TY  - JOUR
A1  - Seyfried, Patrick
A1  - Heinz, Marcel
A1  - Pintér, György
A1  - Klötzner, Dean-Paulos
A1  - Becker, Yvonne
A1  - Bolte, Michael
A1  - Jonker, Hendrik R. A.
A1  - Stelzl, Lukas S.
A1  - Hummer, Gerhard
A1  - Schwalbe, Harald
A1  - Heckel, Alexander
T1  - Optimal destabilization of DNA double strands by single-nucleobase caging
T2  - Chemistry
N2  - Photolabile protecting groups are widely used to trigger oligonucleotide activity. The ON/OFF‐amplitude is a critical parameter. An experimental setup has been developed to identify protecting group derivatives with superior caging properties. Bulky rests are attached to the cage moiety via Cu‐catalyzed azide–alkyne cycloaddition post‐synthetically on DNA. Interestingly, the decrease in melting temperature upon introducing o‐nitrobenzyl‐caged (NPBY‐) and diethylaminocoumarin‐cages (DEACM‐) in DNA duplexes reaches a limiting value. NMR spectroscopy was used to characterize individual base‐pair stabilities and determine experimental structures of a selected number of photocaged DNA molecules. The experimental structures agree well with structures predicted by MD simulations. Combined, the structural data indicate that once a sterically demanding group is added to generate a tri‐substituted carbon, the sterically less demanding cage moiety points towards the neighboring nucleoside and the bulkier substituents remain in the major groove.
KW  - click chemistry
KW  - computational chemistry
KW  - DNA
KW  - NMR spectroscopy
KW  - nucleobases
KW  - oligonucleotides
KW  - photochemistry
Y1  - 2019
UR  - http://publikationen.ub.uni-frankfurt.de/frontdoor/index/index/docId/51614
UR  - https://nbn-resolving.org/urn:nbn:de:hebis:30:3-516147
N1  - Gefördert durch: European Union: Horizon 2020. Infrastructure for NMR, EM and X-rays for Translational Research, iNEXT, H2020 Grant # 653706
VL  - 24
SP  - 17568
EP  - 17576
ER  -