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The Biophysics of Photosynthesis pp 141–170Cite as

Spin in Photosynthetic Electron Transport

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Part of the book series: Biophysics for the Life Sciences ((BIOPHYS,volume 11))

Abstract

Photosynthetic charge separation also leads to electron spin separation. The two separated electron spins form a spin-correlated radical pair initially in a pure singlet state. This high electron spin order can be detected by EPR spectroscopy as CIDEP (chemically induced dynamic electron polarization). The radical pair undergoes spin evolution leading to periodic intersystem crossing. Interactions with nuclear spins lead to CIDNP (chemically induced dynamic nuclear polarization), which is often referred to as “photo-CIDNP” if it is of photochemical origin. NMR spectroscopy is able to observe such nuclear spin hyperpolarization. Both CIDEP EPR and CIDNP NMR allow for the early steps of photosynthesis to be studied in great detail. History and examples of these studies are presented. Finally, the question whether the occurrence of the spin-polarization is simply a by-product of the charge separation is discussed. Concepts for a possible functional relevance are proposed.

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Abbreviations

B :

Magnetic field strength

B L :

Local magnetic field strength

BChl:

Bacteriochlorophyll

C. :

Chlorobium

Chl:

Chlorophyll

CIDEP:

Chemically induced dynamic electron polarization

CIDNP:

Chemically induced dynamic nuclear polarization

DD:

Differential decay

DR:

Differential relaxation

EPR:

Electron paramagnetic resonance

ESR:

Electron spin resonance

ESEEM:

Electron spin echo envelope modulation

ET:

Electron transport

g :

g- or Landé value of an electron

G-pair:

Geminate radical pair

Hb. :

Heliobacillus

hfc, hfi:

Hyperfine coupling or interaction

ISC:

Intersystem crossing

J :

Exchange coupling

MAS:

Magic-angle spinning

MFE:

Magnetic field effects

m S :

Spin quantum number

NMR:

Nuclear magnetic resonance

OMAR:

Organic magnetoresistance effect

RC:

Reaction center

P:

Primary electron donor

PSI:

Photosystem I

PSII:

Photosystem II

Q:

Quinone

r :

Inter-radical distance

Rb. :

Rhodobacter

Rps. :

Rhodopseudomonas

RPM:

Radical pair mechanism

S:

Singlet spin state of a radical pair

S :

Spin quantum number

SCRP:

Spin-correlated radical pair

T:

Triplet spin state of a radical pair

TSM:

Three spin mixing

Φ:

Bacteriopheophytin

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Acknowledgments

The authors thank Profs. P.A. Bobbert, P. Hore, G. Jeschke, B. Koopmans, A. van der Est and M. Wohlgenannt for the stimulating discussions. This work has been financially supported by the Netherlands Organization for Scientific Research (NWO) through an ECHO grant (713.012.001).

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

    Isaac F. Céspedes-Camacho Dr.

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

    Isaac F. Céspedes-Camacho Dr. & Jörg Matysik Dr. rer. nat.

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Correspondence to Jörg Matysik Dr. rer. nat. .

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  1. Dept of Biochemistry & Molecular Biology, Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania, USA

    John Golbeck

  2. Dept of Chemistry, Brock University, St. Catharines, Ontario, Canada

    Art van der Est

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Céspedes-Camacho, I.F., Matysik, J. (2014). Spin in Photosynthetic Electron Transport. In: Golbeck, J., van der Est, A. (eds) The Biophysics of Photosynthesis. Biophysics for the Life Sciences, vol 11. Springer, New York, NY. https://doi.org/10.1007/978-1-4939-1148-6_5

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