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@ARTICLE{Mieczkowski:462564,
author = {Mieczkowski, Mateusz and Steinmetzger, Christian and Bessi,
Irene and Lenz, Ann-Kathrin and Schmiedel, Alexander and
Holzapfel, Marco and Lambert, Christoph and Pena, Vladimir
and Hoebartner, Claudia},
title = {{L}arge {S}tokes shift fluorescence activation in an {RNA}
aptamer by intermolecular proton transfer to guanine},
journal = {Nature Communications},
volume = {12},
number = {1},
issn = {2041-1723},
address = {[London]},
publisher = {Nature Publishing Group UK},
reportid = {PUBDB-2021-03466},
pages = {3549},
year = {2021},
abstract = {Fluorogenic RNA aptamers are synthetic functional RNAs that
specifically bind and activate conditional fluorophores. The
Chili RNA aptamer mimics large Stokes shift fluorescent
proteins and exhibits high affinity for
3,5-dimethoxy-4-hydroxybenzylidene imidazolone (DMHBI)
derivatives to elicit green or red fluorescence emission.
Here, we elucidate the structural and mechanistic basis of
fluorescence activation by crystallography and time-resolved
optical spectroscopy. Two co-crystal structures of the Chili
RNA with positively charged DMHBO+ and DMHBI+ ligands
revealed a G-quadruplex and a trans-sugar-sugar edge G:G
base pair that immobilize the ligand by π-π stacking. A
Watson-Crick G:C base pair in the fluorophore binding site
establishes a short hydrogen bond between the N7 of guanine
and the phenolic OH of the ligand. Ultrafast excited state
proton transfer (ESPT) from the neutral chromophore to the
RNA was found with a time constant of 130 fs and revealed
the mode of action of the large Stokes shift fluorogenic RNA
aptamer.},
cin = {DOOR ; HAS-User / UWuerzburg},
ddc = {500},
cid = {I:(DE-H253)HAS-User-20120731 /
I:(DE-H253)UWuerzburg-20140802},
pnm = {6G3 - PETRA III (DESY) (POF4-6G3) / FS-Proposal: I-20190778
(I-20190778) / FS-Proposal: I-20200799 (I-20200799)},
pid = {G:(DE-HGF)POF4-6G3 / G:(DE-H253)I-20190778 /
G:(DE-H253)I-20200799},
experiment = {EXP:(DE-H253)P-P11-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:34112799},
UT = {WOS:000663750600005},
doi = {10.1038/s41467-021-23932-0},
url = {https://bib-pubdb1.desy.de/record/462564},
}