Paramagnetic Chemical Probes for Studying Biological Macromolecules

Chemical Reviews, vol. 122, pp. 9571–9642

Abstract

Paramagnetic chemical probes have been used in electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopy for more than four decades. Recent years witnessed a great increase in the variety of probes for the study of biological macromolecules (proteins, nucleic acids, and oligosaccharides). This Review aims to provide a comprehensive overview of the existing paramagnetic chemical probes, including chemical synthetic approaches, functional properties, and selected applications. Recent developments have seen, in particular, a rapid expansion of the range of lanthanoid probes with anisotropic magnetic susceptibilities for the generation of structural restraints based on residual dipolar couplings and pseudocontact shifts in solution and solid state NMR spectroscopy, mostly for protein studies. Also many new isotropic paramagnetic probes, suitable for NMR measurements of paramagnetic relaxation enhancements, as well as EPR spectroscopic studies (in particular double resonance techniques) have been developed and employed to investigate biological macromolecules. Notwithstanding the large number of reported probes, only few have found broad application and further development of probes for dedicated applications is foreseen.

Authors 6

1. Qing Miao Aachen

   Leiden University · Shaanxi University of Science and Technology

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, Leiden 2333 CC, The Netherlands

   School of Chemistry &Chemical Engineering, Shaanxi University of Science & Technology, Xi’an710021, China

2. Christoph Nitsche

   Australian National University

   Affiliation as printed

   Research School of Chemistry, The Australian National University, Sullivans Creek Road, Canberra, Australian Capital Territory 2601, Australia

3. Henry W. Orton

   Australian National University · ARC Centre of Excellence for Innovations in Peptide and Protein Science

   Affiliation as printed

   ARC Centre of Excellence for Innovations in Peptide & Protein Science, Research School of Chemistry, Australian National University, Sullivans Creek Road, Canberra, Australian Capital Territory 2601, Australia

   Research School of Chemistry, The Australian National University, Sullivans Creek Road, Canberra, Australian Capital Territory 2601, Australia

4. Mark Overhand Aachen

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, Leiden 2333 CC, The Netherlands

5. Gottfried Otting

   Australian National University · ARC Centre of Excellence for Innovations in Peptide and Protein Science

   Affiliation as printed

   ARC Centre of Excellence for Innovations in Peptide & Protein Science, Research School of Chemistry, Australian National University, Sullivans Creek Road, Canberra, Australian Capital Territory 2601, Australia

   Research School of Chemistry, The Australian National University, Sullivans Creek Road, Canberra, Australian Capital Territory 2601, Australia

6. Marcellus Ubbink corresponding Aachen

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, Leiden 2333 CC, The Netherlands