A Double-Armed, Hydrophilic Transition Metal Complex as a Paramagnetic NMR Probe

Qing Miao; Wei-Min Liu; Thomas Kock; Anneloes Blok; Monika Timmer; Mark Overhand; Marcellus Ubbink

doi:10.1002/anie.201906049

A Double-Armed, Hydrophilic Transition Metal Complex as a Paramagnetic NMR Probe

Angew Chem Int Ed Engl. 2019 Sep 9;58(37):13093-13100. doi: 10.1002/anie.201906049. Epub 2019 Aug 13.

Authors

Qing Miao¹, Wei-Min Liu², Thomas Kock¹, Anneloes Blok¹, Monika Timmer¹, Mark Overhand¹, Marcellus Ubbink¹

Affiliations

¹ Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC, Leiden, The Netherlands.
² Department of Chemistry, Fu Jen Catholic University, No. 510, Zhongzheng Rd., Xinzhuang Dist., New, Taipei City, 24205, Taiwan.

Abstract

Synthetic metal complexes can be used as paramagnetic probes for the study of proteins and protein complexes. Herein, two transition metal NMR probes (TraNPs) are reported. TraNPs are attached through two arms to a protein to generate a pseudocontact shift (PCS) using cobalt(II), or paramagnetic relaxation enhancement (PRE) with manganese(II). The PCS analysis of TraNPs attached to three different proteins shows that the size of the anisotropic component of the magnetic susceptibility depends on the probe surroundings at the surface of the protein, contrary to what is observed for lanthanoid-based probes. The observed PCS are relatively small, making cobalt-based probes suitable for localized studies, such as of an active site. The obtained PREs are stronger than those obtained with nitroxide spin labels and the possibility to generate both PCS and PRE offers advantages. The properties of TraNPs in comparison with other cobalt-based probes are discussed.

Keywords: NMR spectroscopy; magnetic susceptibility tensors; paramagnetic relaxation enhancements; pseudocontact shifts; transition metals.

Publication types

Review
Research Support, Non-U.S. Gov't

Abstract

Publication types

Grants and funding