Fakultät für Biologie und Biotechnologie, AG Photobiotechnologie , Ruhr Universität Bochum , Universitätsstraße 150 , 44801 Bochum , Germany.
Nano Lett. 2019 Sep 11;19(9):6621-6628. doi: 10.1021/acs.nanolett.9b02880. Epub 2019 Aug 15.
Sequence-specific aptamers act as functional scaffolds for the assembly of photosynthetic model systems. The Ru(II)--bipyridine photosensitizer is conjugated by different binding modes to the antityrosinamide aptamer to yield a set of photosensitizer-aptamer binding scaffolds. The -methyl--(3-aminopropane)-4,4-bipyridinium electron acceptor, MV, is covalently linked to tyrosinamide, TA, to yield the conjugate TA-MV. The tyrosinamide unit in TA-MV acts as a ligand for anchoring TA-MV to the Ru(II)--bipyridine-aptamer scaffold, generating the diversity of photosensitizer-aptamer/electron acceptor supramolecular conjugates. Effective electron transfer quenching in the photosynthetic model systems is demonstrated, and the quenching efficiencies are controlled by the structural features of the conjugates. The redox species generated by the photosensitizer-aptamer/electron acceptor supramolecular systems mediate the ferredoxin-NADP reductase, FNR, catalyzed synthesis of NADPH, and the Pt-nanoparticle-catalyzed evolution of hydrogen (H). The novelty of the study rests on the unprecedented use of aptamer scaffolds as functional units for organizing photosynthetic model systems.
序列特异性适体可作为组装光合模型系统的功能支架。钌（II）-联吡啶光敏剂通过不同的结合模式与抗酪氨酸酰胺适体偶联，得到一组光敏剂-适体结合支架。-甲基--(3-氨基丙基)-4,4-联吡啶鎓电子受体 MV 与酪氨酸酰胺 TA 发生共价连接，生成 TA-MV 缀合物。TA-MV 中的酪氨酸酰胺单元作为配体，将 TA-MV 锚定在 Ru(II)-联吡啶-适体支架上，生成多种光敏剂-适体/电子受体超分子缀合物。在光合模型系统中证明了有效的光诱导电子转移猝灭，并且猝灭效率由缀合物的结构特征控制。光敏剂-适体/电子受体超分子体系产生的氧化还原物种介导了铁氧还蛋白-NADP 还原酶 FNR 催化合成 NADPH 以及 Pt 纳米颗粒催化的氢气（H）的产生。该研究的新颖之处在于前所未有地将适体支架用作组织光合模型系统的功能单元。
