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Construction of a DNA‐Based Supramolecular Nanosheet That Emits Bluish‐White Light from Charge‐Transfer Excited States of the Nucleobases
Author(s) -
Iwaura Rika
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201804960
Subject(s) - nucleobase , nanosheet , excited state , supramolecular chemistry , oligonucleotide , photochemistry , materials science , chemistry , crystallography , dna , nanotechnology , crystal structure , biochemistry , physics , nuclear physics
Abstract 1,ω‐Inosinic acid‐bearing bolaamphiphiles dI(18), dI(19), and dI(20) with a 3′‐phosphorylated inosine as a universal base connected to each end of an oligomethylene chain were synthesized for the first time. Single‐component self‐assemblies of these bolaamphiphiles and their binary self‐assemblies with salmon sperm DNA were studied by AFM; temperature‐dependent UV absorption, fluorescence, and circular dichroism spectroscopy; and gel electrophoresis. The binary self‐assembly of dI(20) and salmon sperm DNA (dI(20)‐DNA) had a nanosheet structure with a homogeneous thickness of about 6 nm and widths of several micrometers. Interestingly, an aqueous solution of the nanosheets showed a broad absorption band originating from the charge‐transfer (CT) states of the nucleobase in the long‐wavelength region (>300 nm), and the molar absorptivity per nucleobase was calculated to be approximately 150 times that of single‐stranded (dT20 and dA20) and double‐stranded (dT20‐dA20) oligonucleotides. In addition, a continuous and broad emission band originating from CT excited states of the nucleobases was observed in the visible region. These observations indicate that CT states of the nucleobases were formed and stabilized in the supramolecular nanosheet and that bluish white light was emitted from CT excited states of the nucleobases.