Operational principles of light-driven electron pumps resolved by photo-CIDNP solid-state NMR


In photosynthetic reaction centres (RCs) of plants, light energy is converted into chemically useful energy and oxygen is produced. The ultimate question of photosynthesis research is: What are the fundamental operational principles, which can guide the construction of artificial devices for a renewable energy supply?
This proposal contains three innovative steps: (i) The functional mechanism of photosynthetic reaction centres is analysed in terms of electron pumping. ?Anomalies? existing in the conventional concepts of photosynthesis are analysed and classified in these terms. (ii) In order to include these ?anomalies? into a coherent concept of photosynthetic electron pumping, new physicochemical mechanisms are presented, based on non-linear mesoscopic phenomena, known in (soft) condensed matter, in particular phase transitions and non-linear dielectric screening of polaronic charges. (iii) Novel solid-state NMR strategies are proposed, including photo-chemically induced dynamic nuclear polarisation (photo-CIDNP) under magic-angle spinning (MAS) conditions, allowing the observation of light-induced electron transfer at atomic resolution. Two interrelated sub-projects are proposed:
- Sub-project 1: Light-induced changes
Comparison of photo-CIDNP solid-state NMR chemical shift data with those obtained in the dark allows the detection of light-induced changes of spatial, protonic and electronic structure. Combination of solid-state NMR with selective isotope labelling allows exploration of the entire photochemical machinery, i.e. the cofactors as well as the surrounding apoprotein. Mapping of light-induced changes at atomic selectivity will reveal the ?electron valve?, and will tell how the slow-down of the back-reaction relies on non-linear mesoscopic effects.
- Sub-project 2: Local electron-spin densities
In order to understand the link between photo-CIDNP intensities and local electron spin densities, we have worked out simulations of two mechanisms suggested in the literature. Now, experiments are required, e.g. magnetic field-dependent and laser-pulse photo-CIDNP experiments, in order to test these concepts. The exact mechanism of electron-nuclear interactions will be revealed. This will provide crucial knowledge on the ?electron wire? in the protein.


Book or monography

  • T.J. Aartsma, J. Matysik(2008): Biophysical Techniques in Photosynthesis, Volume II pp. 520 , Dordrecht


  • E. Daviso(2008): The solid-state photo-CIDNP effect  November 18, 2008

Chapter in book

  • G Jeschke, J. Matysik, P. Gast, A. Alia, A Diller(2008): Energy from the sun
  • A. Diller, J Matysik, P. Gast, G Jeschke, A. Alia(2008): Energy from the sun
  • P. Gast, E. Roy, G Jeschke, J. Matysik, A. Alia, HJ van Gorkom(2008): Energy from the sun
  • K.B. Sai Sankar Gupta, A Alia, E. Daviso, G Jeschke, J. Matysik(2008): Energy from the sun
  • J Matysik, T.J. Aartsma, J. Matysik, T.J. Aartsma(2008): Biophysical Techniques in Photosynthesis, Volume II pp. i - v , Dordrecht
  • E. Daviso, G Jeschke, J. Matysik(2009): Biophysical Techniques in Photosynthesis, Volume II pp. 389 - 399
  • J. Matysik, W. Koeckenberger(2009): Encyclopedia of Spectroscopy and Spectrometry, 2nd edition

Scientific article

  • J Matysik, P Gast, HJM de Groot, A Alia, HJ van Gorkom, G Jeschke, E Roy: Photochemically induced dynamic nuclear polarisation in photosystem I of plants observed by 13C magic-angle spinning NMR J. Am. Chem. Soc. pp. 12819 - 12826
  • HJ van Gorkom, P Gast, HJM de Groot, I de Boer, A. Alia, J Matysik: Heteronuclear 2D (1H-13C) MAS NMR resolves the electronic structure of coordinated histidines in light-harvesting complex II: Assessment of charge transfer and electronic delocalization effect J. Biomol. NMR. pp. 157 - 164
  • HJ van Gorkom, J Matysik, A Alia, C Glaubitz, P Gast, HJM de Groot, J Zaanen, A Diller, E. Roy(2004): Photo-CIDNP solid-state NMR on photosystems I and II: What makes P680 special? Photosynth. Res. pp. 303 - 308
  • HJM de Groot, G Jeschke, J Matysik, S. Prakash, P Gast, A Alia(2005): Magnetic field dependence of photo-CIDNP MAS NMR on photosynthetic reaction centres of Rhodobacter sphaeroides WT J. Am. Chem. Soc. pp. 14290 - 14298
  • H Strauss, T Rohmer, P Schmieder, J. Matysik, H de Groot, W Gaertner, J Hughes(2006): 15N CP/MAS NMR on phytochrome Cph1Δ2: Protonation state and dynamics of the tetrapyrrole cofactor J Phys Chem B pp. 20580 - 20585
  • P Gast, S Prakash, HJM de Groot, A Alia, J. Matysik, G Jeschke(2006): Photo-CIDNP MAS NMR in intact cells of Rhodobacter sphaeroides R26: Molecular and atomic resolution at nanomolar concentration J. Am. Chem. Soc. pp. 12794 - 12799
  • E Roy(2007): Magnetic field dependence of 13C photo-CIDNP MAS NMR in plant photosystems I and II Appl. Magn. Reson. pp. 193 - 204
  • E. Roy(2007): Photochemically induced dynamic nuclear polarisation observed in the reaction center of the green sulphur bacteria Chlorobium tepidum by 13C MAS NMR Biochem. Biophys. Acta pp. 610 - 615
  • A. Diller(2007): Signals in solid-state photochemically induced dynamic nuclear polarization recover faster than with the longitudinal relaxation time J. Phys. Chem. B pp. 10606 - 10614
  • A. Diller(2007): 15N-photo-CIDNP MAS NMR analysis of the electron donor of photosystem II Proc. Natl. Acad. Sci. USA pp. 12843 - 12848
  • E. Daviso(2007): Photo-CIDNP MAS NMR beyond the T1 limit by fast cycles of polarization extinction and polarization generation J. Magn. Reson. pp. 170 - 178
  • S. Prakash(2007): 13C chemical shift map of the active cofactors in photosynthetic reaction centers of Rhodobacter sphaeroides revealed by photo-CIDNP MAS NMR Biochemistry pp. 8953 - 8960
  • J Hughes, L-O Essen, J. Matysik, Chr. Lang, W Gaertner, T. Rohmer(2008): Light-induced chromophore activity and signal transduction in phytochromes observed by 13C and 15N magic-angle spinning NMR Proc. Natl. Acad. Sci. USA pp. 15229 - 15234
  • T. Rohmer, E. Roy, A. Alia, J. Matysik, P. Gast, G Jeschke(2008): Characterization of the primary electron pair in reaction centers of Heliobacillus mobilis by 13C photo-CIDNP MAS NMR Biochemistry pp. 4629 - 4635
  • J. Matysik, E. Daviso, A Diller, A Alia, G Jeschke(2008): Photo-CIDNP MAS NMR beyond the T1 limit by fast cycles of polarization extinction and polarization generation J. Magn. Reson. pp. 170 - 178
  • A. Alia, J. Matysik, A Diller, E. Roy(2008): The solid-state photo-CIDNP effect Photosynth. Res.
  • A. Diller, E. Roy, J. Matysik, A. Alia(2009): The solid-state photo-CIDNP effect Photosynthetic Research pp. 427
  • G Jeschke, J. Matysik, A Alia, S Prakash, E Daviso, J Lugtenburg, A Diller, P Gast(2009): Electron-nuclear spin dynamics in a bacterial photosynthetic reaction center J. Phys Chem C pp. 10269


Project number


Main applicant

Dr. J. Matysik

Affiliated with

Universität Leipzig, Fakultät für Chemie und Mineralogie, Institut für Analytische Chemie

Team members

E. Daviso MSc


15/02/2004 to 26/05/2009