1 Introduction to NMR

The chemist calls it NMR and the medical doctor MRI. Nuclear magnetic resonance
(NMR) is the most popular tool in chemistry to analyze molecular structures, and mag-
netic resonance imaging (MRI) is a non-invasive diagnostic tool in the hospital that
provides high-contrast images of tissues depicting the brain functions and the beat-
ing heart. In both cases large and expensive superconducting magnets are employed
(Fig. 1.0.1), which magnetize the object by aligning the atomic nuclei inside the mag-
net. The resulting magnetization can be triggered by radio frequency waves to rotate
around the direction of the magnetic field. Depending on the operating mode, the
frequency spectrum of the rotating nuclear magnetization provides the chemist with
molecular information and the medical doctor with anatomical images, while the ma-
terials scientist may be interested in the decay of the impulse response to learn about
physical properties of a solid object like a wet wall.

1.1 NMR: Nuclear Magnetic Resonance

NMR can be defined as a physical phenomenon which is utilized to investigate molec-

ular properties of matter by irradiating atomic nuclei in a magnetic field with electro-
magnetic radio waves. Many nuclear isotopes possess an angular momentum called
spin. In classical terms, spins appear to rotate around an axis like a bicycle wheel
(Fig. 1.1.2a). For atomic nuclei, however, the somewhat unusual laws of quantum me-
chanics apply. For example, every spin is associated with a magnetic moment like the

Figure 1.0.1. High-field NMR machines with superconducting magnets and compact, low-field ma-
chines with permanent magnets (insets). (a) Magnets for chemical analysis. (b) Magnets for mag-
netic resonance imaging (MRI). The patient or the object is positioned in the center of the magnet
hole. The bulky electronics of medical MRI machines are typically hidden in a separate room.

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2 | 1 Introduction to NMR

Figure 1.1.1. Schematic drawing of 49 out of 1023 proton spins which are aligned in a magnetic field.
(a) Each spin appears to rotate or ‘precess’ around the direction of the magnetic field in a manner
similar to a spinning bicycle wheel, which precesses around the direction of the gravitational field
(Fig. 1.1.2a). (b) The up and down states of the spins are more easily recognized when only the part
of the spin vector parallel to the direction of the magnetic field is drawn. Because each spin is a
magnet, each of these arrows represents a magnet. The nuclear magnetization M is the sum of the
magnetizations from each component magnet.

needle of a compass. Depending on the magnitude of the spin, it can align with a mag-
netic field in different stable orientations, which differ in their inclination angles with
respect to the magnetic field and therefore also differ in their energies (Fig. 1.1.1a). Pro-
tons, the most abundant nuclear spins in organic matter, align in two states, called up
(↑) and down (↓). The relative numbers n↑ and n↓ of spins for the two states with ener-
gies E↑ and E↓ follow the Boltzmann distribution, where kB is the Boltzmann constant
and T is the temperature in Kelvin,
n↓
= exp{−(E↓ − E↑ )/(kB T )}. (1.1.1)
n↑

The nuclear magnetization M of a macroscopic sample with some 1023 spins is formed
by the difference n↑ − n↓ of the number of spins with different orientations (Fig. 1.1.1b).
Because the resulting magnetization M is composed of an unimaginably large
number of quantum mechanical entities, it behaves like a classical magnet, which
spins around its magnetization axis. It interacts with a magnetic field B0 in the same
way as a gyroscope e.g., in the way a spinning bicycle wheel interacts with the grav-
itational field (Fig. 1.1.2a): When not aligned with the direction of the field, the mag-
netization axis rotates around the direction of the field (Fig. 1.1.2b). This rotation is
called precession. The precession frequency or Larmor frequency !0 is proportional to
the strength B0 of the applied field,

!0 = 2⁄ 0 = ıB0 (1.1.2)

where the gyromagnetic ratio ı is a constant specific to the type of atomic nucleus,
and 0 = (E↓ − E↑ )/h , where h is Planck’s constant. For example, the frequency 0 for

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 1.1 NMR: Nuclear Magnetic Resonance | 3

protons 1 H is 21.29 MHz in a magnetic field with B0 = 0. 5 T, which is a typical value

for compact permanent magnets of mobile NMR instruments.
When a sample is exposed to a magnetic field, it takes time for the spins to align
with the field and establish the nuclear magnetization along the field direction (cf.
Fig. 1.1.1). This time is characterized by the longitudinal relaxation time T1 . The resul-
tant magnetization can be tipped away from the direction of the magnetic field B0 by
a radio frequency (rf) magnetic field impulse (Fig. 1.1.2c). The impulse is applied to
the sample by means of a current pulse through an rf coil (Fig. 1.1.2b), which usually
is part of an rf resonance circuit. This coil produces an oscillating magnetic field B1
perpendicular to the static magnetic field B0 (Fig. 1.1.2b), and the magnetization also
rotates around this field with frequency !1 = ıB1 . The flip angle ˛ by which the mag-
netization is tipped away from the direction of the magnetic field B0 is adjusted by the
amplitude B1 of the rf field and the duration tp of the rf impulse according to

˛ = ıB1 tp . (1.1.3)

Figure 1.1.2. Precession and impulse response. (a) A bicycle wheel spins around its axis and pre-
cesses in the gravitational field. (b) The nuclear magnetization M follows the same motion in a mag-
netic field B0 . (c) A magnetic rf impulse with its frequency rf tuned to the precession frequency can
excite this precession of nuclear magnetization. The impulse response decays with the time constant
T2 in a homogeneous magnetic field B0 . (d) In an inhomogeneous field the impulse response decays
with the time constant T2∗ . Echoes can be generated by two and more excitation impulses. Ideally,
the echo amplitudes stroboscopically sample the envelope of the impulse decay from a homoge-
neous magnetic field.

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4 | 1 Introduction to NMR

With a single impulse for excitation, maximum signal is generated when the flip an-
gle is 90∘, so that the magnetization after the impulse is perpendicular to the B0 field
direction.
In conventional NMR and MRI the sample rests inside the coil, which is inside the
magnet; in single-sided NMR, the sample is placed outside in the stray field of the coil
and the magnet. Following the excitation impulse, the precessing magnetization in-
duces an oscillating voltage in the coil in the same way as a bicycle dynamo generates
electricity. The induced voltage decays with a time constant T2 when the magnetic field
is homogeneous (Fig. 1.1.2c). The decay results from destructive interference of dif-
ferent magnetization components in the sample, because fluctuating magnetic fields
caused by the motion of the molecules randomly change the precession frequencies of
the components so that fewer and fewer magnetization components are aligned in the
same direction as they precess, and the resulting magnetization amplitude decreases.
The impulse response contains all the information that can be measured. It pro-
vides oscillation frequencies, decay times, and amplitudes. The chemist evaluates the
oscillating part of the impulse response by Fourier transformation to analyze com-
ponents with small shifts of precession frequencies caused by weak magnetic fields
associated with the currents of the electrons orbiting in the chemical bonds of the
molecules. These shifts and the associated component amplitudes are the fingerprints
of chemical groups and their concentrations, i.e. of the molecular structure. The physi-
cist determines the decay time of the impulse response, the so-called relaxation time
T2 to study the physics of matter associated with the mobility of the molecules. In het-
erogeneous matter the impulse response is the sum of responses for each component.
When relaxation times differ for different components, the component amplitudes can
be determined from the distribution of relaxation times. The relative component am-
plitudes are proportional to concentrations.
In inhomogeneous fields the precession frequencies differ in each voxel of the
sample because the applied magnetic field differs from voxel to voxel. Then the
impulse response decays faster with a relaxation time T2∗ which is shorter than T2
(Fig. 1.1.2d). The fraction of the signal amplitude that is only affected by the static
inhomogeneity of the applied field and not by the fluctuating fields can be recovered
in a so-called spin echo after effectively reverting the sense of precession of the mag-
netization components by a second rf impulse. This fundamental phenomenon was
discovered by Erwin Hahn. In his honor the spin echo is also called the Hahn echo. The
echo-generating process can be repeated many times to generate a train of echoes.
The only signal loss is then due to T2 relaxation invoked by the ever present fluctuat-
ing fields so that the echo train envelope ideally corresponds to the signal decay in
a homogeneous magnetic field. Following the initials of the inventors Carr, Purcell,
Meiboom and Gill, a train of many Hahn echoes is also called a CPMG echo train.
The generation of echo trains is the fundamental principle followed when measuring
signals in the inhomogeneous fields of the permanent magnets frequently used for
portable stray-field NMR devices like the NMR-MOUSE.

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 1.2 Mobile NMR | 5

1.2 Mobile NMR

Today NMR with portable and compact machines is experiencing a period of rapid
growth. This process started when scientists learned how to measure NMR signals
with simple magnets and with inhomogeneous magnetic fields from objects outside
the magnet. A further push came when it was demonstrated that magnets with ex-
tremely homogeneous magnetic fields could be assembled from blocks of permanent
magnets that show large variations in their magnetic properties.
There are now portable NMR magnets for all three types of basic NMR measure-
ments. These are NMR relaxometry for analysis of material properties by relaxation
measurements, NMR imaging for measuring 2D and 3D images, and NMR spectroscopy
for chemical analysis (Fig. 1.2.1). While in high-field NMR, the object is always nearly
placed inside the magnet (Fig. 1.0.1), mobile low-field NMR also uses magnets that are
placed near the object so that the object is exposed to the stray field of the magnet.
Here the object can be arbitrarily large, because its size is not restricted by the magnet
bore, and the volume inside the object from which the signal is collected is well de-
fined. These two magnet geometries are often referred to as open and closed. In either
case, the demands on magnetic field homogeneity increase from relaxometry to imag-
ing to spectroscopy. Relaxation measurements can be performed by echo techniques
in arbitrarily shaped magnetic fields, images are best acquired in linearly varying mag-
netic fields with constant field gradients, and spectra are best acquired in extremely
homogeneous fields.

Figure 1.2.1. Compact magnets for mobile NMR. Left: Closed magnets that accommodate the sample
in their center. Right: Open magnets that are placed close to the object to measure NMR signals from
selected volume regions of the object. An early small stray-field NMR device of this kind is the NMR-
MOUSE® .

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6 | 1 Introduction to NMR

Figure 1.2.2. Mobile NMR magnets and spectrometers. (a) Halbach magnet for NMR spectroscopy.
(b) Profile NMR-MOUSE® on a computer-controlled lift for depth profiling.

The first, small device with an open design was named NMR-MOUSE for Nuclear
Magnetic Resonance MObile Universal Surface Explorer. It can be shifted around like
a computer mouse to scan large objects (Figs. 1.2.1, top right and 1.2.2b). The mag-
net of the NMR-MOUSE can be designed in different ways so that the field is either
parallel or perpendicular to the sensor surface. There are also different ways of build-
ing closed magnets from permanent magnet pieces. A particularly ingenious way is
due to Klaus Halbach and many closed NMR magnets follow the original Halbach
design (Fig. 1.2.2a). They possess maximal magnetic field strength inside and ideally
zero stray field outside. While the NMR-MOUSE is good for testing material properties
of large objects, closed magnets are suitable for analysis of substances transported
in tubes through their centers and for process control by imaging of objects passing
through the magnet.
The compact NMR magnets most important for practical applications are the
NMR-MOUSE for relaxometry and the Halbach magnet for imaging and spectroscopy.
Because the field strength of permanent magnets varies with temperature, many ap-
plications require temperature control. This is essential when measuring data with
high resolution, for example, depth profiles with the NMR-MOUSE and spectra with a
Halbach magnet.

1.2.1 Halbach magnets

Halbach discovered the principle of arranging a collection of magnet blocks in such

a way that the resulting magnetic-field distribution has the desired shape. One shape
is the homogeneous field, which is the most desirable field for any NMR measurement.
The magnet blocks are positioned on a circle forming a ring with the polarization of
each block aligned in the plane of the circle but rotated from block to block in such
a way that the orientation of the magnetization performs two rotations when passing
full circle around the ring (Fig. 1.2.3). Ideally, the field is uniform and maximal inside
the ring and zero outside. Several such rings can be stacked to form a cylinder mag-
net that accommodates the sample inside just like a conventional superconducting
magnet.

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 1.2 Mobile NMR | 7

Figure 1.2.3. Halbach magnets. (a) Section of a Halbach ring with trapezoidal and rectangular mag-
net pieces. The rectangular blocks in the gaps can be shifted to eliminate the field distortions result-
ing from magnet imperfections. (b) Depending on the displacements r of the rectangular magnet
blocks, different field correction terms can be generated.

The field inside a simple Halbach magnet is not sufficiently homogeneous to mea-
sure spectra or images but quite sufficient to measure NMR relaxation. The residual
field inhomogeneity originates from the use of a finite number of blocks in place of
polarization varying continuously within the ring, the statistics of the magnetic do-
mains within the magnet blocks, which are made from sintered granular material,
and the finite precision of their dimensions and magnetizations. A clever way to com-
pensate for this inhomogeneity is to shim the field by radially displacing rectangular
magnet blocks positioned in gaps between the trapezoidal magnet pieces (Fig. 1.2.3b).
Depending on the relative diameter of the hole, typical field strengths of such Halbach
magnets are 0.5 T to 2 T.

1.2.2 Magnets for stray-field NMR: The NMR-MOUSE

To measure a sample positioned in the stray field outside a magnet is a well-known

idea. The oil industry started to use it with well-logging sensors to measure the NMR
relaxation of fluids confined to the pores of the borehole wall. Early materials studies
employed this principle to measure moisture in soil, bridge decks, and other building
materials. Subsequently the stray field of superconducting spectroscopy and imaging
magnets was used to measure images and diffusion coefficients, because the high field
gradient of 50 T/m and more, together with the high field strength, promised superior
resolution and sensitivity. Similarly strong gradients of some 20 T/m at lower field
strengths can also be obtained with small permanent magnets. However, rather than
the gradient it was the simplicity of the device that led to the construction of the NMR-
MOUSE, a small stray-field NMR sensor, which turned out to be well suited to test all
kinds of hydrogen-containing materials such as rubber, polymers, wood, food, and
moisture in porous media.
The NMR-MOUSE is obtained from a classical C-shaped magnet that produces a
largely homogeneous magnetic field between its poles (Fig. 1.2.4a) by opening up the
C (Fig. 1.2.4b). A sample positioned near the surface experiences the stray field of this

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8 | 1 Introduction to NMR

Figure 1.2.4. Permanent magnet assemblies for stray-field NMR. (a) The NMR magnet used in the
early days of NMR produces a homogeneous magnetic field in a gap between two magnet poles.
(b) The NMR-MOUSE® is obtained from this design by opening it up. The stray fields of both the
magnet and the rf coil are inhomogeneous. (c) The most simple stray-field NMR magnet is just a bar
magnet. (d) With additional magnet blocks, the stray field can be shimmed locally in a sensitive vol-
ume to good enough homogeneity to resolve the small frequency differences in proton NMR spectra.

magnet and the stray field of the rf coil between the two magnet poles (Fig. 1.2.4b). The
sensitive volume of such a simple sensor is oddly shaped more like an upside-down
soup dish than a flat slice. A different shape for the sensitive volume is obtained with a
simple bar magnet (Fig. 1.2.4c). The best homogeneity of the magnetic field in a plane
above the rf coil is produced by the Profile NMR-MOUSE, which looks like two of the
u-shaped magnets in Fig. 1.2.4b placed side by side. In this case the magnetic field
varies within the sensitive volume only in the direction perpendicular to the sensor
surface. Signals could be measured in this way from slices as thin as 2.3 micrometers.
The ultra-high magnetic-field homogeneity required to measure NMR spectra is typi-
cally only obtained inside the magnet, but by shimming the magnetic field profile of
the u-shaped NMR-MOUSE with additional magnets, field homogeneity sufficient to
resolve the chemical shift of protons could be obtained (Fig. 1.3.4b).

1.3 Measuring methods

The measuring methods can be grouped into two types (Fig. 1.3.1). Those in one group
(Fig. 1.3.1a) require a homogeneous field to resolve the oscillations in the measured sig-
nal that result from the precession of the transverse magnetization generated by an rf
impulse. Those in the other group (Fig. 1.3.1b) only measure the signal decay from the
envelope of several echoes generated at different times in an inhomogeneous field. In
the following, the oscillating impulse response measured in a homogeneous or lin-
early and weakly space-dependent magnetic field is called the free induction decay or
FID. The train of echoes measured in an inhomogeneous field is called the CPMG echo
train because it is most often measured in a way that follows the pioneering work of
Carr, Purcell, Meiboom, and Gill.

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 1.3 Measuring methods | 9

Figure 1.3.1. NMR signals and processing. (a) Free induction decay acquired in a homogeneous mag-
netic field. Its Fourier transform is a distribution of frequencies known as the NMR spectrum, which
is used to derive molecular structures. When acquired in a linearly varying magnetic field, the NMR
spectrum is a projection of the object, i.e. a one-dimensional image. (b) Multi-echo envelope mea-
sured with the CPMG sequence. Its inverse Laplace transform is a distribution of relaxation times.

Either signal is further analyzed to extract information in terms of parameters or

distributions of parameters (Fig. 1.3.1). The FID is almost always converted into a distri-
bution of frequencies by Fourier transformation. This distribution is the NMR spectrum
when measured in a homogeneous magnetic field or a 1D projection image of an ob-
ject when measured in a linearly space-dependent field. The CPMG train is either fitted
with model functions like an exponential or a bi-exponential decay to extract ampli-
tudes and relaxation times, or it is converted into a distribution of relaxation times by
operations similar to an inverse Laplace transformation.
Both schemes can be expanded to acquire multi-dimensional data sets (Fig. 1.3.2).
The underlying idea is to start the data acquisition not with the nuclear magnetiza-
tion in the thermodynamic equilibrium established when the samples have been ex-
posed sufficiently long and undisturbed to the magnetic field, but rather in a non-
equilibrium state that is generated by manipulation of the initial magnetization prior
to acquisition. Such manipulations are achieved by further rf impulses and waiting
times. When carried out in a systematic manner, the evolution of the nuclear spin sys-
tem before acquisition is also oscillatory or follows some type of multi-exponential
curve. By measuring many FIDs or CPMG trains for systematically changing initial
conditions, multidimensional data sets are acquired that can be analyzed by multidi-
mensional Fourier and Laplace transformations and combinations thereof to obtain
multi-dimensional distributions of frequencies and relaxation times. Such multidimen-
sional parameter distributions reveal more detailed information about the system un-
der study than one-dimensional distributions.
A well-known two-dimensional distribution of signal amplitude versus frequency
is an NMR image. In magnetic fields with a constant gradient, i.e., in magnetic fields
that vary linearly in space, the NMR frequency in a particular voxel is proportional
to the position of the object. Other important examples are correlation and exchange

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10 | 1 Introduction to NMR

Figure 1.3.2. NMR data acquisition schemes. (a) One-dimensional NMR. Following a waiting time
during which the magnetization reaches thermodynamic equilibrium, an FID or a CPMG echo train
are acquired depending on the magnetic field homogeneity. (b) Two-dimensional NMR. The initial
state of the spin system is varied from acquisition to acquisition in a systematic fashion so that en-
coding parameters are changed in a systematic fashion. This introduces a second dimension to the
acquired data set, which can also be processed by Fourier or Laplace transformations. Which en-
coding parameter is varied depends on the particular setup of the rf impulses and gradient impulses
which is defined in the NMR experiment.

NMR spectra where cross peaks in the plane of a two-dimensional spectrum identify
interactions between magnetization components that precess with different frequen-
cies in the evolution and detection periods of the measurement scheme. Frequency
distributions or NMR spectra can have hundreds of discrete resonance lines in high-
resolution NMR spectroscopy, and two-dimensional Fourier NMR helps to identify the
structures and dynamics of the molecules investigated. On the other hand, relaxation
time distributions and distributions of diffusion coefficients may show only up to about
five different peaks, and two-dimensional Laplace NMR helps to identify the nature of
relaxation centers and the geometry of the pore spaces explored by fluid molecules.

1.3.1 Relaxometry

Relaxometry denotes the measurement of relaxation curves. Such measurements are

the least demanding on magnetic field homogeneity. Compared to spectroscopy, the
magnetic field can be highly inhomogeneous as in the case of the stray field of an ordi-
nary magnet and the fields inside an unshimmed Halbach magnet. In fact, the use of
well-logging NMR instruments and of the NMR-MOUSE relies mostly on measurements
of transverse and longitudinal relaxation curves. For example, water saturating the
pores of rock may produce the CPMG decay shown in Fig. 1.3.1b when measured with

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 1.3 Measuring methods | 11

Figure 1.3.3. Applications of NMR relaxometry. (a) 2D relaxation-exchange NMR of water saturated
soil with a simple Halbach magnet operated by a Bruker Minispec spectrometer enclosed in a pilot’s
carrying case. The 2D Laplace exchange map identifies different relaxation sites by peaks on the
diagonal. Cross peaks indicate spatial proximity of the sites that can be accessed by water molecules
diffusing between them during a mixing time of 10 ms. (b) Depth profiling with the Profile NMR-
MOUSE. By varying the distance between the sensor and the object, the sensitive slice is displaced
inside the object. The amplitude of the CPMG signal from the sensitive slice defines the amplitude in
proton-density profiles shown here through a mosaic at Herculaneum measured at different times
and different parts of the mosaic.

a simple Halbach magnet, which transforms into the distribution of relaxation times
shown along with it.
Such simple instrumentation can deliver detailed information on the pore space
when measuring 2D relaxation maps (Fig. 1.3.3a) of the fluid molecules moving inside
the porous matrix. For example, following the 2D scheme of Fig. 1.3.2, the distribution
of transverse relaxation times is measured twice in a relaxation exchange experiment,
once at an initial time and once at a final time separated by a time delay or mixing
time tm during which the magnetization is carried by the fluid molecules from one re-
laxation site to another. In many cases the fluid molecules are water molecules moving
by self-diffusion in the pores of soil or rock where the different relaxation sites mark
different positions in the complex pore space formed by compacted irregular grains.
From a computer simulation of the experimental exchange map, the exchange rates
can be extracted and from those the distances between the relaxation centers can be
calculated.
Much simpler 1D relaxation curves like CPMG trains (Fig. 1.3.1b) are routinely mea-
sured with the NMR-MOUSE. When using the Profile NMR-MOUSE, the sensitive volume
is a thin slice at a well-defined position which can be shifted through the object by
varying the distance between the sensor and the object (Fig. 1.3.3b). The amplitude of
the CPMG signal from the sensitive slice is proportional to the number of protons in

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12 | 1 Introduction to NMR

Figure 1.3.4. NMR imaging. (a) Different voxels are discriminated by means of their NMR frequen-
cies. Because the field varies linearly across the object, the NMR frequency is proportional to the
voxel position. The linear field variation is achieved with current-driven coils inside the magnet.
Amplitude and timing of the currents are determined by the particular sequence of commands to
the spectrometer hardware when acquiring the image data. (b) Stray-field NMR imaging of tire tread
with the NMR-MOUSE: Photo of a tread section, NMR image, and setup. (c) Kea NMR spectrometer
and 0.5 T Halbach imaging magnet. The field of the Halbach magnet is so homogeneous that the fine
structure of the resonances in the 1 H ethanol spectrum can be resolved within a sample volume of
1 cm3 . (d) NMR images through a mouse measured with the 0.5 T Halbach magnet.

the sensitive slice, which may correspond to the water or wax content in some porous
building material like a concrete wall or a Roman mosaic. The amplitude values as a
function of the sensor displacement define a 1D image of the proton content versus
depth into the object. Instead of the signal amplitude, the relaxation time or another
parameter of the measured signal can be plotted depending on how one wants to de-
fine the contrast.
To measure depth profiles by scanning the object voxel by voxel is a slow process.
This had already been observed in the early days of medical MRI. A much faster way is
to measure the impulse response in a magnetic field with a weak gradient, where the
positions of the voxels can be identified from their different NMR frequencies in the
direction in which the magnetic field strength changes, i.e., in the gradient direction
(Fig. 1.3.4a). For the NMR-MOUSE this is the direction away from the surface. Indeed,
the signal from a narrow distance range covering the depth of the sensitive slice can be
measured by a CPMG train without displacing the sensor. The depth profile across the
sensitive slice is then obtained in terms of the Fourier transform of an NMR echo. This

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 1.3 Measuring methods | 13

approach to imaging is basic to almost all imaging schemes in diagnostic medicine,

but the field gradients used there are much smaller than those produced by the NMR-
MOUSE, so that larger objects can be imaged albeit at lower resolution.

1.3.2 Imaging

Imaging requires magnetic field profiles to be better defined than for relaxometry. Ide-
ally the magnetic field varies linearly across the object and the direction of field vari-
ation should be adjustable during the measurement (Fig. 1.3.4a). The linear field vari-
ation corresponds to a constant spatial derivative or gradient. In practice these de-
mands are met by a magnet that consists of two parts. One part produces a homoge-
neous field across the extension of the object. This would be a superconducting mag-
net in clinical MRI (Fig. 1.0.1b) or a Halbach magnet (Fig. 1.2.1 left, middle) in compact
NMR. The switchable gradient field is produced in either case by currents through sets
of electrical coils inside the magnet or on top of the NMR-MOUSE. Depending on which
of the so-called gradient coils is powered up, the field gradient is applied in a different
direction but with the direction of the gradient field always aligned with that of the
homogeneous field.
Because the magnetic field strength B is proportional to the NMR frequency !
(eqn. (1.1.2)), each group of spins at different positions along the direction of the field
gradient experiences a different frequency, so that the frequency distribution or the
spectrum of the NMR signal measured in a magnetic field with constant gradient is
a 1D image of the magnetization distribution along the gradient direction. The art of
magnetic resonance imaging consists of orchestrating the sequence of radio frequency
impulses and current impulses through the gradient coils in such a way that the infor-
mation about the signal distribution inside the object is measured in the optimum way
with the best contrast. Typically this distribution or image is obtained by Fourier trans-
formation of the measured signal, because the Fourier transformation disentangles
the different frequency components of the impulse response. The contrast is achieved
by further manipulations in the measuring schemes that result in weighting the signal
from each voxel with functions of the relaxation times and diffusion coefficients of the
molecules in the object. There are numerous ways of doing this, and the wide range
of contrast values that can be accessed by NMR makes NMR imaging superior to any
other method of imaging when applied to soft matter like fluids, moisture in porous
materials, biological tissue, food, plants, rubber, and polymers.
Compact, single-sided MRI was first realized by an NMR-MOUSE fitted with gra-
dient coils to supply the gradient fields needed to measure Fourier images of slices
through objects parallel to the sensor surface (Fig. 1.3.4b). The strong field gradient
in the direction perpendicular to the scanner surface, however, results in a very thin
slice, so that measurement times are long. With today’s technology, the field gradi-
ent of the NMR-MOUSE could be lowered to boost the sensitivity by measuring signal

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14 | 1 Introduction to NMR

from thicker slices. Moreover, Halbach magnets can be built with outstanding homo-
geneity over extended volumes for imaging of objects a few centimeters in diameter
(Fig. 1.3.4c). Within seconds and up to a few minutes, 2D NMR images can be acquired
from various soft-matter objects such as a mouse (Fig. 1.3.4d) but also rheological
properties of fluids passing through the magnet can be studied with it by flow imaging.

1.3.3 Spectroscopy

NMR spectroscopy requires extreme homogeneity of the magnetic field across the sam-
ple, because the differences in NMR frequency for protons that are usually caused by
differences in chemical structure are in the range of one part per million and less. It is
far less difficult to achieve this level of homogeneity within small volumes inside big
magnets. But as the homogeneous volume increases and the magnet size decreases,
such field homogeneity is more and more difficult to obtain. In this respect, the homo-
geneity of the Halbach magnet in Fig. 1.3.4c is already outstanding, because typical
sample diameters are less than 5 mm in high-resolution NMR spectroscopy, while the
high-resolution spectrum shown in Fig. 1.3.4c is from a 10 mm diameter sample. The
worst-case scenario is to measure a 1 H NMR spectrum in the stray field outside the
magnet. While for a long time this was believed to be an impossible task, an NMR-
MOUSE could nevertheless be shimmed well enough by placing additional magnets
in the gap (Fig. 1.2.4d) so that the field becomes sufficiently homogeneous in a finite
volume region outside the magnet assembly to measure 1 H NMR spectra that resolve
the chemical shift (Fig. 1.3.5). It should be noted that this is a proof-of-principle demon-
stration only. Before this technology can be used in routine applications, the drift of
the magnetic field from temperature fluctuations has to be eliminated.

Figure 1.3.5. Stray-field NMR spectroscopy. The stray field of the NMR-MOUSE can be shimmed in the
sensitive volume to such extreme homogeneity that the chemical shift can be resolved to measure
1
H NMR spectra. (a) For measurement, a flask with the solution to be measured is positioned on
top of the magnet so that the sensitive volume resides inside the flask. (b) NMR spectrum of toluene
measured in this way with a single excitation impulse.

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 1.4 Hardware | 15

1.4 Hardware

Essentially an NMR instrument is a device that enables two-way radio communication

between the operator and the atomic nuclei in a magnetic field (Fig. 1.4.1). It consists
of a console, which is connected to the probe that communicates with the sample and
is positioned in a magnetic field. The console is operated by a computer, which times
all events of the measurement and is often also used for data processing. A transmit-
ter TX sends the excitation impulses, a receiver RX detects the NMR signal, and the
computer inside the console controls the currents that power the gradient field coils
in imaging experiments. The magnet and the probe usually form an entity separate
from the console. This entity is either an NMR-MOUSE, which consists of a stray-field
magnet and an rf resonant circuit, or it is a Halbach magnet or another magnet which
encloses the probe with the rf coil containing the sample.
The probe is shared between the transmitter and the receiver and connected on de-
mand to one or the other by a transmit/receive switch, which is also called a duplexer.
The probe can typically be exchanged to fit different types of samples. Its resonant
circuit needs to be tuned to the NMR frequency of the sample and matched to 50 ˝
impedance. From time to time this tuning and matching may need to be checked and
adjusted for optimum performance of the instrument.

Figure 1.4.1. The three main components of an NMR machine are the computer, the console, and the
magnet with the probe. When setting up the NMR equipment, these three components often need to
be physically and electrically connected and the proper communication between them established.
The magnet produces the constant magnetic field B0 to which the sample is exposed in close prox-
imity to the probe. The main component of the probe is an rf resonant circuit which produces the
magnetic rf field B1 of the excitation impulses and receives the NMR signal. The console contains a
transmitter TX, a receiver RX, and a gradient modulator. The transmitter is connected to the rf res-
onant circuit only when the rf impulse is sent. Otherwise the receiver is connected to the resonant
circuit for detection of the NMR signal. A current modulator is needed to turn gradient fields on and
off. TX, RX and the gradient modulator are timed by a computer, which often also processes the
data, for example, by executing the Fourier and Laplace transformations.

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16 | 1 Introduction to NMR

In the receiver, the voltage induced in the coil by the precessing nuclear mag-
netization is amplified and converted from the radio frequency regime to the audio
frequency regime in the same way a radio converts the radio waves received via the
antenna to audio signals. In NMR rotating waves are processed which, when written
in complex notation, consist of a real and an imaginary part. Essentially each part
passes through one receiver channel. The signal from both channels is referred to as
the quadrature signal. The quadrature audio signal is digitized in an analog-to-digital
converter, stored in the computer, and further processed, for example, by Fourier and
Laplace transformation.
Often a gradient controller is also part of the spectrometer. It produces time-
dependent currents to drive gradient coils located near the rf coil that generate addi-
tional magnetic fields in the sensitive volume of the object parallel to the main mag-
netic field and with well-defined gradients. Such gradient fields are used to encode
the positions of magnetization components within the sensitive volume in imaging
experiments and to destroy unwanted transverse magnetization by spoiling the ho-
mogeneity of the magnetic field. In the latter case the gradients are called homospoil
gradients or crusher gradients. While the magnet and the spectrometer are specific to
the demands of NMR, the computer can typically be a general one, which is capable
of running the NMR software package that comes along with the NMR spectrometer.

1.5 Summary

– Compact NMR employs small permanent NMR magnets with open and closed ge-
ometry
– Nuclear spins precess in a magnetic field
– The precession frequency is proportional to the strength of the magnetic field
– The sensitivity of NMR is low according to the Boltzmann distribution
– A single impulse suffices to measure NMR signals in homogeneous fields
– Spin echoes are used to measure NMR signals in inhomogeneous fields
– The NMR signal provides amplitudes, frequencies and relaxation times of signal
components
– Longitudinal and transverse relaxation times are determined by molecular mobil-
ity
– Distributions of relaxation times can be measured with simple magnets
– NMR imaging requires linear magnetic field profiles
– NMR spectroscopy needs homogeneous magnetic fields
– Depth profiles of different NMR parameters can be measured with open magnets

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 1.6 Further reading | 17

1.6 Further reading

Casanova F, Perlo P, Blümich B, editors. Single-Sided NMR. Berlin: Springer; 2011.

Soltner H, Blümler P. Dipolar Halbach magnet stacks made from identically shaped
permanent magnets for magnetic resonance. Conc Magn Reson 2010; 36A:211–222.

Kose GK, Haishi T, Handa S. Applications of Permanent-Magnet Compact NMR Sys-

tems. In: Codd S, Seymour JD, editors. Magnetic Resonance Microscopy. Weinheim:
Wiley-VCH; 2009, pp. 365–380.

Blümich B, Casanova F, Perlo J. Mobile single-sided NMR. Prog Nucl Magn Reson
Spectr 2008; 52: 197–26.

Mitchell J, Blümler P, McDonald PJ. Spatially resolved nuclear magnetic resonance

studies of planar samples. Prog Nucl Magn Reson Spectr 2006; 48: 161–181.

Stapf S, Han SI, editors. NMR Imaging in Chemical Engineering. Weinheim: Wiley-
VCH; 2006.

Blümich B. Essential NMR. Berlin: Springer; 2005.

Freeman R. Magnetic Resonance in Chemistry and Medicine. Oxford: Oxford Univer-

sity Press; 2003.

Fukushima E, Roeder SBW. Experimental Pulse NMR: A Nuts and Bolts Approach.
Reading: Addison Wesley; 1981.

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