The objective of the research contained in this application is to elucidate how the structural features of carotenoids determine their photochemical properties in vivo. Carotenoids are essential for the survival of photosynthetic organisms. The systems to be studied in this investigation are several different photosynthetic bacterial reaction center and antenna complexes that have been isolated, pigment-reconstituted, pigment-exchanged, crystallized or genetically altered. X-ray crystallography and NMR analyses will be used as direct structural probes. Optical and EPR spectroscopy will allow the correlation of structure with spectroscopic observables and function. These data will provide a basis from which to understand more complex systems; e.g. higher plant pigment-protein complexes whose properties are more complex than the bacterial systems.
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; (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 preliminary studies have already been carried out by us in support of the methods which we propose to employ.

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
5R01GM030353-08
Application #
2175772
Study Section
Molecular and Cellular Biophysics Study Section (BBCA)
Project Start
1987-09-01
Project End
1997-08-31
Budget Start
1994-09-01
Budget End
1995-08-31
Support Year
8
Fiscal Year
1994
Total Cost
Indirect Cost
Name
University of Connecticut
Department
Chemistry
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
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
Kajikawa, Takayuki; Hasegawa, Shinji; Iwashita, Takashi et al. (2009) Syntheses of C33-, C35-, and C39-peridinin and their spectral characteristics. Org Lett 11:5006-9
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

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