Magnetic field dependence of photo-CIDNP MAS NMR on photosynthetic reaction centers of Rhodobacter sphaeroides WT.
Photochemically induced dynamic nuclear polarization (photo-CIDNP) is observed in frozen and quinone depleted photosynthetic reaction centers of the purple bacteria Rhodobacter sphaeroides wild type (WT) by (13)C solid-state NMR at three different magnetic fields. All light-induced signals appear to be emissive at all three fields. At 4.7 T (200 MHz proton frequency), the strongest enhancement of NMR signals is observed, which is more than 10 000 above the Boltzmann polarization. At higher fields, the enhancement factor decreases. At 17.6 T, the enhancement factor is about 60. The field dependence of the enhancement appears to be the same for all nuclei. The observed field dependence is in line with simulations that assume two competing mechanisms of polarization transfer from electrons to nuclei, three-spin mixing (TSM) and differential decay (DD). These simulations indicate a ratio of the electron spin density on the special pair cofactors is 3:2 in favor of the L-BChl during the radical cation state. The good agreement of simulations with the experiments raises expectations that artificial solid reaction centers can be tuned to show photo-CIDNP in the near future.
Prakash
Shipra
S
Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Alia
Gast
Peter
P
de Groot
Huub J M
HJ
Jeschke
Gunnar
G
Matysik
Jörg
J
D002247:Carbon Isotopes; D003198:Computer Simulation; D009682:Magnetic Resonance Spectroscopy / Q000379:methods* / Q000592:standards; D008280:Magnetics; D015394:Molecular Structure; D010777:Photochemistry; D045322:Photosynthetic Reaction Center Complex Proteins / Q000737:chemistry*; D012015:Reference Standards; D012242:Rhodobacter sphaeroides / Q000737:chemistry*
D002247:Carbon Isotopes; D045322:Photosynthetic Reaction Center Complex Proteins