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  Cross relaxation in nitroxide spin labels.

Marsh, D. (2016). Cross relaxation in nitroxide spin labels. Journal of Magnetic Resonance, 272, 172-180. doi:10.1016/j.jmr.2016.09.014.

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Marsh, D.1, Author           
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1Department of NMR Based Structural Biology, MPI for biophysical chemistry, Max Planck Society, ou_578567              

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 Abstract: Calibrations are given to extract orientation order parameters from pseudo-powder electron paramagnetic resonance line shapes of 14N-nitroxide spin labels undergoing slow rotational diffusion. The nitroxide z-axis is assumed parallel to the long molecular axis. Stochastic-Liouville simulations of slow-motion 9.4-GHz spectra for molecular ordering with a Maier–Saupe orientation potential reveal a linear dependence of the splittings, 2Amax and 2Amin, of the outer and inner peaks on order parameter Szz that depends on the diffusion coefficient DR⊥ which characterizes fluctuations of the long molecular axis. This results in empirical expressions for order parameter and isotropic hyperfine coupling: Szz=s1×(Amax−Amin)−so and ao=13(fmaxAmax+fminAmin)+δao, respectively. Values of the calibration constants s1, so, fmax, fmin and δao are given for different values of DR⊥ in fast and slow motional regimes. The calibrations are relatively insensitive to anisotropy of rotational diffusion (DR//≥DR⊥), and corrections are less significant for the isotropic hyperfine coupling than for the order parameter.

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Language(s): eng - English
 Dates: 2016-10-032016-11
 Publication Status: Issued
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 Rev. Type: Peer
 Identifiers: DOI: 10.1016/j.jmr.2016.09.014
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Title: Journal of Magnetic Resonance
Source Genre: Journal
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Pages: - Volume / Issue: 272 Sequence Number: - Start / End Page: 172 - 180 Identifier: -