The solid state photo-CIDNP effect
Daviso, E.
Citation
Daviso, E. (2008, November 18). The solid state photo-CIDNP effect. Retrieved from https://hdl.handle.net/1887/13264
Version: Corrected Publisher’s Version
License: Licence agreement concerning inclusion of doctoral thesis in the Institutional Repository of the University of Leiden
Downloaded from: https://hdl.handle.net/1887/13264
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THE SOLID-STATE
PHOTO-CIDNP EFFECT
PROEFSCHRIFT
ter verkrijging van
de graad van Doctor aan de Universiteit Leiden, op gezag van de Rector Magnificus P.F. van der Heijden,
volgens besluit van het College voor Promoties te verdedigen op dinsdag 18 november 2008
klokke 13:45 uur
door
Eugenio Daviso
geboren te Alba, Italië in 1977
Promotiecommissie:
Promotor:
Prof. dr. H. J. M. de Groot
Copromotor:
Dr. J. Matysik
Referent:
Prof. dr. P. J. Hore
Overige leden:
Prof. dr. J. Lugtenburg Prof. dr. M. T. M. Koper Prof. dr. M. C. van Hemert Prof. dr. J. Brouwer
ISBN: 978-90-6464-309-5
This work was supported by grants of the Netherlands Organization for Scientific Research (NWO) Vidi (700.53.423) to Jörg Matysik and by the European Molecular Biology Organization (EMBO) short term fellowship (ASTF-131-2005) to Eugenio Daviso.
Financial support for the publication of this thesis was provided by Newport Spectra- Physics and Bruker BioSpin BV.
a mio fratello, ai miei genitori to my brother, to my parents
5
TABLE OF CO"TE"TS
LIST OF ABBREVIATIO"S ... 7
LIST OF SYMBOLS ... 8
1 I"TRODUCTIO" ... 11
1.1THEORYOFPHOTO-CIDNPINSOLIDS ... 11
1.1.1 Magnetic field effect ... 11
1.1.2 Primary sources of enhanced nuclear magnetization ... 13
1.1.3 Three spin mixing ... 15
1.1.4 Differential decay ... 17
1.1.5 Differential relaxation ... 18
1.1.6 Donor excited triplet state ... 19
1.2CONTINUOUSILLUMINATIONPHOTO-CIDNPINSOLIDS ... 20
1.2.1 Steady state build-up ... 20
1.2.2 Polarization transfer between nuclei ... 21
1.3SIMULATIONS ... 22
1.4PHOTO-CIDNPMASNMRSET-UP ... 23
1.4.1 Continuous illumination setup ... 23
1.4.2 Laser setup ... 25
1.4.3 Pulse sequences ... 26
1.5APPLICATIONS ... 26
1.5.1 Electronic structure of the special pair ... 26
1.5.2 Entire chromatophores and cells ... 27
1.5.3 Photosystems of plants ... 28
1.5.4 Relaxation measurements ... 29
1.6SCOPEOFTHETHESIS ... 29
2 PHOTO-CID"P MAS "MR BEYO"D THE T1 LIMIT BY FAST CYCLES OF POLARIZATIO" EXTI"CTIO" A"D POLARIZATIO" GE"ERATIO" ... 33
2.1INTRODUCTION ... 33
2.2MATERIALSANDMETHODS ... 36
2.2.1 Sample preparation ... 36
2.2.2 MAS 0MR measurements ... 37
2.3EXPERIMENTAL ... 37
2.3.1 0anosecond-flash laser set-up ... 37
2.3.2 Electronic coupling of laser and 0MR ... 38
2.3.3 Optical coupling of laser and 0MR ... 38
2.4THEORY ... 39
2.4.1 General considerations ... 39
2.4.2 Residual polarization ... 40
2.4.3 Relative phase of the pulses ... 43
2.5RESULTSANDDISCUSSION ... 44
2.5.1 PE-PG experiments on histidine ... 44
2.5.2 Time-resolved 13C PE-PG photo-CID0P MAS 0MR ... 45
2.6CONCLUSIONS ... 48
3 ELECTRO"-"UCLEAR SPI" DY"AMICS I" A BACTERIAL PHOTOSY"THETIC REACTIO" CE"TRE ... 51
3.1INTRODUCTION ... 51
6
3.2MATERIALSANDMETHODS ... 54
3.2.1 Sample preparation and 0MR measurements ... 54
3.2.2 Spectral fitting and nuclear polarization evolution ... 54
3.2.3 0umerical simulations ... 55
3.3RESULTSANDDISCUSSION ... 57
3.3.1 13C photo-CID0P MAS 0MR on WT RCs of Rb. sphaeroides ... 57
3.3.2 13C photo-CID0P MAS 0MR on natural abundance R26 RCs of Rb. sphaeroides ... 60
3.3.3 0uclear polarization dynamics towards steady state for R26 RCs ... 61
3.3.4 Evidence for a fraction of long-living carotenoid triplet states ... 66
4 ELECTRO"IC STRUCTURE OF THE PRIMARY ELECTRO" DO"OR OF RHODOBACTER SPHAEROIDES AT ATOMIC RESOLUTIO" ... 67
4.1INTRODUCTION ... 67
4.2MATERIALSANDMETHODS ... 69
4.2.1 Sample preparation ... 69
4.2.2 MAS 0MR experiments ... 69
4.2.3 Spectral fitting ... 70
4.3RESULTSANDDISCUSSION ... 71
4.3.1 Time resolved ns-flash photo-CID0P MAS 0MR ... 71
4.3.2 Electron densities in the ground state of P ... 73
4.3.3 Electron spin densities in the radical cation state ... 74
5 GE"ERAL DISCUSSIO" A"D FUTURE OUTLOOK ... 79
5.1INTRODUCTION ... 79
5.2APPLICATIONSOFNS-FLASHPHOTO-CIDNPMASNMR ... 81
5.2.1 Towards liquid state ... 81
5.2.2 The electronic structure of the primary photosynthetic radical pair ... 81
5.2.3 Action spectroscopy ... 83
5.3FUTUREOUTLOOK ... 84
5.3.1 0s-flash photo-CID0P MAS 0MR 2-dimensional spectroscopy ... 84
5.3.2 Labeled carotenoid in RCs ... 85
5.3.3 Imaging with microstrips ... 85
APPE"DICES ... 87
APPENDIX A ... 87
DFT calculations of hyperfine tensors ... 87
Electron-electron exchange and dipolar coupling, g tensor ... 99
APPENDIX B ... 101
Photo-CID0P MAS 0MR simulations ... 101
REFERE"CES ... 105
SUMMARY ... 113
SAME"VATTI"G ... 115
LIST OF PUBLICATIO"S ... 117
CURRICULUM VITAE ... 119
"AWOORD ... 121
