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Modelling Photosynthesis with Zn II ‐Protoporphyrin All‐DNA G‐Quadruplex/Aptamer Scaffolds
Author(s) -
Luo GuoFeng,
Biniuri Yonatan,
Chen WeiHai,
Wang Jianbang,
Neumann Ehud,
Marjault HenriBaptiste,
Nechushtai Rachel,
Winkler Martin,
Happe Thomas,
Willner Itamar
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202002915
Subject(s) - chemistry , g quadruplex , aptamer , electron transfer , photochemistry , protoporphyrin ix , photosystem ii , alcohol dehydrogenase , photosystem i , quenching (fluorescence) , stereochemistry , dna , photosynthesis , photodynamic therapy , biochemistry , enzyme , fluorescence , organic chemistry , physics , biology , genetics , quantum mechanics
Abstract All‐DNA scaffolds act as templates for the organization of photosystem I model systems. A series of DNA templates composed of Zn II ‐protoporphyrin IX (Zn II PPIX)‐functionalized G‐quadruplex conjugated to the 3′‐ or 5′‐end of the tyrosinamide (TA) aptamer and Zn II PPIX/G‐quadruplex linked to the 3′‐ and 5′‐ends of the TA aptamer through a four‐thymidine bridge. Effective photoinduced electron transfer (ET) from Zn II PPIX/G‐quadruplex to bipyridinium‐functionalized tyrosinamide, TA‐MV 2+ , bound to the TA aptamer units is demonstrated. The effectiveness of the primary ET quenching of Zn II PPIX/G‐quadruplex by TA‐MV 2+ 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.