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Effect of Lanthanide and Cobalt Ions on Electron Spin Relaxation of Tempone in Glassy Water:Glycerol at 20 to 200 K

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Abstract

The enhancement of X-band spin–lattice and spin–spin relaxation rates for the nitroxide tempone (2,2,6,6-tetramethyl-4-oxo-piperidin-1-oxyl) in 1:1 water:glycerol by Dy3+, Er3+, Tm3+ or Co2+ was examined between 20 and 200 K. Nitroxide relaxation rates were measured by two-pulse spin echo and three-pulse inversion recovery. The impact of the rapidly relaxing metal aquo ions on 1/T 1 of the nitroxide increases in the order Co2+ ~ Er3+ < Dy3+ < Tm3+. The maximum spin–lattice relaxation enhancement occurs at about 35 K for Dy3+, 40 K for Er3+, and 60 K for Co2+. When the metal ion is bound to the chelator diethylenetriamine pentaacetic acid (DTPA) the maximum enhancements for Dy(DTPA)2− and Er(DTPA)2− shift to about 80 K. The maximum enhancement is proposed to occur when 1/T 1 for the metal ion is approximately equal to the resonance frequency for the nitroxide. Interaction with the paramagnetic metal ion causes a much larger fractional change in 1/T 1 than for 1/T 2. Below about 20 K the enhancement of nitroxide 1/T 2 increases, which is attributed to relaxation of the metal ions at rates comparable to the electron–electron dipolar coupling, expressed in frequency units.

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Acknowledgments

Partial funding of this work by the University of Denver is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of Denver, Denver, CO, 80210, USA

    Priyanka Aggarwal, Sandra S. Eaton & Gareth R. Eaton

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  1. Priyanka Aggarwal
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  2. Sandra S. Eaton
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Correspondence to Gareth R. Eaton.

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Aggarwal, P., Eaton, S.S. & Eaton, G.R. Effect of Lanthanide and Cobalt Ions on Electron Spin Relaxation of Tempone in Glassy Water:Glycerol at 20 to 200 K. Appl Magn Reson 47, 1123–1134 (2016). https://doi.org/10.1007/s00723-016-0820-6

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