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Proton spinlattice relaxation rate constants have been measured as a function of magnetic field strength for water, water
glycerol solution, cyclohexane, methanol, benzene, acetone, acetonitrile, and dimethyl sulfoxide. The magnetic relaxation dispersion
is well approximated by a Lorentzian shape. The origin of the
relaxation dispersion is identified with the paramagnetic contribution from molecular oxygen. In the small molecule cases studied
here, the effective correlation time for the electron-nuclear coupling may include contributions from both translational diffusion
and the electron T 1. The electron T 1 for molecular oxygen dissolved in several solvents was found to be approximately 7.5 ps
and nearly independent of solvent or viscosity. 2001 Academic Press
Key Words: oxygen; magnetic relaxation; relaxation dispersion;
MRD; electron-spin relaxation.
1090-7807/01 $35.00
Copyright 2001 by Academic Press
All rights of reproduction in any form reserved.
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TENG ET AL.
platform and Mathematica 3.0 (Wolfram Research Inc., Champaign, IL) for the Unix computer platform.
RESULTS AND DISCUSSION
Proton spinlattice relaxation rates for cyclohexane, benzene, methanol, acetone, acetonitrile, and dimethyl sulfoxide
equilibrated with oxygen at 1 atm are shown in Fig. 1 as a
function of magnetic field strength plotted as the proton Larmor frequency on the bottom axis. The electron Larmor frequency is shown on the top axis. Data for aqueous systems are
shown in Fig. 2 where the water was in equilibrium with 1 atm
oxygen but the 50% glycerol solution was in equilibrium with
air. In the absence of oxygen, there is no significant magnetic
field dependence of the solventproton spinlattice relaxation
rate constants over the range of fields studied. The rotational
and translational motions that dominate the protonproton dipole dipole contributions to nuclear spin relaxation disperse at
Larmor frequencies more than an order of magnitude larger
than those studied here because the correlation times are in the
range of tens to hundreds of picoseconds. The internal chair
chair conformational interconversions in cyclohexane, which
may be detected by spinlattice relaxation dispersion measurements in the radiofrequency field (11), make no significant
contribution to the dispersion in the Zeeman field because the
relaxation contribution is proportional to the square of the
chemical shift difference and, therefore, to the square of the
magnetic field strength. The chair chair interconversion would
correspond to a dispersion near 1 MHz but at this low field the
chemical shift differences are so small that the relaxation
contribution is negligible compared with those from other
relaxation mechanisms. Therefore, the magnetic relaxation dispersion observed in the proton relaxation rate of the different
solvents in contact with oxygen derives from the paramagnetism of the dissolved oxygen.
The MRD profiles for the different solvents are remarkably
similar. Different relaxation rates are expected because the
relaxation rate is generally linear in the concentration of the
paramagnetic center. However, the effective correlation time or
the inflection frequency should not depend on the oxygen
concentration unless the concentration becomes sufficiently
large that oxygen oxygen interactions become important.
There is no evidence for oxygen oxygen effects in these data.
The paramagnetic contribution to the relaxation dispersion
profile is expected to be dominated by the relative translational
motion of the oxygen molecule and the solvent protons. The
relaxation equations for this problem have been developed by
Freed and colleagues (12, 13) and by Ayant et al. (14). These
theories, which are appropriate for the current data set, include
four parameters: the translational correlation time or the relative diffusion constant, the distance of closest approach between the interacting spins, the low-field electron spin relaxation time, and the correlation time for the electron spin
relaxation process. The inflection frequencies in the data of
Fig. 1 correspond to correlation times that are shorter than most
measures of solventmolecule translational correlation times.
Thus, the electron relaxation time must make a significant
contribution to the effective correlation time for the electronnuclear coupling. The problem in fitting data to the translational relaxation equations is that the short electron spin relaxation time makes the fit relatively insensitive to the choices of
the translational correlation time or, equivalently, the translational diffusion constant and the distance of closest approach.
We minimize these problems by assuming the Lorentzian
function in Eq. [1], which is the form of the translational model
in the limit that the electron spin relaxation time is very short.
33
OXYGEN RELAXATION
TABLE 1
Electron Spin Relaxation Parameters
Cyclohexane
Benzene
Methanol (CH 3)
Acetone
Acetonitrile
DMSO
Glycerol/water (1:1)
Water
(ps)
A (10 10 )
7.2 0.2
5.2 0.2
4.5 0.3
4.0 0.2
4.2 0.3
6.7 0.4
5.7 0.9
6.8 0.5
4.9 0.2
3.3 0.2
3.1 0.3
3.6 0.3
2.7 0.2
1.4 0.1
3.0 0.7
1.2 0.1
1.14 0.02
0.47 0.01
0.43 0.02
0.38 0.02
0.47 0.01
0.48 0.01
1.00 0.01
0.50 0.01
A
B,
T1
1 S2 2
[1]
[2]
,
T 1e tr
[3]
.
tr
l2
[4]
1
1
mw
CD solvent
T 1e
2/3
[5]
34
TENG ET AL.
the interpretation of experiments in which the oxygen paramagnetism is used to probe interactions with cosolute macromolecules by measuring the oxygen-induced changes in macromolecule 1H spinlattice relaxation rates.
ACKNOWLEDGMENTS
This work was supported by the National Institutes of Health, GM34541 and
GM54067. We appreciate helpful discussions with Jack Freed and the assistance of Charles Holmes and Shawn Wagner.
REFERENCES