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.
In a recent MAS NMR study, two types of histidine residues in the light-harvesting complex II (LH2) of Rhodopseudomonas acidophila were resolved: Type 1 (neutral) and Type 2 (positively charged) (Alia et al. J. Am. Chem. Soc. ). The isotropic (13)C shifts of histidines coordinating to B850 BChl a are similar to fully positively charged histidine, while the (15)N shift anisotropy shows a predominantly neutral character. In addition the possibility that the ring currents are quenched by overlap in the superstructure of the complete ring of 18 B850 molecules in the LH2 complex could not be excluded. In the present work, by using two-dimensional heteronuclear ((1)H-(13)C) dipolar correlation spectroscopy with phase-modulated Lee-Goldburg homonuclear (1)H decoupling applied during the t(1) period, a clear and unambiguous assignment of the protons of histidine interacting with the magnesium of a BChl a molecule is obtained and a significant ring current effect from B850 on the coordinating histidine is resolved. Using the ring current shift on (1)H, we refine the (13)C chemical shift assignment of the coordinating histidine and clearly distinguish the electronic structure of coordinating histidines from that of fully positively charged histidine. The DFT calculations corroborate that the coordinating histidines carry approximately 0.2 electronic equivalent of positive charge in LH2. In addition, the data indicate that the ground state electronic structures of individual BChl a /His complexes is largely independent of supermolecular pi interactions in the assembly of 18 B850 ring in LH2.
Alia
Leiden Institute of Chemistry, Gorlaeus Laboratoria, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Matysik
Jörg
J
de Boer
Ido
I
Gast
Peter
P
van Gorkom
Hans J
HJ
de Groot
Huub J M
HJ
D000818:Animals; D002247:Carbon Isotopes / Q000737:chemistry; D006639:Histidine / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D045342:Light-Harvesting Protein Complexes / Q000737:chemistry*; D019906:Nuclear Magnetic Resonance, Biomolecular / Q000379:methods*; D045332:Photosystem II Protein Complex / Q000737:chemistry*
D002247:Carbon Isotopes; D045342:Light-Harvesting Protein Complexes; D045332:Photosystem II Protein Complex; D006639:Histidine; D006859:Hydrogen