A Highly Stabilizing Silver(I)‐Mediated Base Pair in Parallel‐Stranded DNA |
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Authors: | Indranil Sinha Dr. Célia Fonseca Guerra Prof. Dr. Jens Müller |
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Affiliation: | 1. Westf?lische Wilhelms‐Universit?t Münster, Institut für Anorganische und Analytische Chemie & NRW Graduate School of Chemistry, Corrensstrasse 28/30, 48149 Münster (Germany);2. Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling (ACMM), VU University Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam (The Netherlands) |
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Abstract: | The first parallel‐stranded DNA duplex with Hoogsteen base pairing that readily incorporates an Ag+ ion into an internal mispair to form a metal‐mediated base pair has been created. Towards this end, the highly stabilizing 6 FP ‐Ag+‐ 6 FP base pair comprising the artificial nucleobase 6‐furylpurine ( 6 FP ) was devised. A combination of temperature‐dependent UV spectroscopy, CD spectroscopy, and DFT calculations was used to confirm the formation of this base pair. The nucleobase 6 FP is capable of forming metal‐mediated base pairs both by the Watson–Crick edge (i.e. in regular antiparallel‐stranded DNA) and by the Hoogsteen edge (i.e. in parallel‐stranded DNA), depending on the oligonucleotide sequence and the experimental conditions. The 6 FP ‐Ag+‐ 6 FP base pair within parallel‐stranded DNA is the most strongly stabilizing Ag+‐mediated base pair reported to date for any type of nucleic acid, with an increase in melting temperature of almost 15 °C upon the binding of one Ag+ ion. |
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Keywords: | bioinorganic chemistry metal‐mediated base pair parallel‐stranded DNA purines silver |
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