Spectroscopic Investigations of Lanthanide Ion Binding to Nucleic Acids

  • Janet R. MorrowEmail author
  • Christopher M. Andolina
Part of the Metal Ions in Life Sciences book series (MILS, volume 10)


Luminescent lanthanide (Ln(III)) ions are valuable spectroscopic probes for metal ion binding sites in nucleic acids. In this chapter, we briefly review Ln(III) luminescence and the information available from these experiments. An emphasis is placed on direct excitation Eu(III) spectroscopy as a tool. Eu(III) excitation spectroscopy is used to show that solutions containing micromolar Eu(III), 100 mM NaCl, and 20 mM MES buffer contain predominantly a mononuclear Eu(III) aqua complex and an Eu(III) hydroxide complexes. The binding of these species to various RNA and DNA sequences are monitored by using Eu(III) excitation spectroscopy. Eu(III) luminescence lifetime data shows that the Eu(III) ion typically loses 1–3 water molecules to form innersphere complexes with RNA and DNA that contain tandem base pair mismatches or hairpin loops. In addition, early studies that used nucleobase-sensitized Eu(III) or Tb(III) luminescence within transfer RNA or in the hammerhead ribozyme are presented. Luminescence resonance energy transfer studies are shown to be useful for determining distances between bound Ln(III) ion and organic fluorophores or between two different Ln(III) ions. To supplement luminescence data, the binding sites of paramagnetic Ln(III) ions are determined by monitoring the chemical shifts of nucleotide protons. Binding sites are identified by following the protons that are influenced by the Ln(III) pseudo-contact shift.


DNAzyme europium fl uorescence resonance energy transfer lanthanide ion aqueous complexes lanthanide ion complexes lanthanide ion coordination chemistry lanthanide ion dimerization lanthanide ion hydrolysis laser induced luminescence luminescence lifetimes lanthanide luminescence lanthanide ion macrocyclic complexes lanthanide ion solution chemistry nucleic acid materials nucleic acid structure pseudo-contact shift ribozyme RNA NMR structure 



We acknowledge Dr. Ryan Matthews of the University at Buffalo and Dr. Matthew Fountain of the State University of New York, College at Fredonia, for contributing to this manuscript. We gratefully acknowledge the National Science Foundation (CHE0911375) for support of this work and for a major instrumentation award (CHE-0321058) to build the MOPO laser system.


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© Springer Science+Business Media B.V. 2012

Authors and Affiliations

  1. 1.Department of ChemistryUniversity at Buffalo, State University of New YorkBuffaloUSA

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