Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2300 RA Leiden, The Netherlands.
Biochemistry. 2012 Jul 24;51(29):5763-73. doi: 10.1021/bi300468y. Epub 2012 Jul 11.
Applying photo-CIDNP (photochemically induced dynamic nuclear polarization) MAS (magic-angle spinning) nuclear magnetic resonance to whole cells of Heliobacillus (Hb.) mobilis, we demonstrate that heliobacterial reaction centers are operational in two different states as indicated by the occurrence of a light-induced spin-correlated radical pair. A culture maintained anaerobically is called "Braunstoff" (German for "brown substance"). After exposure to oxygen, Braunstoff is converted to "Grünstoff" ("green substance") as indicated by a color change due to the conversion of BChl g to Chl a(F). It is shown that electron transfer occurs symmetrically via both branches of cofactors in both forms. The donor and acceptor cofactors remain identical and unchanged upon conversion, while the intermediate accessory cofactors are transformed from BChl g to Chl a(F). The donor triplet state in Braunstoff is localized on the special pair donor and lives for 100 μs, demonstrating the absence of nearby carotenoids. In Grünstoff, the donor triplet becomes mobile and appears to be formed on an accessory cofactor.
应用光诱导的 CIDNP(光化学诱导动态核极化)MAS(魔角旋转)核磁共振技术于弛豫菌(Hb.) mobilis 的完整细胞,我们证明了嗜硫菌反应中心以两种不同的状态运作,这可以通过光诱导的自旋相关自由基对的出现来指示。在无氧条件下培养的细菌称为“Braunstoff”(德语为“棕色物质”)。暴露于氧气后,Braunstoff 会因 BChl g 向 Chl a(F)的转化而发生颜色变化,转化为“Grünstoff”(“绿色物质”)。结果表明,在两种形式中,电子通过辅助因子的两个分支对称地转移。在转化过程中,供体和受体辅助因子保持相同且不变,而中间辅助因子则从 BChl g 转化为 Chl a(F)。Braunstoff 中的供体三重态定位于特殊对供体上,并存在 100 μs,表明不存在附近的类胡萝卜素。在 Grünstoff 中,供体三重态变得移动,并似乎在辅助因子上形成。