Sequence‐Dependent Duplex Stabilization upon Formation of a Metal‐Mediated Base Pair |
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| Authors: | Dr. Philipp Scharf Biswarup Jash Dr. Jissy A. Kuriappan Dr. Mark P. Waller Prof. Dr. Jens Müller |
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| Affiliation: | 1. Westf?lische Wilhelms‐Universit?t Münster, Institut für Anorganische und Analytische Chemie, Corrensstrasse 28/30, 48149 Münster (Germany);2. Current address: University of Iceland, Science Institute, Dunhagi 3, 107 Reykjavík (Iceland);3. Westf?lische Wilhelms‐Universit?t Münster, Graduate School of Chemistry, Corrensstrasse 28/30, 48149 Münster (Germany);4. Westf?lische Wilhelms‐Universit?t Münster, Organisch‐Chemisches Institut and Center for Multiscale Theory and Computation, Corrensstrasse 40, 48149 Münster (Germany) |
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| Abstract: | An artificial nucleoside surrogate with 1H‐imidazo[4,5‐f][1,10]phenanthroline ( P ) acting as an aglycone has been introduced into DNA oligonucleotide duplexes. This nucleoside surrogate can act as a bidentate ligand, and so is useful in the context of metal‐mediated base pairs. Several duplexes involving a hetero base pair with an imidazole nucleoside have been investigated. The stability of DNA duplexes incorporating the respective AgI‐mediated base pairs strongly depends on the sequence context. Quantum mechanical/molecular mechanical (QM/MM) calculations have been performed in order to gain insight into the factors determining this sequence dependence. The results indicated that, in addition to the stabilizing effect that results from the formation of coordinative bonds, destabilizing effects may occur when the artificial base pair does not fit optimally into the surrounding B‐DNA duplex. |
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| Keywords: | bioinorganic chemistry DNA phenanthroline quantum mechanics/molecular mechanics silver |
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