Pulsed
nuclear magnetic resonance (NMR) is a powerful and flexible scientific
tool which manipulates the magnetic moments
µ and angular
momentum of atoms to draw conclusions about their local environment. The
phenomena can observed in many particles (Magnetic moments of various
atoms can be found
here
), but is most commonly observed in hydrogen atoms. A sample is placed in
a permanent magnetic field
B, and dipoles align along the magnetic
field because their energy E = -
µ .
Bo is at a minimum
along the field. The net result is a magnetic moment
M aligning
with the field (See Figure 1).
Once
the magnetization aligns, radio waves are directed at the sample, applying
a rotating magnetic field
H to the net magnetization. The
H
field rotates in the xy plane, or perpendicular to the permanent magnet
field. Magnetizations perpendicular to magnetic fields precess around the
field axis, and the precession rate for the atoms is ω = γD, where γ is the
atom's
gyromagnetic ratio
and D is the field strength. The inclusion of
H to the sample then
rotates
M out of alignment with
B, and the magnetization precess
about
H and
B fields. The end result is a very complex motion
of
M which can be simplified in the resonance condition where the frequency
of the precession is equal to the frequency of the radio waves. The
H and
M vectors rotating at the same rate allows
us to easily view the situation in a frame rotating at the resonant frequency.
In this frame,
H is constant, and
B isn't observed because
of the transformation into a rotating frame. So
M can be rotated away
from the z-axis by varying the time that
H is present, or the duration
of the radio pulse (See Figure 2, b) being a time t later than a)).
One scientifically interesting position
for
M to be is perpendicular to
B, so the maximum magnetization
is precessing about the permanent magnetic field. The radio pulse that
rotates the magnetization perpendicular to permanent magnetic is called
90º. In this position, the net magnetization of the sample decreases
with time partly because the magnetic field is not constant over the sample.
Different local magnetic fields throughout the sample create slightly different
B values for each atom, which changes the precession rates for individual
µ s. The range of precession rates causes the individual
moments to get out of phase, which causes
M to decay (See
Figure 3). The observation of
M decaying is called a
Free Induction Decay
(FID). If an FID signal is
Fourier transformed
, the different precession frequencies which drive the FID can be found
(see Figure 4
1). This allows us to back calculate
the local magnetic fields at the atoms in the sample, which often elucidates,
among other things, the molecular structure of the sample, as in
the NMR facility at UCSC
. Unfortunately, the equipment in the Senior Lab is not sufficient to study
molecular structure in this way, as it requires NMR system with a high homogeniety
magnet, such as those offered by
Varian Inc.
. For some of the basics ideas of structure analysis, please go
here
.
Pulsed
NMR can go beyond molecular structure and analyze molecular interactions.
Two of these are the spin lattice relaxation time T
1
and the spin spin relaxation time T
2. T
1 is calculated by rotating
M until it is anti-parallel to
H, and observing the behavior of the magnetization. The
pulse which rotates
M in this manner is called a 180º pulse.
The majority of spins are anti-aligned with the permanent magnetic field,
so, as the atoms thermally interact, the spins realign with permanent magnetic
field. The equation which describes the behavior of the magnetization over
time (with t = 0 when the magnetization is rotated) is M(t) = Mo(1 – 2e(-t/ T
1)). For more on the specific techniques used to calculate T
1 and factors which influence it, please go
here
Go
here
for research on the Spin-Lattice Relaxation of boron of SrB
6.
The spin-spin interaction is the
propensity of oppositely aligned spin pairs to simultaneously flip, which
disturbs the phase relationship between the two spins. This causes the magnetic
moments of the atoms to dephase much like the varying magnetic field. To
study T
2 involves the use of the spin-echo technique,
first pioneered by
Erwin Hahn
. The sample is pulsed with a 90º pulse, then a series of 180º
pulses a time τ separated from each other. The 90º pulse rotates the
magnetization to the perpendicular plane, where the magnetization begins
to dephase as discussed earlier (See Figure 3b). The effect of a 180º
pulse causes the magnetizations to rotate out of the plane, and then back
into it, essentially reflecting the magnetizations across an axis (See
Figure 3c & 3d). Since the magnetizations continue rotating at their
relative rates, they rephase momentarily before they begin to dephase again
(See Figure 3e & 3f). The 180º pulse can be repeated to get an accurate
picture of the decay of the magnetizations, thus sidestepping the issue of
dephasing due to magnetic field inhomogeniety. A Meiboom-Gill pulse sequence
introduces a π/2 phase shift between the 90º and 180º pulses, which
reduces the effect of the 180º pulse not being exactly the correct duration. T
2 is a scientifically interesting quantity because it may help
identify diseases and tumors within the lungs
. A more complex use of 90º and 180º pulses is the
nuclear Overhauser effect
, which involves the coupling of electron and nuclear magnetic moments to
magnify the nuclear moment.
NMR has various practical applications, the most visible of which
is magnetic resonance imaging (MRI). MRI is a technique used for imaging
sections of the human body by studying the different resonance frequencies
under a spatially varying magnetic field. The technique was first demonstrated
in organic tissue by
Paul C. Launterbur
in 1973, and the technique has progressed from a series of two-dimensional
pictures (right above
2) to also allow volumetric
imaging (right below
3). MRI is also being applied
to
non-
medical tasks
: radiation dosage in gels and flow measurements. For more on the techniques
and underlying physics of MRI, please visit
here
.
As you can see, NMR is
important scientific tool for understanding molecular structure and environment,
and holds promise for future practical applications. In the coming years,
NMR will hopefully expand it application outside the medical and scientific
fields to industry, and further enrich our lives.
1. Picture courtesy of Spektroscopy [sic] Online,
http://www.chem.uni-potsdam.de/tools/
2. Picture courtesy of Graphics and Visualization Center, http://www.gg.caltech.edu/sitevis/mri_research.html
3. Picture courtesy of Emory University Cardiac MRI, http://www.emory.edu/RADIOLOGY/MRI/FPMRRCb.html