Journal
JOURNAL OF MAGNETIC RESONANCE
Volume 205, Issue 1, Pages 38-49Publisher
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jmr.2010.03.019
Keywords
Gd(III) spin labels; High-field DEER; Ka- and W-bands
Funding
- Binational Science Foundation (USA-Israel) [BSF 2006179]
- NIH [1R01 EB005866-01]
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In this work, we continue to explore Gd(III) as a possible spin label for high-field Double Electron-Electron Resonance (DEER) based distance measurements in biological molecules with flexible geometry. For this purpose, a bis-Gd(III) complex with a flexible bridge was used as a model. The distances in the model were expected to be distributed in the range of 5-26 angstrom. allowing us to probe the shortest limits of accessible distances which were found to be as small as 13 angstrom. The upper distance limit for these labels was also evaluated and was found to be about 60 angstrom. Various pulse duration setups can result in apparent differences in the distribution function derived from DEER kinetics due to short distance limit variations. The advantages, such as the ability to perform measurements at cryogenic temperatures and high repetition rates simultaneously, the use of very short pumping and observation pulses without mutual interference, the lack of orientational selectivity, as well as the shortcomings, such as the limited mw operational frequency range and intrinsically smaller amplitude of oscillation related to dipolar interaction as compared with nitroxide spin labels are discussed. Most probably the use of nitroxide and Gd-based labels for distance measurements will be complementary depending on the particulars of the problem and the availability of instrumentation. (C) 2010 Elsevier Inc. All rights reserved.
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