4.6 Article

Intramolecular Folding of PolyT Oligonucleotides Induced by Cooperative Binding of Silver(I) Ions

Journal

MOLECULES
Volume 27, Issue 22, Pages -

Publisher

MDPI
DOI: 10.3390/molecules27227842

Keywords

cooperative binding; DNA; intramolecular folding; metal-mediated base pairs; silver ions

Funding

  1. National Science Foundation of China (NSFC) [21775159, 22174157, 21927807]
  2. National Basic Research Program of China [2015CB932003]
  3. Youth Innovation Promotion Association of CAS [2013028]
  4. Sanming Project of Medicine in Shenzhen [21775159, SZsm201811070]

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It has been discovered that Ag+ can interact with polyT oligonucleotides to form an Ag+-bridged T-Ag+-T structure once the concentration of Ag+ in solution exceeds a certain threshold value. The intramolecular folding of the polyT oligonucleotide has a higher thermal stability than the duplex and can be reversibly modulated by cysteine.
Ag+-bridged T-Ag+-T was recently discovered in a Ag+-DNA nanowire crystal, but it was reported that Ag+ had little to no affinity to T nucleobases and T-rich oligonucleotides in solution. Therefore, the binding mode for the formation of this type of novel metallo base pair in solution is elusive. Herein, we demonstrate that Ag+ can interact with polyT oligonucleotides once the concentration of Ag+ in solution exceeds a threshold value. The threshold value is independent of the concentration of the polyT oligonucleotide but is inversely proportional to the length of the polyT oligonucleotide. The polyT oligonucleotides are intramolecularly folded due to their positively cooperative formation and the stack of T-Ag+-T base pairs, resulting in the 5 '- and 3 '-ends being in close proximity to each other. The intramolecular Ag+-folded polyT oligonucleotide has a higher thermal stability than the duplex and can be reversibly modulated by cysteine.

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