Gd(iii) and Mn(ii) complexes for dynamic nuclear polarization: small molecular chelate polarizing agents and applications with site-directed spin labeling of proteins. Issue 39 (22nd August 2016)

• Record Type: Journal Article
• Authors: Kaushik, Monu; Bahrenberg, Thorsten; Can, Thach V.; Caporini, Marc A.; Silvers, Robert; Heiliger, Jörg; Smith, Albert A.; Schwalbe, Harald; Griffin, Robert G.; Corzilius, Björn
• Is Part Of: Physical chemistry chemical physics. Volume 18:Issue 39(2016)
• Page Start: 27205
• Page End: 27218
• Publication Date: 2016-08-22
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c6cp04623a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Metal complexes based on Gd(iii ) and Mn(ii ) spin-labels can be utilized for dynamic nuclear polarization of 1 H, 13 C, and 15 N. Abstract : We investigate complexes of two paramagnetic metal ions Gd 3+ and Mn 2+ to serve as polarizing agents for solid-state dynamic nuclear polarization (DNP) of 1 H, 13 C, and 15 N at magnetic fields of 5, 9.4, and 14.1 T. Both ions are half-integer high-spin systems with a zero-field splitting and therefore exhibit a broadening of the m S = −1/2 ↔ +1/2 central transition which scales inversely with the external field strength. We investigate experimentally the influence of the chelator molecule, strong hyperfine coupling to the metal nucleus, and deuteration of the bulk matrix on DNP properties. At small Gd-DOTA concentrations the narrow central transition allows us to polarize nuclei with small gyromagnetic ratio such as 13 C and even 15 N via the solid effect. We demonstrate that enhancements observed are limited by the available microwave power and that large enhancement factors of >100 (for 1 H) and on the order of 1000 (for 13 C) can be achieved in the saturation limit even at 80 K. At larger Gd(iii ) concentrations (≥10 mM) where dipolar couplings between two neighboring Gd 3+ complexes become substantial a transition towards cross effect as dominating DNP mechanism is observed. Furthermore, the slow spin-diffusion between 13 C and 15 N, respectively, allows for temporally resolved observation of enhanced polarization spreading from nuclei close to the paramagnetic ion towards nuclei further removed. Subsequently, we present preliminary DNP experiments on ubiquitin by site-directed spin-labeling with Gd 3+ chelator tags. The results hold promise towards applications of such paramagnetically labeled proteins for DNP applications in biophysical chemistry and/or structural biology.