Singlet and triplet energy transfer in the peridinin-chlorophyll a-protein from Amphidinium carterae

Journal Article · Thu Apr 08 04:00:00 EDT 1999 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory

DOI:https://doi.org/10.1021/jp983943f· OSTI ID:338458

Bautista, J A; Frank, H A ^[1]; Hiller, R G; Sharples, F P ^[2]; Gosztola, D ^[3]; Wasielewski, M ^[3]

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1. Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemistry
2. Marquarie Univ., New South Wales (Australia). School of Biological Sciences
3. Argonne National Lab., IL (United States). Chemistry Div.

The spectroscopic properties of peridinin in solution, and the efficiency and dynamics of energy transfer from peridinin to chlorophyll a in the peridinin-chlorophyll-protein (PCP) from Amphidinium carterae, were studied by steady-state absorption, fluorescence, fluorescence excitation, and fast transient optical spectroscopy. Steady-state measurements of singlet energy transfer from peridinin to chlorophyll revealed an 88 {+-} 2% efficiency. Fast-transient absorption experiments showed that the excited S{sub 1} state of peridinin decayed in 13.4 {+-} 0.6 ps in methanol and 3.1 {+-} 0.4 ps in the PCP complex after direct excitation of the carotenoid. The onset of the bleaching of the chlorophyll absorption band at 672 nm, signifying the arrival of the excitation from the carotenoid, occurred in 3.2 {+-} 0.3 ps. These data show that the primary route of energy transfer from peridinin to chlorophyll in the PCP complex is through the S{sub 1} state of peridinin. Nanosecond time-resolved transient optical spectroscopy revealed that chlorophyll triplet states are efficiently quenched by peridinin whose triplet state subsequently decays with a lifetime of 10 {+-} 1 {micro}s in the PCP complex. Close association between the peridinins and chlorophyll, which is clearly evident in the 3-D structure of the PCP complex, along with proper alignment of pigments and energy state matching are responsible for the high efficiencies of the photochemical processes.

• Research Organization: Argonne National Laboratory (ANL), Argonne, IL
• Sponsoring Organization: National Insts. of Health, Bethesda, MD (United States); USDOE, Washington, DC (United States)
• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 338458
• Journal Information: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 14 Vol. 103; ISSN 1089-5639; ISSN JPCAFH
• Country of Publication: United States
• Language: English

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PHYSICAL PROPERTIES
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