photosynthetic light-harvesting studied by time-resolved fluorescence journal December 2009
Enhancement of the ΔpH-dependent dissipation of excitation energy in spinach chloroplasts by light-activation: correlation with the synthesis of zeaxanthin journal October 1989
The relationship between zeaxanthin, energy-dependent quenching of chlorophyll fluorescence, and trans-thylakoid pH gradient in isolated chloroplasts journal May 1991
Acclimation- and mutation-induced enhancement of PsbS levels affects the kinetics of non-photochemical quenching in Arabidopsis thaliana journal February 2011
Far-red fluorescence: A direct spectroscopic marker for LHCII oligomer formation in non-photochemical quenching journal October 2008
Role of electron-transfer quenching of chlorophyll fluorescence by carotenoids in non-photochemical quenching of green plants journal August 2005
Carotenoid Cation Formation and the Regulation of Photosynthetic Light Harvesting journal January 2005
Identification of a mechanism of photoprotective energy dissipation in higher plants journal November 2007
Singlet Energy Dissipation in the Photosystem II Light-Harvesting Complex Does Not Involve Energy Transfer to Carotenoids journal April 2010
Nanoscale process systems engineering: Toward molecular factories, synthetic cells, and adaptive devices journal January 2005
Solar Fuels via Artificial Photosynthesis journal December 2009
Mimicking Photosynthetic Solar Energy Transduction journal January 2001
The design and synthesis of artificial photosynthetic antennas, reaction centres and membranes journal October 2002
Self-regulation of photoinduced electron transfer by a molecular nonlinear transducer journal May 2008
Mimicking the Role of the Antenna in Photosynthetic Photoprotection journal March 2011
Optical Modulation of Molecular Conductance journal July 2011
Artificial photosynthetic antenna-reaction center complexes based on a hexaphenylbenzene core journal October 2005
Fulleropyrrolidines:  A Family of Full-Fledged Fullerene Derivatives journal September 1998
On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I journal May 1956
Energy and Photoinduced Electron Transfer in Porphyrin−Fullerene Dyads journal January 1996
Linkage and Solvent Dependence of Photoinduced Electron Transfer in Zincporphyrin-C 60 Dyads journal January 1996
Solvent Dependence of Charge Separation and Charge Recombination Rates in Porphyrin−Fullerene Dyad journal December 2000
Photoinduced electron transfer in a symmetrical diporphyrin–fullerene triad journal January 2004
Liquid-crystalline fullerene–ferrocene dyads journal January 2004
Femtosecond relaxation of photoexcited para-nitroaniline: solvation, charge transfer, internal conversion and cooling journal June 2000
Ultrafast intramolecular charge transfer in the merocyanine dye DCM journal March 1995
Ultrafast Dynamics of Porphyrins in the Condensed Phase:  II. Zinc Tetraphenylporphyrin journal October 2002
Energiewanderung und Fluoreszenz journal January 1946
Zwischenmolekulare Energiewanderung und Fluoreszenz journal January 1948
Soluble Synthetic Multiporphyrin Arrays. 2. Photodynamics of Energy-Transfer Processes journal January 1996