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Biomolecular DNP‐Supported NMR Spectroscopy using Site‐Directed Spin Labeling
Author(s) -
van der Cruijsen Elwin A. W.,
Koers Eline J.,
Sauvée Claire,
Hulse Raymond E.,
Weingarth Markus,
Ouari Olivier,
Perozo Eduardo,
Tordo Paul,
Baldus Marc
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201501376
Subject(s) - site directed spin labeling , nuclear magnetic resonance spectroscopy , spectroscopy , nuclear magnetic resonance , chemistry , materials science , physics , electron paramagnetic resonance , quantum mechanics
Dynamic nuclear polarization (DNP) has been shown to greatly enhance spectroscopic sensitivity, creating novel opportunities for NMR studies on complex and large molecular assemblies in life and material sciences. In such applications, however, site‐specificity and spectroscopic resolution become critical factors that are usually difficult to control by current DNP‐based approaches. We have examined in detail the effect of directly attaching mono‐ or biradicals to induce local paramagnetic relaxation effects and, at the same time, to produce sizable DNP enhancements. Using a membrane‐embedded ion channel as an example, we varied the degree of paramagnetic labeling and the location of the DNP probes. Our results show that the creation of local spin clusters can generate sizable DNP enhancements while preserving the intrinsic benefits of paramagnetic relaxation enhancement (PRE)‐based NMR approaches. DNP using chemical labeling may hence provide an attractive route to introduce molecular specificity into DNP studies in life science applications and beyond.