Freer A, Prince S, Sauer K, Papiz M, Hawthornthwaite-Lawless A, McDermott G, Cogdell R, Isaacs N W
Department of Chemistry, University of Glasgow, UK.
Structure. 1996 Apr 15;4(4):449-62. doi: 10.1016/s0969-2126(96)00050-0.
Photosynthesis starts with the absorption of solar radiation by antenna pigment molecules. In purple bacteria these chromophores, (bacteriochlorophyll a and carotenoid) are embedded in the membrane; they are non-covalently bound to apoproteins which have the ability to modulate the chromophores' absorbing characteristics. The first structure of the bacterial antenna complex from Rhodopseudomonas acidophila, strain 10050, shows a ring of nonameric symmetry. Two concentric cylinders of apoproteins enclose the pigment molecules. The current resolution of the structure, to 2.5 A, allows us to begin to explore the mechanism of energy transfer among these pigments.
The mechanism of energy transfer, from the short- to long-wavelength-absorbing pigments, is largely determined by the relative distances and orientations of the chromophores. In this paper we provide evidence that energy transfer between the B800 and B850 bacteriochlorophylls is largely via Förster induced dipole-dipole resonance. Strong Coulombic (exciton) coupling among the 18 short distanced chromophores in the B850 macrocycle is promoted by good alignment of the Qy dipoles. Singlet-singlet energy transfer from carotenoid to the B800 macrocycle appears to be minimal, with most of the energy transfer going to B850. The higher energy state of both chromophores dominates in more complex situations.
The structure of the antenna complex not only shows Nature at its most aesthetic but also illustrates how clever and efficient the energy transfer mechanism has become, with singlet-singlet excitation being passed smoothly down the spectral gradient to the reaction centre.
光合作用始于天线色素分子对太阳辐射的吸收。在紫色细菌中,这些发色团(细菌叶绿素a和类胡萝卜素)嵌入膜中;它们与能够调节发色团吸收特性的脱辅基蛋白非共价结合。嗜酸红假单胞菌10050菌株的细菌天线复合体的首个结构显示出九聚体对称环。两个同心的脱辅基蛋白圆柱体包围着色素分子。目前该结构的分辨率为2.5埃,这使我们能够开始探索这些色素之间的能量转移机制。
从吸收短波长到长波长色素的能量转移机制,很大程度上由发色团的相对距离和取向决定。在本文中,我们提供证据表明,B800和B850细菌叶绿素之间的能量转移主要是通过福斯特诱导偶极 - 偶极共振。B850大环中18个近距离发色团之间强烈的库仑(激子)耦合是由Qy偶极的良好排列促进的。从类胡萝卜素到B800大环的单重态 - 单重态能量转移似乎最小,大部分能量转移到B850。在更复杂情况下,两种发色团的较高能态占主导。
天线复合体的结构不仅展现了大自然最精妙的一面,还说明了能量转移机制变得多么巧妙和高效,单重态 - 单重态激发能沿着光谱梯度顺利传递到反应中心。