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Excited state properties of chlorophyll f in organic solvents at ambient and cryogenic temperatures

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Abstract

Chlorophyll f is a photosynthetic pigment that was discovered in 2010. In this study, we present investigations on spectral and dynamic characteristics of singlet-excited and triplet states of Chl f with the application of ultrafast time-resolved absorption and fluorescence spectroscopies. The pigment was studied at room temperature in two organic solvents: pyridine and diethyl ether that have different characters of coordination of the chlorophyll magnesium (Mg) atom (hexa- and penta-coordination, respectively). Cryogenic measurements (77 K) were performed in 2-methyltetrahydrofuran (hexa-coordination). The singlet-excited state lifetime was measured to be 5.6 ns at room temperature regardless of Mg coordination and 8.1 ns at 77 K. The fluorescence quantum yield of Chl f was also determined in pyridine to be 0.16. The triplet state lifetime was studied in detail in pyridine at room temperature, and the inherent lifetime was estimated to ~150 μs. Selective measurements at 77 K demonstrated that the metastability of the triplet state greatly enhances, and its lifetime increases by a factor of more than three.

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Abbreviations

2-MTHF:

2-Methyl tetrahydrofuran

CCD:

Charge couple device

Chl:

Chlorophyll

DE:

Diethyl ether

EADS:

Evolution-associated difference spectra

ESA:

Excited state absorption

FWHM:

Full width at half maximum

HOMO:

Highest occupied molecular orbital

ICP-MS:

Inductively coupled plasma-mass spectrometry

LUMO:

Lowest unoccupied molecular orbital

OPO:

Optical parametric oscillator

Pyr:

Pyridine

RT:

Room temperature

TA:

Transient absorption

TRF:

Time-resolved fluorescence

T-S:

Triplet-minus-singlet

References

  • Brody SS, Rabinowitch E (1957) Excitation lifetime of photosynthetic pigments in vitro and in vivo. Science 125:555

    Article  CAS  PubMed  Google Scholar 

  • Chen M, Blankenship RE (2011) Expanding the solar spectrum used by photosynthesis. Trends Plant Sci 16:427–431

    Article  CAS  PubMed  Google Scholar 

  • Chen M, Schliep M, Willows RD, Cai ZL, Neilan BA, Scheer H (2010) A red-shifted chlorophyll. Science 329:1318–1319

    Article  CAS  PubMed  Google Scholar 

  • Chen M, Li YQ, Birch D, Willows RD (2012) A cyanobacterium that contains chlorophyll f—a red-absorbing photopigment. FEBS Lett 586:3249–3254

    Article  CAS  PubMed  Google Scholar 

  • Connolly JS, Janzen AF, Samuel EB (1982) Fluorescence lifetimes of chlorophyll a—solvent, concentration and oxygen dependence. Photochem Photobiol 36:559–563

    Article  CAS  Google Scholar 

  • Fujimori E, Livingston R (1957) Interactions of chlorophyll in its triplet state with oxygen, carotene, etc. Nature 180:1036–1038

    Article  CAS  Google Scholar 

  • Gouterman M (1959) Study of the effects of substitution on the absorption spectra of porphyrin. J Chem Phys 30:1139–1161

    Article  CAS  Google Scholar 

  • Gouterman M (1961) Spectra of porphyrins. J Mol Spectrosc 6:138–163

    Article  CAS  Google Scholar 

  • Gouterman M (1978) Optical spectra and electronic structure of porphyrins and related rings. In: Dolphin D (ed) Physical chemistry: Part A. Academic Press, New York, pp 1–166

    Google Scholar 

  • Hindman JC, Kugel R, Svirmickas A, Katz JJ (1978) Stimulated fluorescence and fluorescence quenching in chlorophyll a and bacteriochlorophyll a. Chem Phys Lett 53:197–200

    Article  CAS  Google Scholar 

  • Latimer P, Bannister TT, Rabinowitch E (1956) Quantum yields of fluorescence of plant pigments. Science 124:585–586

    Article  CAS  PubMed  Google Scholar 

  • Li YQ, Scales N, Blankenship RE, Willows RD, Chen M (2012) Extinction coefficient for red-shifted chlorophylls: chlorophyll d and chlorophyll f. Biochim Biophys Acta 1817:1292–1298

    Article  CAS  PubMed  Google Scholar 

  • Li Y, Cai ZL, Chen M (2013) Spectroscopic properties of chlorophyll f. J Phys Chem B 117:11309–11317

    Article  CAS  PubMed  Google Scholar 

  • Manning WM, Strain HH (1943) Chlorophyll d, a green pigment of red algae. J Biol Chem 151:1–19

    CAS  Google Scholar 

  • Miyashita H, Ikemoto H, Kurano N, Adachi K, Chihara M, Miyachi S (1996) Chlorophyll d as a major pigment. Nature 383:402

    Article  CAS  Google Scholar 

  • Natarajan LV, Ricker JE, Blankenship RE, Chang R (1984) Solvent influences on the singlet quenching of chlorophyll a by 2,5-dimethyl-para-benzoquinone. Photochem Photobiol 39:301–306

    Article  CAS  Google Scholar 

  • Niedzwiedzki DM, Blankenship RE (2010) Singlet and triplet excited state properties of natural chlorophylls and bacteriochlorophylls. Photosynth Res 106:227–238

    Article  CAS  PubMed  Google Scholar 

  • Niedzwiedzki DM, Fuciman M, Frank HA, Blankenship RE (2011) Energy transfer in an LH4-like light harvesting complex from the aerobic purple photosynthetic bacterium Roseobacter denitrificans. Biochim Biophys Acta 1807:518–528

    Article  CAS  PubMed  Google Scholar 

  • Pelletier PJ, Caventou JB (1818) Sur la matière verte des feuilles. Ann Chim Phys 9:194–196

    Google Scholar 

  • Strain HH (1958) Chloroplast pigments and chromatographic analysis. Pennsylvania State University, University Park

    Google Scholar 

  • van Stokkum IH, Larsen DS, van Grondelle R (2004) Global and target analysis of time-resolved spectra. Biochim Biophys Acta 1657:82–104

    Article  PubMed  Google Scholar 

  • Weiss C (1972) π-electron structure and absorption spectra of chlorophylls in solution. J Mol Spectrosc 44:37–80

    Article  CAS  Google Scholar 

  • Williams ATR, Winfield SA, Miller JN (1983) Relative fluorescence quantum yields using a computer-controlled luminescence spectrometer. Analyst 108:1067–1071

    Article  CAS  Google Scholar 

  • Yamijala SRKCS, Periyasamy G, Pati SK (2011) Computational studies on structural and excited-state properties of modified chlorophyll f with various axial ligands. J Phys Chem A 115:12298–12306

    Article  CAS  PubMed  Google Scholar 

  • Zapata M, Garrido J, Jeffrey SW (2006) Chlorophyll c pigments: current status. In: Grimm B, Porra RJ, Rudiger W, Scheer H (eds) Chlorophylls and bacteriochlorophylls: biochemistry, biophysics, function and applications (advances in photosynthesis and respiration). Springer, New York, pp 39–53

    Chapter  Google Scholar 

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Acknowledgments

This research was performed in the Photosynthetic Antenna Research Center (PARC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC 0001035 to R.E.B. M.C. is an Australian Future Fellow and thanks Australia Research Council for financial support.

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Authors and Affiliations

  1. Photosynthetic Antenna Research Center, Washington University in St. Louis, Campus Box 1138, St. Louis, MO, 63130, USA

    Dariusz M. Niedzwiedzki, Haijun Liu & Robert E. Blankenship

  2. Department of Biology, Washington University in St. Louis, St. Louis, MO, 63130, USA

    Haijun Liu & Robert E. Blankenship

  3. School of Biological Sciences, University of Sydney, Sydney, NSW, 2006, Australia

    Min Chen

  4. Department of Chemistry, Washington University in St. Louis, St. Louis, MO, 63130, USA

    Robert E. Blankenship

Authors
  1. Dariusz M. Niedzwiedzki
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  2. Haijun Liu
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  3. Min Chen
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  4. Robert E. Blankenship
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Correspondence to Dariusz M. Niedzwiedzki.

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Niedzwiedzki, D.M., Liu, H., Chen, M. et al. Excited state properties of chlorophyll f in organic solvents at ambient and cryogenic temperatures. Photosynth Res 121, 25–34 (2014). https://doi.org/10.1007/s11120-014-9981-z

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  • DOI: https://doi.org/10.1007/s11120-014-9981-z

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