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The Equilibrium Binding Constant and Binding Strength

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Protocol for the Solid-phase Synthesis of Oligomers of RNA Containing a 2'-O-thiophenylmethyl Modification and Characterization via Circular Dichroism
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Molybdenocene-oligonucleotide binding study at physiological pH using NMR spectroscopy and cyclic voltammetry.

José L Vera1, Félix R Román, Enrique Meléndez

  • 1University of Puerto Rico, Department of Chemistry, PO Box 9019, Mayagüez 00681, Puerto Rico.

Bioorganic & Medicinal Chemistry
|September 2, 2006
PubMed
Summary

Molybdenocene dichloride exhibits weak binding interactions with DNA, primarily interacting with nucleotide bases rather than forming strong coordination bonds. This study used NMR and cyclic voltammetry to analyze these interactions.

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Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR

Published on: December 16, 2013

Area of Science:

  • Bioinorganic Chemistry
  • Medicinal Chemistry
  • Nuclear Magnetic Resonance (NMR) Spectroscopy

Background:

  • Molybdenocene dichloride is investigated as a potential antitumor agent.
  • Understanding the interaction of metal complexes with DNA is crucial for drug development.
  • Oligonucleotides serve as model systems for studying DNA-metal complex binding.

Purpose of the Study:

  • To elucidate the binding interactions between molybdenocene dichloride and a model self-complementary oligonucleotide (CGCATATATGCG).
  • To characterize the behavior of molybdenocene dichloride in various solution conditions (pH, buffer).
  • To determine the nature and strength of molybdenocene dichloride-DNA interactions.

Main Methods:

  • Characterization of the oligonucleotide using proton (1H), NOESY, and DQF-COSY NMR.
  • Analysis of molybdenocene dichloride speciation in solution using 1H NMR spectroscopy.
  • Study of molybdenocene dichloride-oligonucleotide interactions via 1H and 31P NMR spectroscopy and cyclic voltammetry.

Main Results:

  • Molybdenocene dichloride exists in equilibrium with its dimeric form at pH 6.5 and above in saline solutions.
  • A new species coordinated by Tris(hydroxymethyl)aminomethane (Tris) buffer is formed at physiological pH.
  • NMR studies indicate downfield shifts and signal broadening upon molybdenocene dichloride addition, suggesting base interactions; no Mo(IV)-OP coordination was observed.
  • Cyclic voltammetry titration revealed a weak interaction (4.9%) between molybdenocene dichloride and the oligonucleotide.

Conclusions:

  • Molybdenocene dichloride interacts weakly with DNA, with binding predominantly occurring at the nucleotide bases.
  • The observed interactions do not involve direct coordination to the phosphate backbone.
  • These findings provide insights into the mechanism of action for potential molybdenocene-based anticancer drugs.