The objective of the research contained in this application is to pinpoint specific structural features which control the rates and efficiencies of the various photochemical processes which take place in photosynthetic complexes. The present proposal focuses on carotenoids which are essential for the survival of photosynthetic organisms. The systems to be studied are photosynthetic bacterial reaction center and antenna pigment-protein complexes which have been isolated, pigment-reconstituted, crystallized and genetically altered. X-ray crystallography and NMR spectroscopy will be used as direct structural probes. Optical and electron paramagnetic resonance spectroscopy will allow the correlation of structure with spectroscopic observables and function. In turn the relationships of the spectroscopic observables to the structures may be extended to interpret spectroscopic studies on systems not yet crystallized, thus providing a basis from which to understand more complex systems; e.g. higher plant and algal protein complexes.
The specific aims of this proposal are: (1) To determine the structures of carotenoids in photosynthetic pigment-protein complexes; (2) To determine the relationships between the carotenoid structures and their spectroscopic properties; and (3) To determine the relationships between the carotenoid structures and their mechanisms of carotenoid-to-bacteriochlorophyll singlet and bacteriochlorophyll-to-- carotenoid triplet energy transfer. Several feasibility studies have already been carried out in support of the methods proposed to be employed.

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
5R01GM030353-05
Application #
3278069
Study Section
Molecular and Cellular Biophysics Study Section (BBCA)
Project Start
1987-09-01
Project End
1993-08-31
Budget Start
1991-09-01
Budget End
1992-08-31
Support Year
5
Fiscal Year
1991
Total Cost
Indirect Cost
Name
University of Connecticut
Department
Type
Schools of Arts and Sciences
DUNS #
City
Storrs-Mansfield
State
CT
Country
United States
Zip Code
06269
Polivka, Tomas; Frank, Harry A (2010) Molecular factors controlling photosynthetic light harvesting by carotenoids. Acc Chem Res 43:1125-34
Cai, Jianfeng; Niedzwiedzki, Dariusz M; Frank, Harry A et al. (2010) Ultrafast energy transfer within pyropheophorbide-a tethered to self-assembling DNA quadruplex. Chem Commun (Camb) 46:544-6
Niedzwiedzki, Dariusz M; Enriquez, Miriam M; Lafountain, Amy M et al. (2010) Ultrafast Time-resolved Absorption Spectroscopy of Geometric Isomers of Xanthophylls. Chem Phys 373:80-89
Schulte, Tim; Niedzwiedzki, Dariusz M; Birge, Robert R et al. (2009) Identification of a single peridinin sensing Chl-a excitation in reconstituted PCP by crystallography and spectroscopy. Proc Natl Acad Sci U S A 106:20764-9
Kajikawa, Takayuki; Aoki, Kazuyoshi; Singh, Ram Shanker et al. (2009) Syntheses of allene-modified derivatives of peridinin toward elucidation of the effective role of the allene function in high energy transfer efficiencies in photosynthesis. Org Biomol Chem 7:3723-33
Ryppa, Claudia; Niedzwiedzki, Dariusz; Morozowich, Nicole L et al. (2009) Stepwise conversion of two pyrrole moieties of octaethylporphyrin to pyridin-3-ones: synthesis, mass spectral, and photophysical properties of mono and bis(oxypyri)porphyrins. Chemistry 15:5749-62
Niedzwiedzki, Dariusz M; Sandberg, Daniel J; Cong, Hong et al. (2009) Ultrafast time-resolved absorption spectroscopy of geometric isomers of carotenoids. Chem Phys 357:4
Niedzwiedzki, Dariusz M; Chatterjee, Nirmalya; Enriquez, Miriam M et al. (2009) Spectroscopic investigation of peridinin analogues having different pi-electron conjugated chain lengths: exploring the nature of the intramolecular charge transfer state. J Phys Chem B 113:13604-12
Niedzwiedzki, Dariusz M; Sandberg, Daniel J; Cong, Hong et al. (2009) Ultrafast Time-resolved Absorption Spectroscopy of Geometric Isomers of Carotenoids. Chem Phys 357:4-16
Chatterjee, Nirmalya; Niedzwiedzki, Dariusz M; Aoki, Kazuyoshi et al. (2009) Effect of structural modifications on the spectroscopic properties and dynamics of the excited states of peridinin. Arch Biochem Biophys 483:146-55

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