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The field-dependence of the solid-state photo-CIDNP effect in two states of heliobacterial reaction centers

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Abstract

The solid-state photo-CIDNP (photochemically induced dynamic nuclear polarization) effect is studied in photosynthetic reaction centers of Heliobacillus mobilis at different magnetic fields by 13C MAS (magic-angle spinning) NMR spectroscopy. Two active states of heliobacterial reaction centers are probed: an anaerobic preparation of heliochromatophores (“Braunstoff”, German for “brown substance”) as well as a preparation of cells after exposure to oxygen (“Grünstoff”, “green substance”). Braunstoff shows significant increase of enhanced absorptive (positive) signals toward lower magnetic fields, which is interpreted in terms of an enhanced differential relaxation (DR) mechanism. In Grünstoff, the signals remain emissive (negative) at two fields, confirming that the influence of the DR mechanism is comparably low.

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Abbreviations

ALA:

Aminolevulinic acid

BChl:

Bacteriochlorophyll

BPhe:

Bacteriopheophytin

Chl:

Chlorophyll

Chla F :

Chlorophyll a with a farnesyl side chain

CI:

Continuous illumination

DD:

Differential decay

DR:

Differential relaxation

EPR:

Electron paramagnetic resonance

FT-IR:

Fourier transform infrared spectroscopy

Hb. :

Heliobacillus

ISC:

Intersystem crossing

MAS:

Magic angle spinning

NMR:

Nuclear magnetic resonance

P:

Special pair primary electron donor

Photo-CIDNP:

Photo-chemically induced dynamic nuclear polarization

PS I:

Photosystem I

PS II:

Photosystem II

Rb.:

Rhodobacter

RC:

Reaction center

RPM:

Radical pair mechanism

S :

Singlet

T 0 :

Triplet

TPPM:

Two-pulse phase-modulation

TR:

Time resolved

TSM:

Electron–electron nuclear three spin mixing

WT:

Wild type

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Acknowledgments

The authors thank to A.H.M de Wit for helping in culturing the bacteria. Helpful discussions with Prof. G. Jeschke and G.J. Janssen are acknowledged. F. Lefeber, K. Erkelens and Bryan Ferlez are gratefully acknowledged. Generous financial support of NWO (818.02.019, 713.012.001) is acknowledged. JHG is supported by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy, via Grant DE-FG02-08ER15989.

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Authors and Affiliations

  1. Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2300 RA, Leiden, The Netherlands

    Smitha Surendran Thamarath, A. Alia, Esha Roy, Karthick Babu Sai Sankar Gupta & Jörg Matysik

  2. Institut für Analytische Chemie, Universität Leipzig, Linnéstr. 3, 04103, Leipzig, Germany

    Smitha Surendran Thamarath, A. Alia & Jörg Matysik

  3. Department of Chemistry, Department of Biochemistry and Molecular Biology, The Pennsylvania State University, 328 South Frear Laboratory, University Park, PA, 16802, USA

    John H. Golbeck

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  1. Smitha Surendran Thamarath
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  2. A. Alia
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  3. Esha Roy
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Correspondence to Jörg Matysik.

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Surendran Thamarath, S., Alia, A., Roy, E. et al. The field-dependence of the solid-state photo-CIDNP effect in two states of heliobacterial reaction centers. Photosynth Res 117, 461–469 (2013). https://doi.org/10.1007/s11120-013-9854-x

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