Modelling Photosynthesis with ZnII‐Protoporphyrin All‐DNA G‐Quadruplex/Aptamer Scaffolds

• Published in: Angewandte Chemie International Edition 2020-06, Vol.59 (23), p.9163-9170
• Main Authors: Luo, Guo‐Feng, Biniuri, Yonatan, Chen, Wei‐Hai, Wang, Jianbang, Neumann, Ehud, Marjault, Henri‐Baptiste, Nechushtai, Rachel, Winkler, Martin, Happe, Thomas, Willner, Itamar
• Format: Article
• Language: English
• Subjects: Acetophenone; Alcohol dehydrogenase; Aptamers; artificial photosynthesis; Deoxyribonucleic acid; DNA; Electron transfer; energy conversion; Ferredoxin; ferredoxin-NADP+ reductase; NADP; nanobiotechnology; Photosynthesis; Photosystem I; Protoporphyrin; Protoporphyrin IX; Reductase; Reductases; Reduction; Scaffolds; Thymidine
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202002915

All‐DNA scaffolds act as templates for the organization of photosystem I model systems. A series of DNA templates composed of ZnII‐protoporphyrin IX (ZnIIPPIX)‐functionalized G‐quadruplex conjugated to the 3′‐ or 5′‐end of the tyrosinamide (TA) aptamer and ZnIIPPIX/G‐quadruplex linked to the 3′‐ and 5′‐ends of the TA aptamer through a four‐thymidine bridge. Effective photoinduced electron transfer (ET) from ZnIIPPIX/G‐quadruplex to bipyridinium‐functionalized tyrosinamide, TA‐MV2+, bound to the TA aptamer units is demonstrated. The effectiveness of the primary ET quenching of ZnIIPPIX/G‐quadruplex by TA‐MV2+ controls the efficiency of the generation of TA‐MV+.. The photosystem‐controlled formation of TA‐MV+. by the different photosystems dictates the secondary activation of the ET cascade corresponding to the ferredoxin‐NADP+ reductase (FNR)‐catalysed reduction of NADP+ to NADPH by TA‐MV+., and the sequestered alcohol dehydrogenase catalysed reduction of acetophenone to 1‐phenylethanol by NADPH. All‐DNA energy conversion: ZnIIPPIX/G‐quadruplex aptamer/electron acceptor nanostructures provide effective scaffolds for mimicking photosynthesis.