Artificial Photosynthesis with Electron Acceptor/Photosensitizer-Aptamer Conjugates.

Abstract

Sequence-specific aptamers act as functional scaffolds for the assembly of photosynthetic model systems. The Ru(II)-<i>tris</i>-bipyridine photosensitizer is conjugated by different binding modes to the antityrosinamide aptamer to yield a set of photosensitizer-aptamer binding scaffolds. The <i>N</i>-methyl-<i>N'</i>-(3-aminopropane)-4,4<i>'</i>-bipyridinium electron acceptor, MV²⁺, is covalently linked to tyrosinamide, TA, to yield the conjugate TA-MV²⁺. The tyrosinamide unit in TA-MV²⁺ acts as a ligand for anchoring TA-MV²⁺ to the Ru(II)-<i>tris</i>-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 (H₂). The novelty of the study rests on the unprecedented use of aptamer scaffolds as functional units for organizing photosynthetic model systems.