The Basics of NMR

Chapter 1 INTRODUCTION
NMR Spectroscopy Units Review

NMR
Nuclear magnetic resonance, or NMR as it is abbreviated by scientists, is a phenomenon which occurs when the nuclei of certain atoms are immersed in a static magnetic field and exposed to a second oscillating magnetic field. Some nuclei experience this phenomenon, and others do not, dependent upon whether they possess a property called spin. You will learn about spin and about the role of the magnetic fields in Chapter 2, but first let's review where the nucleus is. Most of the matter you can examine with NMR is composed of molecules. Molecules are composed of atoms. Here are a few water molecules. Each water molecule has one oxygen and two hydrogen atoms. If we zoom into one of the hydrogens past the electron cloud we see a nucleus composed of a single proton. The proton possesses a property called spin which: 1. can be thought of as a small magnetic field, and 2. will cause the nucleus to produce an NMR signal. Not all nuclei possess the property called spin. A list of these nuclei will be presented in Chapter 3 on spin physics.

Spectroscopy
Spectroscopy is the study of the interaction of electromagnetic radiation with matter. Nuclear magnetic resonance spectroscopy is the use of the NMR phenomenon to study physical, chemical, and biological properties of matter. As a consequence, NMR spectroscopy finds applications in several areas of science. NMR spectroscopy is routinely used by chemists to study chemical structure using simple one-dimensional techniques. Two-dimensional techniques are used to determine the structure of more complicated molecules. These techniques are replacing x-ray crystallography for the determination of protein structure. Time domain NMR spectroscopic techniques are used to probe molecular dynamics in solutions. Solid state NMR spectroscopy is used to determine the molecular

structure of solids. Other scientists have developed NMR methods of measuring diffusion coefficients. The versatility of NMR makes it pervasive in the sciences. Scientists and students are discovering that knowledge of the science and technology of NMR is essential for applying, as well as developing, new applications for it. Unfortunately many of the dynamic concepts of NMR spectroscopy are difficult for the novice to understand when static diagrams in hard copy texts are used. The chapters in this hypertext book on NMR are designed in such a way to incorporate both static and dynamic figures with hypertext. This book presents a comprehensive picture of the basic principles necessary to begin using NMR spectroscopy, and it will provide you with an understanding of the principles of NMR from the microscopic, macroscopic, and system perspectives.

Units Review
Before you can begin learning about NMR spectroscopy, you must be versed in the language of NMR. NMR scientists use a set of units when describing temperature, energy, frequency, etc. Please review these units before advancing to subsequent chapters in this text. Units of time are seconds (s). Angles are reported in degrees (o) and in radians (rad). There are 2 radians in 360o. The absolute temperature scale in Kelvin (K) is used in NMR. The Kelvin temperature scale is equal to the Celsius scale reading plus 273.15. 0 K is characterized by the absence of molecular motion. There are no degrees in the Kelvin temperature unit. Magnetic field strength (B) is measured in Tesla (T). Rochester, New York is approximately 5x10-5 T. The earth's magnetic field in

The unit of energy (E) is the Joule (J). In NMR one often depicts the relative energy of a particle using an energy level diagram. The frequency of electromagnetic radiation may be reported in cycles per second or radians per second. Frequency in cycles per second (Hz) have units of inverse seconds (s -1) and are given the symbols or f. Frequencies represented in radians per second (rad/s) are given the symbol . Radians tend to be used more to describe periodic circular motions. The conversion between Hz and rad/s is easy to remember. There are 2 radians in a circle or cycle, therefore 2 rad/s = 1 Hz = 1 s-1. Power is the energy consumed per time and has units of Watts (W).

Finally, it is common in science to use prefixes before units to indicate a power of ten. For example, 0.005 seconds can be written as 5x10-3 s or as 5 ms. The m implies 10-3. The animation window contains a table of prefixes for powers of ten. In the next chapter you will be introduced to the mathematical beckground necessary to begin your study of NMR.

The Basics of NMR

Chapter 2 THE MATHEMATICS OF NMR
Exponential Functions Trigonometric Functions Differentials and Integrals Vectors Matrices Coordinate Transformations Convolutions Imaginary Numbers The Fourier Transform

Exponential Functions
The number 2.71828183 occurs so often in calculations that it is given the symbol e. When e is raised to the power x, it is often written exp(x). ex = exp(x) = 2.71828183x Logarithms based on powers of e are called natural logarithms. If x = ey then ln(x) = y, Many of the dynamic NMR processes are exponential in nature. For example, signals decay exponentially as a function of time. It is therefore essential to understand the nature of exponential curves. Three common exponential functions are

y = e-x/t y = (1 - e-x/t) y = (1 - 2e-x/t) where t is a constant.

Trigonometric Functions
The basic trigonometric functions sine and cosine describe sinusoidal functions which are 90o out of phase. The trigonometric identities are used in geometric calculations. Sin( ) = Opposite / Hypotenuse Cos( ) = Adjacent / Hypotenuse Tan( ) = Opposite / Adjacent The function sin(x) / x occurs often and is called sinc(x).

Differentials and Integrals

A differential can be thought of as the slope of a function at any point. For the function

the differential of y with respect to x is

An integral is the area under a function between the limits of the integral.

An integral can also be considered a sumation; in fact most integration is performed by computers by adding up values of the function between the integral limits.

Vectors
A vector is a quantity having both a magnitude and a direction. The magnetization from nuclear spins is represented as a vector emanating from the origin of the coordinate system. Here it is along the +Z axis.

In this picture the vector is in the XY plane between the +X and +Y axes. The vector has X and Y components and a magnitude equal to ( X2 + Y2 )1/2

Matrices
A matrix is a set of numbers arranged in a rectangular array. This matrix has 3 rows and 4 columns and is said to be a 3 by 4 matrix. To multiply matrices the number of columns in the first must equal the number of rows in the second. Click sequentially on the next start buttons to see the individual steps associated with the multiplication.

Coordinate Transformations
A coordinate transformation is used to convert the coordinates of a vector in one coordinate system (XY) to that in another coordinate system (X"Y").

Convolution
The convolution of two functions is the overlap of the two functions as one function is passed over the second. The convolution symbol is . The convolution of h(t) and g(t) is defined mathematically as The above equation is depicted for rectangular shaped h(t) and g(t) functions in this animation.

Imaginary Numbers
Imaginary numbers are those which result from calculations involving the square root of -1. Imaginary numbers are symbolized by i. A complex number is one which has a real (RE) and an imaginary (IM) part. The real and imaginary parts of a complex number are orthogonal. Two useful relations between complex numbers and exponentials are e+ix = cos(x) +isin(x) and e-ix = cos(x) -isin(x).

Fourier Transforms

The Fourier transform (FT) is a mathematical technique for converting time domain data to frequency domain data, and vice versa. The Fourier transform will be explained in detail in Chapter 5.

The Basics of NMR

Chapter 3 SPIN PHYSICS
Spin Properties of Spin Nuclei with Spin Energy Levels Transitions Energy Level Diagrams Continuous Wave NMR Experiment Boltzmann Statistics Spin Packets T1 Processes Precession T2 Processes Rotating Frame of Reference Pulsed Magnetic Fields Spin Relaxation Spin Exchange Bloch Equations

Spin
What is spin? Spin is a fundamental property of nature like electrical charge or mass. Spin comes in multiples of 1/2 and can be + or -. Protons, electrons, and neutrons possess spin. Individual unpaired electrons, protons, and neutrons each possesses a spin of 1/2. In the deuterium atom ( 2H ), with one unpaired electron, one unpaired proton, and one unpaired neutron, the total electronic spin = 1/2 and the total nuclear spin = 1.

Two or more particles with spins having opposite signs can pair up to eliminate the observable manifestations of spin. An example is helium. In nuclear magnetic resonance, it is unpaired nuclear spins that are of importance.

Properties of Spin
When placed in a magnetic field of strength B, a particle with a net spin can absorb a photon, of frequency . The frequency depends on the gyromagnetic ratio, of the particle. = B For hydrogen, = 42.58 MHz / T.

Nuclei with Spin

The shell model for the nucleus tells us that nucleons, just like electrons, fill orbitals. When the number of protons or neutrons equals 2, 8, 20, 28, 50, 82, and 126, orbitals are filled. Because nucleons have spin, just like electrons do, their spin can pair up when the orbitals are being filled and cancel out. Almost every element in the periodic table has an isotope with a non zero nuclear spin. NMR can only be performed on isotopes whose natural abundance is high enough to be detected. Some of the nuclei routinely used in NMR are listed below. U Nuclei n p a i r e d N e u t r o n s N e t S p i

n ( M H z / T )
Peak Ratios 42.58 2H 1 1 1 6.54 31P 1 0 1/2 17.25 23Na 1 2 3/2 11.27 14N 1 1 1 3.08 13C 0 1 1/2 10.71 19F 1 0 1/2 40.08 Energy Levels 1

Unpaired Protons To understand how particles with spin behave in a magnetic field, consider a proton. This proton has the property called spin. Think of the spin of this proton as a magnetic moment vector, causing the proton to behave like a tiny magnet with a north and south pole. When the proton is placed in an external magnetic field, the spin vector of the particle aligns itself

with the external field, just like a magnet would. There is a low energy configuration or state where the poles are aligned N-S-NS and a high energy state NN-S-S.

Transitions
This particle can undergo a transition between the two energy states by the absorption of a photon. A particle in the lower energy state absorbs a photon and ends up in the upper energy state. The energy of this photon must exactly match the energy difference between the two states. The energy, E, of a photon is related to its frequency, , by Planck's constant (h = 6.626x10-34 J s).

E=h In NMR and MRI, the quantity is called the resonance frequency and the Larmor frequency.

Energy Level Diagra ms

The energy of the two spin states can be represented by an energy level diagram. We have seen that = B and E = h , therefore the energy of the photon needed to cause a transition between the two spin states is E=h B When the energy of the photon matches the energy difference between the two spin states an absorption of energy

occurs. In the NMR experiment, the frequency of the photon is in the radio frequency (RF) range. In NMR spectroscopy, is between 60 and 800 MHz for hydrogen nuclei. In clinical MRI, is typically between 15 and 80 MHz for hydrogen imaging.

CW

NMR Experi ment

The simplest NMR experiment is the continuous wave (CW) experiment. There are two ways of performing this experiment. In the first, a constant frequency, which is continuously on, probes the energy levels while the

magnetic field is varied. The energy of this frequency is represented by the blue line in the energy level diagram. The CW experiment can also be performed with a constant magnetic field and a frequency which is varied. The magnitude of the constant magnetic field is represented by the position of the vertical blue line in the energy level diagram.

Boltzmann Statist ics

When a group of spins is placed in a magnetic field, each spin aligns in one of the two possible orientations. At room temperature, the number of

spins in the lower energy level, N+, slightly outnumbers the number in the upper level, N-. Boltzmann statistics tells us that N-/N+ = e-E/kT. E is the energy difference between the spin states; k is Boltzmann's constant, 1.3805x10-23 J/Kelvin; and T is the temperature in Kelvin. As the temperature decreases, so does the ratio N- /N+. As the temperature increases, the ratio approaches one. The signal in NMR spectroscopy results from the difference between the energy absorbed by

the spins which make a transition from the lower energy state to the higher energy state, and the energy emitted by the spins which simultaneously make a transition from the higher energy state to the lower energy state. The signal is thus proportional to the population difference between the states. NMR is a rather sensitive spectroscopy since it is capable of detecting these very small population differences. It is the resonance, or exchange of energy at a specific frequency between the spins and the spectrometer, which gives NMR its

sensitivity.

Spin Packets
It is cumbersome to describe NMR on a microscopic scale. A macroscopic picture is more convenient. The first step in developing the macroscopic picture is to define the spin packet. A spin packet is a group of spins experiencing the same magnetic field strength. In this example, the spins within each grid section represent a spin packet. At any instant in time, the magnetic field due to the spins in each spin packet can be represented by a magnetization vector.

The size of each vector is proportional to (N+ - N-). The vector sum of the magnetization vectors from all of the spin packets is the net magnetization. In order to describe pulsed NMR is necessary from here on to talk in terms of the net magnetization. Adapting the conventional NMR coordinate system, the external magnetic field and the net magnetization vector at equilibrium are both along the Z axis.

T1 Processes
At equilibrium, the net magnetization vector lies along the direction of the

applied magnetic field Bo and is called the equilibrium magnetization Mo. In this configuration, the Z component of magnetization MZ equals Mo. MZ is referred to as the longitudinal magnetization. There is no transverse (MX or MY) magnetization here. It is possible to change the net magnetization by exposing the nuclear spin system to energy of a frequency equal to the energy difference between the spin states. If enough energy is put into the system, it is possible to saturate the spin system and make MZ=0. The time constant which

describes how MZ returns to its equilibrium value is called the spin lattice relaxation time (T1). The equation governing this behavior as a function of the time t after its displacement is: Mz = Mo ( 1 - et/T1 ) T1 is therefore defined as the time required to change the Z component of magnetization by a factor of e. If the net magnetization is placed along the -Z axis, it will gradually return to its equilibrium position along the +Z axis at a rate governed by T1. The equation governing this behavior as a function of the time t after its

displacement is: Mz = Mo ( 1 2e-t/T1 ) The spinlattice relaxation time (T1) is the time to reduce the difference between the longitudinal magnetization (MZ) and its equilibrium value by a factor of e.

Precession
If the net magnetization is placed in the XY plane it will rotate about the Z axis at a frequency equal to the frequency of the photon which would cause a transition between the two energy levels of the spin. This frequency is called the Larmor frequency.

T2 Processes
In addition to the rotation, the net magnetization starts to dephase because each of the spin packets making it up is experiencing a slightly different magnetic field and rotates at its own Larmor frequency. The longer the elapsed time, the greater the phase difference. Here the net magnetization vector is initially along +Y. For this and all dephasing examples think of this vector as the overlap of several thinner vectors from the individual spin packets. The time constant which describes the return to

equilibrium of the transverse magnetization, MXY, is called the spin-spin relaxation time, T2. MXY =MXYo e-t/T2 T2 is always less than or equal to T1. The net magnetization in the XY plane goes to zero and then the longitudinal magnetization grows in until we have Mo along Z. Any transverse magnetization behaves the same way. The transverse component rotates about the direction of applied magnetization and dephases. T1 governs the rate of recovery of the longitudinal magnetization. In summary, the spin-spin relaxation

time, T2, is the time to reduce the transverse magnetization by a factor of e. In the previous sequence, T2 and T1 processes are shown separately for clarity. That is, the magnetization vectors are shown filling the XY plane completely before growing back up along the Z axis. Actually, both processes occur simultaneously with the only restriction being that T2 is less than or equal to T1. Two factors contribute to the decay of transverse magnetization. 1) molecular interactions (said to lead to a pure pure T2 molecular effect) 2) variations in Bo (said to lead

to an inhomogeneou s T2 effect The combination of these two factors is what actually results in the decay of transverse magnetization. The combined time constant is called T2 star and is given the symbol T2*. The relationship between the T2 from molecular processes and that from inhomogeneitie s in the magnetic field is as follows. 1/T2* = 1/T2 + 1/T2inhomo.

Rotating Frame of Refere nce

We have just looked at the behavior of spins in the laboratory frame of reference. It is

convenient to define a rotating frame of reference which rotates about the Z axis at the Larmor frequency. We distinguish this rotating coordinate system from the laboratory system by primes on the X and Y axes, X'Y'. A magnetization vector rotating at the Larmor frequency in the laboratory frame appears stationary in a frame of reference rotating about the Z axis. In the rotating frame, relaxation of MZ magnetization to its equilibrium value looks the same as it did in the laboratory frame. A transverse magnetization

vector rotating about the Z axis at the same velocity as the rotating frame will appear stationary in the rotating frame. A magnetization vector traveling faster than the rotating frame rotates clockwise about the Z axis. A magnetization vector traveling slower than the rotating frame rotates counterclockwise about the Z axis . In a sample there are spin packets traveling faster and slower than the rotating frame. As a consequence, when the mean frequency of the sample is equal to the rotating frame, the dephasing

of MX'Y' looks like this.

Pulsed Magne tic Fields

A coil of wire placed around the X axis will provide a magnetic field along the X axis when a direct current is passed through the coil. An alternating current will produce a magnetic field which alternates in direction. In a frame of reference rotating about the Z axis at a frequency equal to that of the alternating current, the magnetic field along the X' axis will be constant, just as in the direct current case in the laboratory frame.

This is the same as moving the coil about the rotating frame coordinate system at the Larmor Frequency. In magnetic resonance, the magnetic field created by the coil passing an alternating current at the Larmor frequency is called the B1 magnetic field. When the alternating current through the coil is turned on and off, it creates a pulsed B1 magnetic field along the X' axis. The spins respond to this pulse in such a way as to cause the net magnetization vector to rotate about the direction of the applied B1 field. The rotation angle depends on the

length of time the field is on, , and its magnitude B1. = 2 B1. In our examples, will be assumed to be much smaller than T1 and T2. A 90o pulse is one which rotates the magnetization vector clockwise by 90 degrees about the X' axis. A 90o pulse rotates the equilibrium magnetization down to the Y' axis. In the laboratory frame the equilibrium magnetization spirals down around the Z axis to the XY plane. You can see why the rotating frame of reference is helpful in describing the behavior of magnetization

in response to a pulsed magnetic field. A 180o pulse will rotate the magnetization vector by 180 degrees. A 180o pulse rotates the equilibrium magnetization down to along the -Z axis. The net magnetization at any orientation will behave according to the rotation equation. For example, a net magnetization vector along the Y' axis will end up along the -Y' axis when acted upon by a 180o pulse of B1 along the X' axis. A net magnetization vector between X' and Y' will end up between X' and Y' after the application of a 180o pulse

of B1 applied along the X' axis. A rotation matrix (described as a coordinate transformation in #2.6 Chapter 2) can also be used to predict the result of a rotation. Here is the rotation angle about the X' axis, [X', Y', Z] is the initial location of the vector, and [X", Y", Z"] the location of the vector after the rotation.

Spin Relaxa tion

Motions in solution which result in time varying magnetic fields cause spin relaxation. Time varying fields at the Larmor

frequency cause transitions between the spin states and hence a change in MZ. This screen depicts the field at the green hydrogen on the water molecule as it rotates about the external field Bo and a magnetic field from the blue hydrogen. Note that the field experienced at the green hydrogen is sinusoidal. There is a distribution of rotation frequencies in a sample of molecules. Only frequencies at the Larmor frequency affect T1. Since the Larmor frequency is proportional to Bo, T1 will therefore vary as a function of magnetic field strength.

In general, T1 is inversely proportional to the density of molecular motions at the Larmor frequency. The rotation frequency distribution depends on the temperature and viscosity of the solution. Therefore T1 will vary as a function of temperature. At the Larmor frequency indicated by o, T1 (280 K ) < T1 (340 K). The temperature of the human body does not vary by enough to cause a significant influence on T1. The viscosity does however vary significantly from tissue to tissue and influences T1 as is seen in the following molecular

motion plot. Fluctuating fields which perturb the energy levels of the spin states cause the transverse magnetization to dephase. This can be seen by examining the plot of Bo experienced by the red hydrogens on the following water molecule. The number of molecular motions less than and equal to the Larmor frequency is inversely proportional to T2. In general, relaxation times get longer as Bo increases because there are fewer relaxationcausing frequency components present in the random motions of the

molecules.

Spin Excha nge

Spin exchange is the exchange of spin state between two spins. For example, if we have two spins, A and B, and A is spin up and B is spin down, spin exchange between A and B can be represented with the following equation. A( ) + B( ) A( ) + B( ) The bidirectional arrow indicates that the exchange reaction is reversible. The energy difference between the upper and lower energy states of A and of B must be the same for spin exchange to occur. On a

microscopic scale, the spin in the upper energy state (B) is emitting a photon which is being absorbed by the spin in the lower energy state (A). Therefore, B ends up in the lower energy state and A in the upper state. Spin exchange will not affect T1 but will affect T2. T1 is not effected because the distribution of spins between the upper and lower states is not changed. T2 will be affected because phase coherence of the transverse magnetization is lost during exchange. Another form of exchange is called chemical exchange. In chemical exchange, the

A and B nuclei are from different molecules. Consider the chemical exchange between water and ethanol. CH3CH2OHA + HOHB CH3CH2OHB + HOHA Here the B hydrogen of water ends up on ethanol, and the A hydrogen on ethanol ends up on water in the forward reaction. There are four senarios for the nuclear spin, represented by the four equations. Chemical exchange will affect both T1 and T2. T1 is now affected because energy is transferred from one nucleus to another. For example, if there are more

nuclei in the upper state of A, and a normal Boltzmann distribution in B, exchange will force the excess energy from A into B. The effect will make T1 appear smaller. T2 is effected because phase coherence of the transverse magnetization is not preserved during chemical exchange.

Bloch Equati ons

The Bloch equations are a set of coupled differential equations which can be used to describe the behavior of a magnetizatiion vector under any conditions. When properly integrated, the Bloch

equations will yield the X', Y', and Z components of magnetization as a function of time.

The Basic s of NM R
Chapter 4 NMR SPEC TRO SCO PY
Chemical Shift Spin-Spin Coupl ing The Time Doma in NMR Signal The +/Frequ

ency Conve ntion

Chemical Shift
When an atom is placed in a magnetic field, its electrons circulate about the direction of the applied magnetic field. This circulation causes a small magnetic field at the nucleus which opposes the externally applied field. The magnetic field at the nucleus (the effective field) is therefore generally less than the applied field by a fraction . B = Bo (1-) In some cases, such as the benzene molecule, the circulation of the electrons in the aromatic orbitals

creates a magnetic field at the hydrogen nuclei which enhances the Bo field. This phenomenon is called deshielding. In this example, the Bo field is applied perpendicular to the plane of the molecule. The ring current is traveling clockwise if you look down at the plane. The electron density around each nucleus in a molecule varies according to the types of nuclei and bonds in the molecule. The opposing field and therefore the effective field at each nucleus will vary. This is called the chemical shift phenomenon. Consider the

methanol molecule. The resonance frequency of two types of nuclei in this example differ. This difference will depend on the strength of the magnetic field, Bo, used to perform the NMR spectroscopy. The greater the value of Bo, the greater the frequency difference. This relationship could make it difficult to compare NMR spectra taken on spectrometers operating at different field strengths. The term chemical shift was developed to avoid this problem. The chemical shift of a nucleus is the difference between the resonance frequency of the nucleus

and a standard, relative to the standard. This quantity is reported in ppm and given the symbol delta, . = ( - REF) x106 / REF In NMR spectroscopy, this standard is often tetramethylsila ne, Si(CH3)4, abbreviated TMS. The chemical shift is a very precise metric of the chemical environment around a nucleus. For example, the hydrogen chemical shift of a CH2 hydrogen next to a Cl will be different than that of a CH3 next to the same Cl. It is therefore difficult to give a detailed list of chemical shifts in a limited space. The animation

window displays a chart of selected hydrogen chemical shifts of pure liquids and some gasses. The magnitude of the screening depends on the atom. For example, carbon-13 chemical shifts are much greater than hydrogen-1 chemical shifts. The following tables present a few selected chemical shifts of fluorine-19 containing compounds, carbon-13 containing compounds, nitrogen-14 containing compounds, and phosphorous31 containing compounds. These shifts are all relative to the bare nucleus. The reader is

directed to a more comprehensive list of chemical shifts for use in spectral interpretation.

Spin-Spin Coupli ng
Nuclei experiencing the same chemical environment or chemical shift are called equivalent. Those nuclei experiencing different environment or having different chemical shifts are nonequivalent. Nuclei which are close to one another exert an influence on each other's effective magnetic field. This effect shows up in the NMR spectrum when the nuclei are nonequivalent. If the distance

between nonequivalent nuclei is less than or equal to three bond lengths, this effect is observable. This effect is called spinspin coupling or J coupling. Consider the following example. There are two nuclei, A and B, three bonds away from one another in a molecule. The spin of each nucleus can be either aligned with the external field such that the fields are N-SN-S, called spin up , or opposed to the external field such that the fields are N-NS-S, called spin down . The magnetic field at nucleus A will be either greater than Bo or less than Bo by a constant amount due to the influence

of nucleus B. There are a total of four possible configurations for the two nuclei in a magnetic field. Arranging these configurations in order of increasing energy gives the following arrangement. The vertical lines in this diagram represent the allowed transitions between energy levels. In NMR, an allowed transition is one where the spin of one nucleus changes from spin up to spin down , or spin down to spin up . Absorptions of energy where two or more nuclei change spin at the same time are not allowed. There are two absorption

frequencies for the A nucleus and two for the B nucleus represented by the vertical lines between the energy levels in this diagram. The NMR spectrum for nuclei A and B reflects the splittings observed in the energy level diagram. The A absorption line is split into 2 absorption lines centered on A, and the B absorption line is split into 2 lines centered on B. The distance between two split absorption lines is called the J coupling constant or the spin-spin splitting constant and is a measure of the magnetic interaction between two nuclei. For the next

example, consider a molecule with three spin 1/2 nuclei, one type A and two type B. The type B nuclei are both three bonds away from the type A nucleus. The magnetic field at the A nucleus has three possible values due to four possible spin configurations of the two B nuclei. The magnetic field at a B nucleus has two possible values. The energy level diagram for this molecule has six states or levels because there are two sets of levels with the same energy. Energy levels with the same energy are said to be degenerate. The vertical lines represent

the allowed transitions or absorptions of energy. Note that there are two lines drawn between some levels because of the degeneracy of those levels. The resultant NMR spectrum is depicted in the animation window. Note that the center absorption line of those centered at A is twice as high as the either of the outer two. This is because there were twice as many transitions in the energy level diagram for this transition. The peaks at B are taller because there are twice as many B type spins than A type spins. The complexity of the splitting pattern in a

spectrum increases as the number of B nuclei increases. The following table contains a few examples. Configuration A0 1/2 AB AB21:1 AB3 AB4 AB5 AB6 1:2:1 1:3:3:1 1:4:6:4:1 1:5:10:10:5:1 1:6:15:20:15:6:1

This series is called Pascal's triangle and can be calculated from the coefficients of the expansion of the equation (x+1)n where n is the number of B nuclei in the above table. When there are two different types of nuclei three bonds away there will be two values of J, one for each pair of nuclei. By now you get the idea of the number of possible configurations and the energy level diagram for these configurations, so we can skip to the spectrum. In the following example JAB is greater JBC.

The Time Domain NMR Signal

An NMR sample may contain many different magnetization components, each with its own Larmor frequency. These magnetization components are associated with the nuclear spin configurations joined by an allowed transition line in the energy level diagram. Based on the number of allowed absorptions due to chemical shifts and spin-spin couplings of the different nuclei in a molecule, an NMR spectrum may contain many different frequency lines. In pulsed NMR spectroscopy, signal is detected after these magnetization vectors are rotated into the XY plane. Once a magnetization vector is in the XY plane it rotates about the direction of the Bo field, the +Z axis. As transverse magnetization rotates about the Z axis, it will induce a current in a coil of wire located around the X axis. Plotting current as

a function of time gives a sine wave. This wave will, of course, decay with time constant T2* due to dephasing of the spin packets. This signal is called a free induction decay (FID). We will see in Chapter 5 how the FID is converted into a frequency domain spectrum. You will see in Chapter 6 what sequence of events will produce a time domain signal.

The +/- Frequency Convention

Transverse magnetization vectors rotating faster than the rotating frame of reference are said to be rotating at a positive frequency relatve to the rotating frame (+). Vectors rotating slower than the rotating frame are said to be rotating at a negative frequency relative to the rotating frame (-). It is worthwhile noting here that in most NMR spectra, the resonance frequency of a nucleus, as well as the magnetic field experienced by the nucleus and the chemical shift of a nucleus, increase from right to left. The frequency plots used in this hypertext book to describe Fourier transforms will use the more conventional mathematical axis of frequency increasing from left to right.

The Basics of NMR

Chapter 5 FOURIER TRANSFORMS
Introduction The + and - Frequency Problem The Fourier Transform Phase Correction Fourier Pairs The Convolution Theorem The Digital FT Sampling Error The Two-Dimensional FT

Introduction
A detailed description of the Fourier transform ( FT ) has waited until now, when you have a better appreciation of why it is needed. A Fourier transform is an operation which converts functions from time to frequency domains. An inverse Fourier transform ( IFT ) converts from the frequency domain to the time domain.

Recall from Chapter 2 that the Fourier transform is a mathematical technique for converting time domain data to frequency domain data, and vice versa.

The + and - Frequency Problem

To begin our detailed description of the FT consider the following. A magnetization vector, starting at +x, is rotating about the Z axis in a clockwise direction. The plot of Mx as a function of time is a cosine wave. Fourier transforming this gives peaks at both + and because the FT can not distinguish between a + and a - rotation of the vector from the data supplied. A plot of My as a function of time is a -sine function. Fourier transforming this gives peaks at + and - because the FT can not distinguish between a positive vector rotating at + and a negative vector rotating at - from the data supplied. The solution is to input both the Mx and My into the FT. The FT is designed to handle two orthogonal input functions called the real and imaginary components. Detecting just the Mx or My component for input into the FT is called linear detection. This was the detection scheme on many older NMR spectrometers and some magnetic resonance imagers. It required the computer to discard half of the frequency domain data. Detection of both Mx and My is called quadrature detection and is the method of detection on modern spectrometers and imagers. It is the method of choice since now the FT can distinguish between + and - , and all of the frequency domain data be used.

The Fourier Transform

An FT is defined by the integral Think of f( ) as the overlap of f(t) with a wave of frequency .

This is easy to picture by looking at the real part of f( ) only.

Consider the function of time, f( t ) = cos( 4t ) + cos( 9t ). To understand the FT, examine the product of f(t) with cos( t) for values between 1 and 10, and then the summation of the values of this product between 1 and 10 seconds. The summation will only be examined for time values between 0 and 10 seconds.
B 3 Y

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o

m a g n e t i c f i e l d c a n b e a c h i e v e d . T h

e o p t i m u m s h i m c u r r e n t s e t t i n g s a r e f o u n d b y e i t h e r m i n

i m i z i n g t h e l i n e w i d t h , m a x i m i z i n g t h e s i z e o f t h e F I D , o

r m a x i m i z i n g t h e s i g n a l f r o m t h e f i e l d l o c k . O n m o s t s p e c

t r o m e t e r s , t h e s h i m c o i l s a r e c o n t r o l l a b l e b y t h e c o m p u

t e r . A c o m p u t e r a l g o r i t h m h a s t h e t a s k o f f i n d i n g t h e b

e s t s h i m v a l u e b y m a x i m i z i n g t h e l o c k s i g n a l .

X
3

Y Z
3

F u

n c t i o n Z
0

Z Z
2

Z
3

Z
4

Z
5

X X Z X Z
2

X
2

Y
2

X Y Y Y Z

Y Z
2

X Z
3

X
2

Y
2

Z = 2 = 3 = 4 = 5 = 6 = 7 = 8 = 9 = 1 0 f ( )

T h e i n v e r s e F o u r i e r t r a n s f o r m ( I F T ) i s b e s t d

e p i c t e d a s a n s u m m a t i o n o f t h e t i m e d o m a i n s p e

c t r a o f f r e q u e n c i e s i n f ( ) .

S
T h e s a m p l e p r o

b e i s t h e n a m e g i v e n t o t h a t p a r t o f t h e s p e c t

r o m e t e r w h i c h a c c e p t s t h e s a m p l e , s e n d s R F e n e r

g y i n t o t h e s a m p l e , a n d d e t e c t s t h e s i g n a l e m a n

a t i n g f r o m t h e s a m p l e . I t c o n t a i n s t h e R F c o i l ,

s a m p l e s p i n n e r , t e m p e r a t u r e c o n t r o l l i n g c i r c u i t

r y , a n d g r a d i e n t c o i l s . T h e R F c o i l a n d g r a d i e n t

c o i l s w i l l b e d e s c r i b e d i n t h e n e x t t w o s e c t i

o n s . T h e s a m p l e s p i n n e r a n d t e m p e r a t u r e c o n t r o l

l i n g c i r c u i t r y w i l l b e d e s c r i b e d h e r e . T h e p u r

p o s e o f t h e s a m p l e s p i n n e r i s t o r o t a t e t h e N

M R s a m p l e t u b e a b o u t i t s a x i s . I n d o i n g s o , e a c

h s p i n i n t h e s a m p l e l o c a t e d a t a g i v e n p o s i t

i o n a l o n g t h e Z a x i s a n d r a d i u s f r o m t h e Z a x

i s , w i l l e x p e r i e n c e t h e a v e r a g e m a g n e t i c f i e l d

i n t h e c i r c l e d e f i n e d b y t h i s Z a n d r a d i u s . T

h e n e t e f f e c t i s a n a r r o w e r s p e c t r a l l i n e w i d t

h . T o a p p r e c i a t e t h i s p h e n o m e n o n , c o n s i d e r t h e

f o l l o w i n g e x a m p l e s . P i c t u r e a n a x i a l c r o s s s e

c t i o n o f a c y l i n d r i c a l t u b e c o n t a i n i n g s a m p l e

. I n a v e r y h o m o g e n e o u s B
o

m a g n e t i c f i e l d t h i s s

a m p l e w i l l y i e l d a n a r r o w s p e c t r u m . I n a m o r e

i n h o m o g e n e o u s f i e l d t h e s a m p l e w i l l y i e l d a b

r o a d e r s p e c t r u m d u e t o t h e p r e s e n c e o f l i n e s

f r o m t h e p a r t s o f t h e s a m p l e e x p e r i e n c i n g d i f

f e r e n t B
o

m a g n e t i c f i e l d s . W h e n t h e s a m p l e i s s p

u n a b o u t i t s z a x i s , i n h o m o g e n e i t i e s i n t h e X

a n d Y d i r e c t i o n s a r e a v e r a g e d o u t a n d t h e N M R

l i n e w i d t h b e c o m e s n a r r o w e r . M a n y s c i e n t i s t s

n e e d t o e x a m i n e p r o p e r t i e s o f t h e i r s a m p l e s

a s a f u n c t i o n o f t e m p e r a t u r e . A s a r e s u l t m a n y

i n s t r u m e n t s h a v e t h e a b i l i t y t o m a i n t a i n t h e

t e m p e r a t u r e o f t h e s a m p l e a b o v e a n d b e l o w r o

o m t e m p e r a t u r e . A i r o r n i t r o g e n w h i c h h a s b e e n

w a r m e d o r c o o l e d i s p a s s e d o v e r t h e s a m p l e t

o h e a t o r c o o l t h e s a m p l e . T h e t e m p e r a t u r e a t

t h e s a m p l e i s m o n i t o r e d w i t h t h e a i d o f a t h e

r m o c o u p l e a n d e l e c t r o n i c c i r c u i t r y m a i n t a i n s

t h e t e m p e r a t u r e b y i n c r e a s i n g o r d e c r e a s i n g t

h e t e m p e r a t u r e o f t h e g a s p a s s i n g o v e r t h e s a

m p l e . M o r e i n f o r m a t i o n o n t h i s t o p i c w i l l b e p

r e s e n t e d i n C h a p t e r 8 .

R
R F c o i l s c r e a t e t h e

B
1

f i e l d w h i c h r o t a t e s t h e n e t m a g n e t i z a t i o n i n

a p u l s e s e q u e n c e . T h e y a l s o d e t e c t t h e t r a n s v e

r s e m a g n e t i z a t i o n a s i t p r e c e s s e s i n t h e X Y p l

a n e . M o s t R F c o i l s o n N M R s p e c t r o m e t e r s a r e o f

t h e s a d d l e c o i l d e s i g n a n d a c t a s t h e t r a n s m i t

t e r o f t h e B
1

f i e l d a n d r e c e i v e r o f R F e n e r g y f r

o m t h e s a m p l e . Y o u m a y f i n d o n e o r m o r e R F c o i l

s i n a p r o b e . E a c h o f t h e s e R F c o i l s m u s t r e s o

n a t e , t h a t i s t h e y m u s t e f f i c i e n t l y s t o r e e n e r

g y , a t t h e L a r m o r f r e q u e n c y o f t h e n u c l e u s b e i

n g e x a m i n e d w i t h t h e N M R s p e c t r o m e t e r . A l l N M R

c o i l s a r e c o m p o s e d o f a n i n d u c t o r , o r i n d u c t i

v e e l e m e n t s , a n d a s e t o f c a p a c i t i v e e l e m e n t s .

T h e r e s o n a n t f r e q u e n c y , , o f a n R F c o i l i s d e t e

r m i n e d b y t h e i n d u c t a n c e ( L ) a n d c a p a c i t a n c e

( C ) o f t h e i n d u c t o r c a p a c i t o r c i r c u i t .

R F c

o i l s u s e d i n N M R s p e c t r o m e t e r s n e e d t o b e t u n

e d f o r t h e s p e c i f i c s a m p l e b e i n g s t u d i e d . A n R

F c o i l h a s a b a n d w i d t h o r s p e c i f i c r a n g e o f f

r e q u e n c i e s a t w h i c h i t r e s o n a t e s . W h e n y o u p l a

c e a s a m p l e i n a n R F c o i l , t h e c o n d u c t i v i t y a n

d d i e l e c t r i c c o n s t a n t o f t h e s a m p l e a f f e c t t h

e r e s o n a n c e f r e q u e n c y . I f t h i s f r e q u e n c y i s d i

f f e r e n t f r o m t h e r e s o n a n c e f r e q u e n c y o f t h e n

u c l e u s y o u a r e s t u d y i n g , t h e c o i l w i l l n o t e f f

i c i e n t l y s e t u p t h e B
1

f i e l d n o r e f f i c i e n t l y d e

t e c t t h e s i g n a l f r o m t h e s a m p l e . Y o u w i l l b e r

o t a t i n g t h e n e t m a g n e t i z a t i o n b y a n a n g l e l e s

s t h a n 9 0 d e g r e e s w h e n y o u t h i n k y o u a r e r o t a

t i n g b y 9 0 d e g r e e s . T h i s w i l l p r o d u c e l e s s t r a

n s v e r s e m a g n e t i z a t i o n a n d l e s s s i g n a l . F u r t h e r

m o r e , b e c a u s e t h e c o i l w i l l n o t b e e f f i c i e n t l y

d e t e c t i n g t h e s i g n a l , y o u r s i g n a l t o n o i s e r a

t i o w i l l b e p o o r . T h e B
1

f i e l d o f a n R F c o i l m u

s t b e p e r p e n d i c u l a r t o t h e B
o

m a g n e t i c f i e l d . A n

o t h e r r e q u i r e m e n t o f a n R F c o i l i n a n N M R s p e

c t r o m e t e r i s t h a t t h e B
1

f i e l d n e e d s t o b e h o m o

g e n e o u s o v e r t h e v o l u m e o f y o u r s a m p l e . I f i t

i s n o t , y o u w i l l b e r o t a t i n g s p i n s b y a d i s t r i

b u t i o n o f r o t a t i o n a n g l e s a n d y o u w i l l o b t a i n

s t r a n g e s p e c t r a .

G
T h e g r a d i e n t c o i l s p r o d u

c e t h e g r a d i e n t s i n t h e B
o

m a g n e t i c f i e l d n e e d e d

f o r p e r f o r m i n g g r a d i e n t e n h a n c e d s p e c t r o s c o p y

, d i f f u s i o n m e a s u r e m e n t s , a n d N M R m i c r o s c o p y . T h e

g r a d i e n t c o i l s a r e l o c a t e d i n s i d e t h e R F p r o b

e . N o t a l l p r o b e s h a v e g r a d i e n t c o i l s , a n d n o t a

l l N M R s p e c t r o m e t e r s h a v e t h e h a r d w a r e n e c e s s a

r y t o d r i v e t h e s e c o i l s . T h e g r a d i e n t c o i l s a r

e r o o m t e m p e r a t u r e c o i l s ( i . e . d o n o t r e q u i r e

c o o l i n g w i t h c r y o g e n s t o o p e r a t e ) w h i c h , b e c a

u s e o f t h e i r c o n f i g u r a t i o n , c r e a t e t h e d e s i r e d

g r a d i e n t . S i n c e t h e v e r t i c a l b o r e s u p e r c o n d u c

t i n g m a g n e t i s m o s t c o m m o n , t h e g r a d i e n t c o i l

s y s t e m w i l l b e d e s c r i b e d f o r t h i s m a g n e t . A s s

u m i n g t h e s t a n d a r d m a g n e t i c r e s o n a n c e c o o r d i n

a t e s y s t e m , a g r a d i e n t i n B
o

i n t h e Z d i r e c t i o n

i s a c h i e v e d w i t h a n a n t i h e l m h o l t z t y p e o f c o

i l . C u r r e n t i n t h e t w o c o i l s f l o w i n o p p o s i t e

d i r e c t i o n s c r e a t i n g a m a g n e t i c f i e l d g r a d i e n t

b e t w e e n t h e t w o c o i l s . T h e B f i e l d a t t h e c e n

t e r o f o n e c o i l a d d s t o t h e B
o

f i e l d , w h i l e t h e

B f i e l d a t t h e c e n t e r o f t h e o t h e r c o i l s u b t r

a c t s f r o m t h e B
o

f i e l d . T h e X a n d Y g r a d i e n t s

i n t h e B
o

f i e l d a r e c r e a t e d b y a p a i r o f f i g u r e

8 c o i l s . T h e X a x i s f i g u r e 8 c o i l s c r e a t e a g

r a d i e n t i n B
o

i n t h e X d i r e c t i o n d u e t o t h e d i r

e c t i o n o f t h e c u r r e n t t h r o u g h t h e c o i l s . T h e Y

a x i s f i g u r e 8 c o i l s p r o v i d e s a s i m i l a r g r a d i

e n t i n B
o

a l o n g t h e Y a x i s .

Q
T h e q u a d r a t u r e

d e t e c t o r i s a d e v i c e w h i c h s e p a r a t e s o u t t h e M
x

'

a n d M
y '

s i g n a l s f r o m t h e s i g n a l f r o m t h e R F c o i

l . F o r t h i s r e a s o n i t c a n b e t h o u g h t o f a s a l a

b o r a t o r y t o r o t a t i n g f r a m e o f r e f e r e n c e c o n v e r

t e r . T h e h e a r t o f a q u a d r a t u r e d e t e c t o r i s a d e

v i c e c a l l e d a d o u b l y b a l a n c e d m i x e r . T h e d o u b l y

b a l a n c e d m i x e r h a s t w o i n p u t s a n d o n e o u t p u t .

I f t h e i n p u t s i g n a l s a r e C o s ( A ) a n d C o s ( B ) , t h e

o u t p u t w i l l b e 1 / 2 C o s ( A + B ) a n d 1 / 2 C o s ( A B ) .

F o r t h i s r e a s o n t h e d e v i c e i s o f t e n c a l l e d a p

r o d u c t d e t e c t o r s i n c e t h e p r o d u c t o f C o s ( A ) a n

d C o s ( B ) i s t h e o u t p u t . T h e q u a d r a t u r e d e t e c t o

r t y p i c a l l y c o n t a i n s t w o d o u b l y b a l a n c e d m i x e

r s , t w o f i l t e r s , t w o a m p l i f i e r s , a n d a 9 0
o

p h a s e s

h i f t e r . T h e r e a r e t w o i n p u t s a n d t w o o u t p u t s o

n t h e d e v i c e . F r e q u e n c y a n d
o

a r e p u t i n a n d t h e

M
X '

a n d M
Y '

c o m p o n e n t s o f t h e t r a n s v e r s e m a g n e t

i z a t i o n c o m e o u t . T h e r e a r e s o m e p o t e n t i a l p r o

b l e m s w h i c h c a n o c c u r w i t h t h i s d e v i c e w h i c h

w i l l c a u s e a r t i f a c t s i n t h e s p e c t r u m . O n e i s c

a l l e d a D C o f f s e t a r t i f a c t a n d t h e o t h e r i s c

a l l e d a q u a d r a t u r e a r t i f a c t .

D
M a n y n e w e r s p

e c t r o m e t e r s e m p l o y a c o m b i n a t i o n o f o v e r s a m p l i

n g , d i g i t a l f i l t e r i n g , a n d d e c i m a t i o n t o e l i m i n a

t e t h e w r a p a r o u n d a r t i f a c t . O v e r s a m p l i n g c r e a t

e s a l a r g e r s p e c t r a l o r s w e e p w i d t h , b u t g e n e r a

t e s t o o m u c h d a t a t o b e c o n v e n i e n t l y s t o r e d . D i

g i t a l f i l t e r i n g e l i m i n a t e s t h e h i g h f r e q u e n c y

c o m p o n e n t s f r o m t h e d a t a , a n d d e c i m a t i o n r e d u c e

s t h e s i z e o f t h e d a t a s e t . T h e f o l l o w i n g f l o w c

h a r t s u m m a r i z e s t h e e f f e c t s o f t h e t h r e e s t e p s

b y s h o w i n g t h e r e s u l t o f p e r f o r m i n g a n F T a f t

e r e a c h s t e p . L e t ' s e x a m i n e o v e r s a m p l i n g , d i g i t

a l f i l t e r i n g , a n d d e c i m a t i o n i n m o r e d e t a i l t o

s e e h o w t h i s c o m b i n a t i o n o f s t e p s c a n b e u s e

d t o r e d u c e t h e w r a p a r o u n d p r o b l e m . O v e r s a m p

l i n g i s t h e d i g i t i z a t i o n o f a t i m e d o m a i n s i g

n a l a t a f r e q u e n c y m u c h g r e a t e r t h a n n e c e s s a r

y t o r e c o r d t h e d e s i r e d s p e c t r a l w i d t h . F o r e x

a m p l e , i f t h e s a m p l i n g f r e q u e n c y , f
s

, i s i n c r e a s e

d b y a f a c t o r o f 1 0 , t h e s w e e p w i d t h w i l l b e 1

0 t i m e s g r e a t e r , t h u s e l i m i n a t i n g w r a p a r o u n d . U

n f o r t u n a t e l y d i g i t i z i n g a t 1 0 t i m e s t h e s p e e d

a l s o i n c r e a s e s t h e a m o u n t o f r a w d a t a b y a f

a c t o r o f 1 0 , t h u s i n c r e a s i n g s t o r a g e r e q u i r e m e

n t s a n d p r o c e s s i n g t i m e . F i l t e r i n g i s t h e r e m

o v a l o f a s e l e c t b a n d o f f r e q u e n c i e s f r o m a s

i g n a l . F o r a n e x a m p l e o f f i l t e r i n g , c o n s i d e r t h

e f o l l o w i n g f r e q u e n c y d o m a i n s i g n a l . F r e q u e n c i

e s a b o v e f
o

c o u l d b e r e m o v e d f r o m t h i s f r e q u e n

c y d o m a i n s i g n a l b y m u l t i p l i n g t h e s i g n a l b y

t h i s r e c t a n g u l a r f u n c t i o n . I n N M R , t h i s s t e p w o

u l d b e e q u i v a l e n t t o t a k i n g a l a r g e s w e e p w i d

t h s p e c t r u m a n d s e t t i n g t o z e r o i n t e n s i t y t h o

s e s p e c t r a l f r e q u e n c i e s w h i c h a r e f a r t h e r t h a

n s o m e d i s t a n c e f r o m t h e c e n t e r o f t h e s p e c t r

u m . D i g i t a l f i l t e r i n g i s t h e r e m o v a l o f t h e s e

f r e q u e n c i e s u s i n g t h e t i m e d o m a i n s i g n a l . R e c

a l l f r o m C h a p t e r 5 t h a t i f t w o f u n c t i o n s a r e

m u l t i p l i e d i n o n e d o m a i n ( i . e . f r e q u e n c y ) , w e

m u s t c o n v o l v e t h e F T o f t h e t w o f u n c t i o n s t o g

e t h e r i n t h e o t h e r d o m a i n ( i . e . t i m e ) . T o f i l t

e r o u t f r e q u e n c i e s a b o v e f
o

f r o m t h e t i m e d o m a

i n s i g n a l , t h e s i g n a l m u s t b e c o n v o l v e d w i t h t

h e F o u r i e r t r a n s f o r m o f t h e r e c t a n g u l a r f u n c t

i o n , a s i n c f u n c t i o n . ( S e e C h a p t e r 5 . ) T h i s p r o

c e s s e l i m i n a t e s f r e q u e n c i e s g r e a t e r t h a n f
o

f r

o m t h e t i m e d o m a i n s i g n a l . F o u r i e r t r a n s f o r m i n

g t h e r e s u l t a n t t i m e d o m a i n s i g n a l y i e l d s a f

r e q u e n c y d o m a i n s i g n a l w i t h o u t t h e h i g h e r f r e

q u e n c i e s . I n N M R , t h i s s t e p w i l l r e m o v e s p e c t r a

l c o m p o n e n t s w i t h f r e q u e n c i e s g r e a t e r t h a n + f

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a t i o n o f d a t a p o i n t s f r o m a d a t a s e t . A d e c i m a

t i o n r a t i o o f 4 / 5 m e a n s t h a t 4 o u t o f e v e r y 5

d a t a p o i n t s a r e d e l e t e d , o r e v e r y f i f t h d a t a

p o i n t i s s a v e d . D e c i m a t i n g t h e d i g i t a l l y f i l t e

r e d d a t a a b o v e , f o l l o w e d b y a F o u r i e r t r a n s f o r

m , w i l l r e d u c e t h e d a t a s e t b y a f a c t o r o f f i v

e . H i g h s p e e d d i g i t i z e r s , c a p a b l e o f d i g i t i z i n

g a t 2 M H z , a n d d e d i c a t e d h i g h s p e e d i n t e g r a t e

d c i r c u i t s , c a p a b l e o f p e r f o r m i n g t h e c o n v o l u t

i o n o n t h e t i m e d o m a i n d a t a a s i t i s b e i n g r e

c o r d e d , a r e u s e d t o r e a l i z e t h i s p r o c e d u r e .

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o n s w h i c h o n e s h o u l d b e f a m i l i a r w i t h b e f o r e u

s i n g a n N M R s p e c t r o m e t e r . T h e s e c o n c e r n t h e u s e

o f s t r o n g m a g n e t i c f i e l d s a n d c r y o g e n i c l i q u i

d s . M a g n e t i c f i e l d s f r o m h i g h f i e l d m a g n e t s c a

n l i t e r a l l y p i c k u p a n d p u l l f e r r o m a g n e t i c i t

e m s i n t o t h e b o r e o f t h e m a g n e t . C a u t i o n m u s t

b e t a k e n t o k e e p a l l f e r r o m a g n e t i c i t e m s a w a y

f r o m t h e m a g n e t b e c a u s e t h e y c a n s e r i o u s l y d

a m a g e t h e m a g n e t , s h i m c o i l s , a n d p r o b e . T h e f o r

c e e x e r t e d o n t h e c o n c e n t r i c c r y o g e n i c d e w a r s

w i t h i n a m a g n e t b y a l a r g e m e t a l o b j e c t s t u c

k t o t h e m a g n e t c a n b r e a k d e w a r s a n d m a g n e t s

u p p o r t s . T h e k i n e t i c e n e r g y o f a n o b j e c t b e i n g

s u c k e d i n t o a m a g n e t c a n s m a s h a d e w a r o r a n

e l e c t r i c a l c o n n e c t o r o n a p r o b e . S m a l l f e r r o m

a g n e t i c o b j e c t s a r e j u s t a s m u c h a c o n c e r n a s

l a r g e r o n e s . A s m a l l m e t a l s l i v e r c a n g e t s u c

k e d i n t o t h e b o r e o f t h e m a g n e t a n d d e s t r o y t

h e h o m o g e n e i t y o f t h e m a g n e t a c h i e v e d w i t h a

s e t o f s h i m s e t t i n g s . T h e r e a r e a d d i t i o n a l c o

n c e r n s r e g a r d i n g t h e e f f e c t o f m a g n e t i c f i e l d

s o n e l e c t r o n i c c i r c u i t r y , s p e c i f i c a l l y p a c e m a

k e r s . A n i n d i v i d u a l w i t h a p a c e m a k e r w a l k i n g t

h r o u g h a s t r o n g m a g n e t i c f i e l d c a n i n d u c e c u r

r e n t s i n t h e p a c e m a k e r c i r c u i t r y w h i c h w i l l c

a u s e i t t o f a i l a n d p o s s i b l y c a u s e d e a t h . A p e

r s o n w i t h a p a c e m a k e r m u s t n o t b e a b l e t o i n a

d v e r t e n t l y s t r a y i n t o a m a g n e t i c f i e l d o f f i v

e o r m o r e G a u s s . A l t h o u g h n o t a s i m p o r t a n t a s

a p a c e m a k e r , m e c h a n i c a l w a t c h e s a n d s o m e d i g i t

a l w a t c h e s w i l l a l s o b e a f f e c t e d b y m a g n e t i c

f i e l d s . M a g n e t i c f i e l d s o f a p p r o x i m a t e l y 5 0 G a

u s s w i l l e r a s e c r e d i t c a r d s a n d m a g n e t i c s t o r

a g e m e d i a . T h e l i q u i d n i t r o g e n a n d l i q u i d h e l

i u m u s e d i n N M R s p e c t r o m e t e r s a r e a t a t e m p e r

a t u r e o f 7 7 . 4 K a n d 4 . 2 K r e s p e c t i v e l y . T h e s e

l i q u i d s c a n c a u s e f r o s t b i t e , w h i c h i s n o t a c o

n c e r n u n l e s s y o u a r e f i l l i n g t h e m a g n e t . I f y o

u a r e f i l l i n g t h e m a g n e t o r i f y o u a r e o p e r a t

i n g t h e s p e c t r o m e t e r , s u f f o c a t i o n i s a n o t h e r c

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h i l e s o m e o f t h e s e m a y b e e a s y f o r y o u t o u n d e

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e n c e s i n t h e w a y t h e s p e c t r a w e r e r e c o r d e d . O n

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f i e l d i n c r e a s e s i n m a g n i t u d e ( i .

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n e r a l l y i n c r e a s e s . T h e s h a p e o f t h e s p e c t r u m m

a y a l s o c h a n g e . F o r e x a m p l e , c o n s i d e r t h e h y d r o

g e n N M R s p e c t r u m f r o m t h r e e c o u p l e d n u c l e i A ,

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r u m . T o s e e a n e s t h e t i c a l l y p l e a s i n g ( a b s o r p t i

o n ) f r e q u e n c y d o m a i n s p e c t r u m , w e w a n t t o i n p u

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n s f o r m i n g t h e p h a s e c o r r e c t e d F I D s g i v e s a n a

b s o r p t i o n s p e c t r u m f o r t h e r e a l o u t p u t o f t h e

F T . T h i s c o r r e c t i o n c a n b e d o n e i n t h e f r e q u e

n c y d o m a i n a s w e l l a s i n t h e t i m e d o m a i n . N M R

s p e c t r a r e q u i r e b o t h c o n s t a n t a n d l i n e a r c o r

r e c t i o n s t o t h e p h a s i n g o f t h e F o u r i e r t r a n s f

o r m e d s i g n a l . = m + b C o n s t a n t p h a s e c o r r e c

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o f u n c t i o n s , t h e f r e q u e n c y d o m a i n f o r m a n d t h e

c o r r e s p o n d i n g t i m e d o m a i n f o r m . H e r e a r e a f e w

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i t u d e o f t h e F o u r i e r p a i r s h a s b e e n n e g l e c t e d

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o r m s i s t h e c o n v o l u t i o n t h e o r e m . T h e c o n v o l u t i o

n t h e o r e m s a y s t h a t t h e F T o f a c o n v o l u t i o n o f

t w o f u n c t i o n s i s p r o p o r t i o n a l t o t h e p r o d u c t s

o f t h e i n d i v i d u a l F o u r i e r t r a n s f o r m s , a n d v i c e

v e r s a . I f f ( ) = F T ( f ( t ) ) a n d g ( ) = F T ( g (

t ) ) t h e n f ( ) g ( ) = F T ( g ( t ) f ( t ) ) a n d f (

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n d o w w e a r e t r y i n g t o f i n d t h e F T o f a s i n e w

a v e w h i c h i s t u r n e d o n a n d o f f . T h e c o n v o l u t i o

n t h e o r e m t e l l s u s t h a t t h i s i s a s i n c f u n c t i

o n a t t h e f r e q u e n c y o f t h e s i n e w a v e . A n o t h e r

a p p l i c a t i o n o f t h e c o n v o l u t i o n t h e o r e m i s i n

n o i s e r e d u c t i o n . W i t h t h e c o n v o l u t i o n t h e o r e m

i t c a n b e s e e n t h a t t h e c o n v o l u t i o n o f a n N M

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o n a n c e s p e c t r o m e t e r , t h e c o m p u t e r d o e s n o t s e e

a c o n t i n u o u s F I D , b u t r a t h e r a n F I D w h i c h i s s a

m p l e d a t a c o n s t a n t i n t e r v a l . E a c h d a t a p o i n t m

a k i n g u p t h e F I D w i l l h a v e d i s c r e t e a m p l i t u d e

a n d t i m e v a l u e s . T h e r e f o r e , t h e c o m p u t e r n e e d s t

o t a k e t h e F T o f a s e r i e s o f d e l t a f u n c t i o n s w

h i c h v a r y i n i n t e n s i t y .

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h e s p e c t r u m o n t h e o p p o s i t e s i d e . I n t e r m s o f a

o n e d i m e n s i o n a l f r e q u e n c y d o m a i n s p e c t r u m , w r a

p a r o u n d i s t h e o c c u r r e n c e o f a l o w f r e q u e n c y

p e a k w h i c h o c c u r s o n t h e h i g h f r e q u e n c y s i d e o

f t h e s p e c t r u m . T h e c o n v o l u t i o n t h e o r e m c a n e x

p l a i n w h y t h i s p r o b l e m r e s u l t s f r o m s a m p l i n g

t h e t r a n s v e r s e m a g n e t i z a t i o n a t t o o s l o w a r a

t e . F i r s t , o b s e r v e w h a t t h e F T o f a c o r r e c t l y s

a m p l e d F I D l o o k s l i k e . W i t h q u a d r a t u r e d e t e c t i

o n , t h e s p e c t r a l w i d t h i s e q u a l t o t h e i n v e r s e

o f t h e s a m p l i n g f r e q u e n c y , o r t h e w i d t h o f t h

e g r e e n b o x i n t h e a n i m a t i o n w i n d o w . W h e n t h e

s a m p l i n g f r e q u e n c y i s l e s s t h a n t h e s p e c t r a l

w i d t h , w r a p a r o u n d o c c u r s .

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o n a l F o u r i e r t r a n s f o r m ( 2 D F T ) i s a n F T p e r f o r

m e d o n a t w o d i m e n s i o n a l a r r a y o f d a t a . C o n s i d

e r t h e t w o d i m e n s i o n a l a r r a y o f d a t a d e p i c t e d

i n t h e a n i m a t i o n w i n d o w . T h i s d a t a h a s a t ' a

n d a t " d i m e n s i o n . A F T i s f i r s t p e r f o r m e d o n

t h e d a t a i n o n e d i m e n s i o n a n d t h e n i n t h e s e c

o n d . T h e f i r s t s e t o f F o u r i e r t r a n s f o r m s a r e p

e r f o r m e d i n t h e t ' d i m e n s i o n t o y i e l d a n f ' b

y t " s e t o f d a t a . T h e s e c o n d s e t o f F o u r i e r t r

a n s f o r m s i s p e r f o r m e d i n t h e t " d i m e n s i o n t o

y i e l d a n f ' b y f " s e t o f d a t a . T h e 2 D F T i s r

e q u i r e d t o p e r f o r m s t a t e o f t h e a r t M R I . I n M R

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t ' a n d t " d i m e n s i o n s , c a l l e d k s p a c e . T h i s r a w

d a t a i s F o u r i e r t r a n s f o r m e d t o y i e l d t h e i m a g

e w h i c h i s t h e e q u i v a l e n t o f t h e f ' b y f " d a t

a d e s c r i b e d a b o v e .

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i n s i g n a l c a n b e c o n v e r t e d i n t o a f r e q u e n c y d o

m a i n s i g n a l . I n t h i s c h a p t e r y o u w i l l l e a r n a f

e w o f t h e w a y s t h a t a t i m e d o m a i n s i g n a l c a n b

e c r e a t e d . T h r e e m e t h o d s a r e p r e s e n t e d h e r e , b u t

t h e r e a r e a n i n f i n i t e n u m b e r o f p o s s i b i l i t i e s

. T h e s e m e t h o d s a r e c a l l e d p u l s e s e q u e n c e s . A p u

l s e s e q u e n c e i s a s e t o f R F p u l s e s a p p l i e d t o

a s a m p l e t o p r o d u c e a s p e c i f i c f o r m o f N M R s i g

n a l .

T
I n t h e 9 0 F I D p u l s e s e q u e n c e , n e t m a g n e

t i z a t i o n i s r o t a t e d d o w n i n t o t h e X ' Y ' p l a n e w

i t h a 9 0
o

p u l s e . T h e n e t m a g n e t i z a t i o n v e c t o r b e g

i n s t o p r e c e s s a b o u t t h e + Z a x i s . T h e m a g n i t u d e

o f t h e v e c t o r a l s o d e c a y s w i t h t i m e . A t i m i n g

d i a g r a m i s a m u l t i p l e a x i s p l o t o f s o m e a s p e

c t o f a p u l s e s e q u e n c e v e r s u s t i m e . A t i m i n g d

i a g r a m f o r a 9 0 F I D p u l s e s e q u e n c e h a s a p l o t

o f R F e n e r g y v e r s u s t i m e a n d a n o t h e r f o r s i g

n a l v e r s u s t i m e . W h e n t h i s s e q u e n c e i s r e p e a t

e d , f o r e x a m p l e w h e n s i g n a l t o n o i s e i m p r o v e m e

n t i s n e e d e d , t h e a m p l i t u d e o f t h e s i g n a l a f t e

r b e i n g F o u r i e r t r a n s f o r m e d ( S ) w i l l d e p e n d o

n T
1

a n d t h e t i m e b e t w e e n r e p e t i t i o n s , c a l l e d t h

e r e p e t i t i o n t i m e ( T R ) , o f t h e s e q u e n c e . I n t h e

s i g n a l e q u a t i o n b e l o w , k i s a p r o p o r t i o n a l i t y

c o n s t a n t a n d i s t h e d e n s i t y o f s p i n s i n t h e

s a m p l e . S = k ( 1 e
T R / T 1

T
A n o t h e r c o m

m o n l y u s e d p u l s e s e q u e n c e i s t h e s p i n e c h o p u l

s e s e q u e n c e . H e r e a 9 0
o

p u l s e i s f i r s t a p p l i e d t o

t h e s p i n s y s t e m . T h e 9 0
o

d e g r e e p u l s e r o t a t e s t h

e m a g n e t i z a t i o n d o w n i n t o t h e X ' Y ' p l a n e . T h e t

r a n s v e r s e m a g n e t i z a t i o n b e g i n s t o d e p h a s e . A t s

o m e p o i n t i n t i m e a f t e r t h e 9 0
o

p u l s e , a 1 8 0
o

p u l s

e i s a p p l i e d . T h i s p u l s e r o t a t e s t h e m a g n e t i z a t

i o n b y 1 8 0
o

a b o u t t h e X ' a x i s . T h e 1 8 0
o

p u l s e c a u s

e s t h e m a g n e t i z a t i o n t o a t l e a s t p a r t i a l l y r e p

h a s e a n d t o p r o d u c e a s i g n a l c a l l e d a n e c h o .

A t i m i n g d i a g r a m s h o w s t h e r e l a t i v e p o s i t i o n s

o f t h e t w o r a d i o f r e q u e n c y p u l s e s a n d t h e s i

g n a l . T h e s i g n a l e q u a t i o n f o r a r e p e a t e d s p i n

e c h o s e q u e n c e a s a f u n c t i o n o f t h e r e p e t i t i o

n t i m e , T R , a n d t h e e c h o t i m e ( T E ) d e f i n e d a s t

h e t i m e b e t w e e n t h e 9 0
o

p u l s e a n d t h e m a x i m u m a

m p l i t u d e i n t h e e c h o i s S = k ( 1 e
T R / T 1

) e
T E / T 2

T
A n i n v e r s i o n r e c o v e r y p u l s e s e q u

e n c e c a n a l s o b e u s e d t o r e c o r d a n N M R s p e c t r u

m . I n t h i s s e q u e n c e , a 1 8 0
o

p u l s e i s f i r s t a p p l i e d

. T h i s r o t a t e s t h e n e t m a g n e t i z a t i o n d o w n t o t h

e Z a x i s . T h e m a g n e t i z a t i o n u n d e r g o e s s p i n l a t

t i c e r e l a x a t i o n a n d r e t u r n s t o w a r d i t s e q u i l i b

r i u m p o s i t i o n a l o n g t h e + Z a x i s . B e f o r e i t r e a c

h e s e q u i l i b r i u m , a 9 0
o

p u l s e i s a p p l i e d w h i c h r o t

a t e s t h e l o n g i t u d i n a l m a g n e t i z a t i o n i n t o t h e X

Y p l a n e . I n t h i s e x a m p l e , t h e 9 0
o

p u l s e i s a p p l i e d

s h o r t l y a f t e r t h e 1 8 0
o

p u l s e . O n c e m a g n e t i z a t i o n

i s p r e s e n t i n t h e X Y p l a n e i t r o t a t e s a b o u t t

h e Z a x i s a n d d e p h a s e s g i v i n g a F I D . O n c e a g a i

n , t h e t i m i n g d i a g r a m s h o w s t h e r e l a t i v e p o s i t

i o n s o f t h e t w o r a d i o f r e q u e n c y p u l s e s a n d t h

e s i g n a l . T h e s i g n a l a s a f u n c t i o n o f T I w h e n

t h e s e q u e n c e i s n o t r e p e a t e d i s S = k ( 1 -

2 e
T I / T 1

) I t s h o u l d b e n o t e d a t t h i s t i m e t

h a t t h e z e r o c r o s s i n g o f t h i s f u n c t i o n o c c u r s

f o r T I = T
1

l n 2 .

T
C N

H M F S S R G

Q D S

H
T h e g r a p h i c s w i n d o w d i s p l a y s a s c h

e m a t i c r e p r e s e n t a t i o n o f t h e m a j o r s y s t e m s o f

a n u c l e a r m a g n e t i c r e s o n a n c e s p e c t r o m e t e r a n d

a f e w o f t h e m a j o r i n t e r c o n n e c t i o n s . T h i s o v e r v

i e w b r i e f l y s t a t e s t h e f u n c t i o n o f e a c h c o m p o n

e n t . S o m e w i l l b e d e s c r i b e d i n d e t a i l l a t e r i n

t h i s c h a p t e r . A t t h e t o p o f t h e s c h e m a t i c r e p r

e s e n t a t i o n , y o u w i l l f i n d t h e s u p e r c o n d u c t i n g

m a g n e t o f t h e N M R s p e c t r o m e t e r . T h e m a g n e t p r o

d u c e s t h e B
o

f i e l d n e c e s s a r y f o r t h e N M R e x p e r i

m e n t s . I m m e d i a t e l y w i t h i n t h e b o r e o f t h e m a g n

e t a r e t h e s h i m c o i l s f o r h o m o g e n i z i n g t h e B
o

i e l d . W i t h i n t h e s h i m c o i l s i s t h e p r o b e . T h e p

r o b e c o n t a i n s t h e R F c o i l s f o r p r o d u c i n g t h e

B
1

m a g n e t i c f i e l d n e c e s s a r y t o r o t a t e t h e s p i n s

b y 9 0
o

o r 1 8 0
o

. T h e R F c o i l a l s o d e t e c t s t h e s i

g n a l f r o m t h e s p i n s w i t h i n t h e s a m p l e . T h e s a m

p l e i s p o s i t i o n e d w i t h i n t h e R F c o i l o f t h e p

r o b e . S o m e p r o b e s a l s o c o n t a i n a s e t o f g r a d i e

n t c o i l s . T h e s e c o i l s p r o d u c e a g r a d i e n t i n B
o

l o n g t h e X , Y , o r Z a x i s . G r a d i e n t c o i l s a r e u s e

d f o r f o r g r a d i e n t e n h a n c e d s p e c t r o s c o p y ( S e e

C h a p t e r 1 1 . ) , d i f f u s i o n ( S e e C h a p t e r 1 1 . ) , a n d

N M R m i c r o s c o p y ( S e e C h a p t e r 1 1 . ) e x p e r i m e n t s

. T h e h e a r t o f t h e s p e c t r o m e t e r i s t h e c o m p u t

e r . I t c o n t r o l s a l l o f t h e c o m p o n e n t s o f t h e s

p e c t r o m e t e r . T h e R F c o m p o n e n t s u n d e r c o n t r o l o

f t h e c o m p u t e r a r e t h e R F f r e q u e n c y s o u r c e a n

d p u l s e p r o g r a m m e r . T h e s o u r c e p r o d u c e s a s i n e

w a v e o f t h e d e s i r e d f r e q u e n c y . T h e p u l s e p r o g

r a m m e r s e t s t h e w i d t h , a n d i n s o m e c a s e s t h e s

h a p e , o f t h e R F p u l s e s . T h e R F a m p l i f i e r i n c r e a

s e s t h e p u l s e s p o w e r f r o m m i l l i W a t t s t o t e n s

o r h u n d r e d s o f W a t t s . T h e c o m p u t e r a l s o c o n t r

o l s t h e g r a d i e n t p u l s e p r o g r a m m e r w h i c h s e t s

t h e s h a p e a n d a m p l i t u d e o f g r a d i e n t f i e l d s . T h

e g r a d i e n t a m p l i f i e r i n c r e a s e s t h e p o w e r o f t

h e g r a d i e n t p u l s e s t o a l e v e l s u f f i c i e n t t o d

r i v e t h e g r a d i e n t c o i l s . T h e o p e r a t o r o f t h e

s p e c t r o m e t e r g i v e s i n p u t t o t h e c o m p u t e r t h r o

u g h a c o n s o l e t e r m i n a l w i t h a m o u s e a n d k e y b o

a r d . S o m e s p e c t r o m e t e r s a l s o h a v e a s e p a r a t e s

m a l l i n t e r f a c e f o r c a r r y i n g o u t s o m e o f t h e m

o r e r o u t i n e p r o c e d u r e s o n t h e s p e c t r o m e t e r . A

p u l s e s e q u e n c e i s s e l e c t e d a n d c u s t o m i z e d f r o

m t h e c o n s o l e t e r m i n a l . T h e o p e r a t o r c a n s e e s

p e c t r a o n a v i d e o d i s p l a y l o c a t e d o n t h e c o n s

o l e a n d c a n m a k e h a r d c o p i e s o f s p e c t r a u s i n g

a p r i n t e r . T h e n e x t s e c t i o n s o f t h i s c h a p t e r

g o i n t o m o r e d e t a i l c o n c e r n i n g t h e m a g n e t , l o

c k , s h i m c o i l s , g r a d i e n t c o i l s , R F c o i l s , a n d R F

d e t e c t o r o f n u c l e a r m a g n e t i c r e s o n a n c e s p e c t r

o m e t e r .

M
T h e N M R m a g n e t i s o n e o f t h e m o s t

e x p e n s i v e c o m p o n e n t s o f t h e n u c l e a r m a g n e t i c r

e s o n a n c e s p e c t r o m e t e r s y s t e m . M o s t m a g n e t s a r e

o f t h e s u p e r c o n d u c t i n g t y p e . T h i s i s a p i c t u r e

o f a 7 . 0 T e s l a s u p e r c o n d u c t i n g m a g n e t f r o m a n

N M R s p e c t r o m e t e r . A s u p e r c o n d u c t i n g m a g n e t h a s

a n e l e c t r o m a g n e t m a d e o f s u p e r c o n d u c t i n g w i r e .

S u p e r c o n d u c t i n g w i r e h a s a r e s i s t a n c e a p p r o x i m

a t e l y e q u a l t o z e r o w h e n i t i s c o o l e d t o a t e m

p e r a t u r e c l o s e t o a b s o l u t e z e r o ( 2 7 3 . 1 5
o

C o r

0 K ) b y e m e r s i n g i t i n l i q u i d h e l i u m . O n c e c u r

r e n t i s c a u s e d t o f l o w i n t h e c o i l i t w i l l c o n

t i n u e t o f l o w f o r a s l o n g a s t h e c o i l i s k e p t

a t l i q u i d h e l i u m t e m p e r a t u r e s . ( S o m e l o s s e s d o

o c c u r o v e r t i m e d u e t o t h e i n f i n i t e s i m a l l y s m a

l l r e s i s t a n c e o f t h e c o i l . T h e s e l o s s e s a r e o n

t h e o r d e r o f a p p m o f t h e m a i n m a g n e t i c f i e l d

p e r y e a r . ) T h e l e n g t h o f s u p e r c o n d u c t i n g w i r e

i n t h e m a g n e t i s t y p i c a l l y s e v e r a l m i l e s . T h i

s w i r e i s w o u n d i n t o a m u l t i t u r n s o l e n o i d o r

c o i l . T h e c o i l o f w i r e i s k e p t a t a t e m p e r a t u

r e o f 4 . 2 K b y i m m e r s i n g i t i n l i q u i d h e l i u m . T

h e c o i l a n d l i q u i d h e l i u m a r e k e p t i n a l a r g e

d e w a r . T h i s d e w a r i s t y p i c a l l y s u r r o u n d e d b y

a l i q u i d n i t r o g e n ( 7 7 . 4 K ) d e w a r , w h i c h a c t s a s

a t h e r m a l b u f f e r b e t w e e n t h e r o o m t e m p e r a t u r

e a i r ( 2 9 3 K ) a n d t h e l i q u i d h e l i u m . A c r o s s s e

c t i o n a l v i e w o f t h e s u p e r c o n d u c t i n g m a g n e t , d e

p i c t i n g t h e c o n c e n t r i c d e w a r s , c a n b e f o u n d i n

t h e a n i m a t i o n w i n d o w . T h e f o l l o w i n g i m a g e i s

a n a c t u a l c u t a w a y v i e w o f a s u p e r c o n d u c t i n g

m a g n e t . T h e m a g n e t i s s u p p o r t e d b y t h r e e l e g s

, a n d t h e c o n c e n t r i c n i t r o g e n a n d h e l i u m d e w a r

s a r e s u p p o r t e d b y s t a c k s c o m i n g o u t o f t h e t

o p o f t h e m a g n e t . A r o o m t e m p e r a t u r e b o r e h o l e

e x t e n d s t h r o u g h t h e c e n t e r o f t h e a s s e m b l y . T

h e s a m p l e p r o b e a n d s h i m c o i l s a r e l o c a t e d w i

t h i n t h i s b o r e h o l e . A l s o d e p i c t e d i n t h i s p i c

t u r e i s t h e l i q u i d n i t r o g e n l e v e l s e n s o r , a n e

l e c t r o n i c a s s e m b l y f o r m o n i t o r i n g t h e l i q u i d

n i t r o g e n l e v e l . G o i n g f r o m t h e o u t s i d e o f t h e

m a g n e t t o t h e i n s i d e , w e s e e a v a c u u m r e g i o n

f o l l o w e d b y a l i q u i d n i t r o g e n r e s e r v o i r . T h e v

a c u u m r e g i o n i s f i l l e d w i t h s e v e r a l l a y e r s o f

a r e f l e c t i v e m y l a r f i l m . T h e f u n c t i o n o f t h e

m y l a r i s t o r e f l e c t t h e r m a l p h o t o n s , a n d t h u s

d i m i n i s h h e a t f r o m e n t e r i n g t h e m a g n e t . W i t h i n

t h e i n s i d e w a l l o f t h e l i q u i d n i t r o g e n r e s e r

v o i r , w e s e e a n o t h e r v a c u u m f i l l e d w i t h s o m e r

e f l e c t i v e m y l a r . T h e l i q u i d h e l i u m r e s e r v o i r c

o m e s n e x t . T h i s r e s e r v o i r h o u s e s t h e s u p e r c o n d

u c t i n g s o l e n o i d o r c o i l o f w i r e . T a k i n g a c l o

s e r l o o k a t t h e s o l e n o i d i t i s c l e a r t o s e e t

h e c o i l a n d t h e b o r e t u b e e x t e n d i n g t h r o u g h t

h e m a g n e t .

F
I n o r d e r t o p r o d u c e a h i g h r e s o

l u t i o n N M R s p e c t r u m o f a s a m p l e , e s p e c i a l l y o n e

w h i c h r e q u i r e s s i g n a l a v e r a g i n g o r p h a s e c y c l

i n g , y o u n e e d t o h a v e a t e m p o r a l l y c o n s t a n t a n d

s p a t i a l l y h o m o g e n e o u s m a g n e t i c f i e l d . C o n s i s t e

n c y o f t h e B
o

f i e l d o v e r t i m e w i l l b e d i s c u s s e d

h e r e ; h o m o g e n e i t y w i l l b e d i s c u s s e d i n t h e n e

x t s e c t i o n o f t h i s c h a p t e r . T h e f i e l d s t r e n g t h

m i g h t v a r y o v e r t i m e d u e t o a g i n g o f t h e m a g n e

t , m o v e m e n t o f m e t a l o b j e c t s n e a r t h e m a g n e t , a n

d t e m p e r a t u r e f l u c t u a t i o n s . H e r e i s a n e x a m p l e

o f a o n e l i n e N M R s p e c t r u m o f c y c l o h e x a n e r e c o

r d e d w h i l e t h e B
o

m a g n e t i c f i e l d w a s d r i f t i n g a

v e r y s i g n i f i c a n t a m o u n t . T h e f i e l d l o c k c a n c o m

p e n s a t e f o r t h e s e v a r i a t i o n s . T h e f i e l d l o c k i

s a s e p a r a t e N M R s p e c t r o m e t e r w i t h i n y o u r s p e

c t r o m e t e r . T h i s s p e c t r o m e t e r i s t y p i c a l l y t u n e

d t o t h e d e u t e r i u m N M R r e s o n a n c e f r e q u e n c y . I t

c o n s t a n t l y m o n i t o r s t h e r e s o n a n c e f r e q u e n c y

o f t h e d e u t e r i u m s i g n a l a n d m a k e s m i n o r c h a n g

e s i n t h e B
o

m a g n e t i c f i e l d t o k e e p t h e r e s o n a n

c e f r e q u e n c y c o n s t a n t . T h e d e u t e r i u m s i g n a l c o

m e s f r o m t h e d e u t e r i u m s o l v e n t u s e d t o p r e p a r

e t h e s a m p l e . T h e a n i m a t i o n w i n d o w c o n t a i n s p l

o t s o f t h e d e u t e r i u m r e s o n a n c e l o c k f r e q u e n c y

, t h e s m a l l a d d i t i o n a l m a g n e t i c f i e l d u s e d t o

c o r r e c t t h e l o c k f r e q u e n c y , a n d t h e r e s u l t a n t

B
o

f i e l d a s a f u n c t i o n o f t i m e w h i l e t h e m a g n e t

i c f i e l d i s d r i f t i n g . T h e l o c k f r e q u e n c y p l o t

d i s p l a y s t h e f r e q u e n c y w i t h o u t c o r r e c t i o n . I n

r e a l i t y , t h i s f r e q u e n c y w o u l d b e k e p t c o n s t a n t

b y t h e a p p l i c a t i o n o f t h e l o c k f i e l d w h i c h o

f f s e t s t h e d r i f t . O n m o s t N M R s p e c t r o m e t e r s t

h e d e u t e r i u m l o c k s e r v e s a s e c o n d f u n c t i o n . I t

p r o v i d e s t h e = 0 r e f e r e n c e . T h e r e s o n a n c e f r e q

u e n c y o f t h e d e u t e r i u m s i g n a l i n m a n y l o c k s o

l v e n t s i s w e l l k n o w n . T h e r e f o r e t h e d i f f e r e n c e

i n r e s o n a n c e f r e q u e n c y o f t h e l o c k s o l v e n t a

n d T M S i s a l s o k n o w n . A s a c o n s e q u e n c e , T M S d o e

s n o t n e e d t o b e a d d e d t o t h e s a m p l e t o s e t =

0 ; t h e s p e c t r o m e t e r c a n u s e t h e l o c k f r e q u e n c

y t o c a l c u l a t e = 0 .

S
T h e p u r p o s e o f s h i m c o i

l s o n a s p e c t r o m e t e r i s t o c o r r e c t m i n o r s p a t i

a l i n h o m o g e n e i t i e s i n t h e B
o

m a g n e t i c f i e l d . T h e s

e i n h o m o g e n e i t i e s c o u l d b e c a u s e d b y t h e m a g n e

t d e s i g n , m a t e r i a l s i n t h e p r o b e , v a r i a t i o n s i n

t h e t h i c k n e s s o f t h e s a m p l e t u b e , s a m p l e p e r m e a

b i l i t y , a n d f e r r o m a g n e t i c m a t e r i a l s a r o u n d t h e

m a g n e t . A s h i m c o i l i s d e s i g n e d t o c r e a t e a s m a

l l m a g n e t i c f i e l d w h i c h w i l l o p p o s e a n d c a n c e l

o u t a n i n h o m o g e n e i t y i n t h e B
o

m a g n e t i c f i e l d . B

e c a u s e t h e s e v a r i a t i o n s m a y e x i s t i n a v a r i e t y

o f f u n c t i o n a l f o r m s ( l i n e a r , p a r a b o l i c , e t c . ) , s

h i m c o i l s a r e n e e d e d w h i c h c a n c r e a t e a v a r i e t

y o f o p p o s i n g f i e l d s . S o m e o f t h e f u n c t i o n a l f o

r m s a r e l i s t e d i n t h e t a b l e b e l o w . S h i m C o i l

F u n c t i o n a l F o r m s S h i m
A (ppm)

XYZ B C

1.89 2.00 2.08 Interaction J (Hz) AB BC4

8Compare the 100 MHz and 400 MHz NMR spectra. The spectral lines from the B type spins are colored red. You can see how easy it would be to make the wrong choice as to the structure of the molecule based on the 100 MHz spectrum, although the chance of error might be reduced if you had further information, eg. the relative areas under the peaks. This topic is described in a later section of this chapter.

Sample Preparation
NMR samples are prepared by dissolving an analyte in a deuterium lock solvent. Several deuterium lock solvents are available . Some of these solvents will readily absorb moisture from the atmosphere and give water signal in your spectrum. It is therefore advisable to keep bottles of these solvents tightly capped when not in use. Most routine high resolution NMR samples are prepared and run in 5 mm glass NMR tubes. Always fill your NMR tubes to the same height with lock solvent. This will

minimize the amount of magnetic field shimming required. The animation window depicts a sample tube filled with solvent such that it fills the RF coil. The concentration of your sample should be great enough to give a good signal-to-noise ratio in your spectrum, yet minimize exchange effects found at high concentrations. The exact concentration of your sample in the lock solvent will depend on the sensitivity of the spectrometer. If you have no guidelines for a specific spectrometer, use one drop of analyte for liquids and one or two crystals for solid samples. The position of spectral absorption lines can be solvent dependent. Therefore, if you are comparing spectra or trying to identify an unknown sample by comparison to reference spectra, use the same solvent. The hydrogen NMR spectrum of ethanol is a good example of this solvent dependence. Compare the positions of the CH3, CH2, and OH absorption lines in a hydrogen NMR spectrum of ethanol in the lock solvents CDCl3 and D2O . Notice also that the relative peak heights are not the same in the two spectra. This is because the linewidths are not equal. The area under a peak, not the height of a peak, is proportional to the number of hydrogens in a sample. This point will be emphasized later in this chapter. Variations in the polarity and dielectric constant of the lock solvent will also effect the tuning of the probe. The correction of these effects are covered in the next section of this chapter on sample probe tuning.

Sample Probe Tuning

Variations in the polarity and dielectric constant of the lock solvent will affect the probe tuning. For this reason the probe should be tuned whenever the lock solvent is changed. Tuning the probe entails adjusting two capacitors on the RF probe. One capacitor is called the matching capacitor and the other the tuning capacitor. The matching capacitor matches the impedance of the loaded probe to that of the 50 Ohm cable coming from the spectrometer. The tuning capacitor changes the resonance frequency of the RF coil. Most spectrometers have a probe tuning mode of operation. This mode of operation presents a display of reflected power vs. frequency on the screen. The goal is to adjust the display so that the reflected power from the probe is zero at the resonance frequency of the nucleus you are examining. As the polarity and dielectric constant of the lock solvent changes, so does the bandwidth of the RF probe. This is significant because it affects the amount of RF power needed to produce a 90 degree pulse. The larger the bandwidth, the more power is needed to produce the 90 degree rotation.

Determinining a 90o Pulse

As pointed out in the previous section of this chapter, changes in the polarity and dielectric constant of the lock solvent affect the bandwidth of the RF probe which in turn affects the

amount of RF power needed to produce a 90 degree rotation. Most NMR spectrometers will not allow you to change the RF power, but they will permit you to change the pulse length. Therefore, if the bandwidth of the RF probe increases, you will need to increase the RF pulse width to produce a 90 degree pulse. To determine the pulse width needed to produce a 90 degree pulse, you should perform the following experiment using a sample which has a single absorption line and a relatively short T1. Record a series of spectra with incrementally longer RF pulse widths. Fourier transform the time domain signals and plot these lines as a function of pulse width. The peak height should vary sinusoidally with increasing pulse width. The 90 degree pulse width will be the first maximum. The 180 degree pulse width will be the first zero crossing. Many spectrometers have routines which will automatically record the data necessary to produce these plots. You should also be aware of the effect of varying the width of the RF pulse on the distribution of frequencies being delivered to your sample. Recall from the discussion of the convolution theorem in Chapter 5 that the Fourier pair of a sine wave which is turned on and off is a sinc function centered at the frequency of the sine wave. When you apply an RF pulse of width t in the time domain, you apply a distribution of frequencies to your sample. Not all of these frequencies will have sufficient B1 magnitude to produce a 90 degree rotation. The range of frequencies from the center of the distribution to the first zeros in the distribution is +/- 1/t. As your pulse width increases, the width of the distribution of frequencies in your pulse decreases. If the distribution is too narrow, you may not be applying the desired rotation to the entire sample.

Field Shimming
The purpose of shimming a magnet is to make the magnetic field more homogeneous and to obtain better spectral resolution. Shimming can be performed manually or by computer control. It is not the intent of this section to teach you a step-by-step procedure for shimming, but to present you with the basic theory so that you can, with the aid of your NMR instruction manual, shim your magnet. The reader is encouraged to write down or save the current shim settings before making changes to any of the current shims coil settings. Broad lines, asymmetric lines, and a loss of resolution are indications that a magnet needs to be shimmed. The shape of an NMR line is a good indication of which shim is misadjusted. Consider a single narrow NMR line. If we zoom in on this line we might see the following shape. . The following series of spectra depict the appearance of this spectral line in the presence of various inhomogeneities. Shim Spectrum Z3Z2 Z4 X, Y, ZX, or ZY

XY or X2-Y2 In general, asymmetric lineshapes result from mis-adjusted even-powered Z shims. This can be seen by looking at the shape of a Z2 shim field. As you go further away from the center of the sample in the +Z or -Z direction, the field increases, giving more components of the spectral line at higher fields. The higher the power of the Z inhomogeneity, the further away the asymmetry is from the center of the line. Symmetrically broadened lines are from mis-adjusted odd-powered Z shims. Consider the shape of the Z3 shim field. The top of the sample (+Z) is at a higher field, resulting in higher field spectral components, while the bottom (-Z) is at a lower field, giving more lower field spectral components. Transverse shims (X,Y) will cause large first order or second order spinning sidebands when the sample is spun. The shape of these inhomogeneities cause the sample, when it is spun, to experience a periodic variation in the magnetic field. Those shims (XY or X2-Y2) causing a spinning sample to experience two variations per cycle will create second order spinning sidebands.

Phase Cycling
There are a few artifacts of the detection circuitry which may appear in your spectrum if you record a single FID and Fourier transform it. Phase cycling is the technique used to eliminate these artifacts. The artifact will be introduced first, followed by the technique used to eliminate it. Electronic amplifiers often have small offsets in their output when no signal is being put in. This is referred to as the DC offset of the amplifier. A DC offset in the time domain is equivalent to a peak at zero frequency in the frequency domain. If there is an FID on top of a DC offset, its Fourier transform will have an additional peak at zero frequency in the spectrum. This picture has been simplified by presenting only the real part of the signal. The DC offset could be eliminated by spending thousands of dollars on better quality amplifiers. Alternatively, the artifact can be removed by taking an FID recorded with a 90 degree pulse applied along +X' , an FID recorded with a 90 degree pulse applied along -X' (note the phase change in the FID) , multiplying the FID recorded with a 90 degree pulse along -X' by -1 , adding the two FIDs, and Fourier transforming. This process only costs a little extra time and a few extra lines of computer code. Another type of artifact is caused by having unequal gains on the real and imaginary outputs of the quadrature detector. For a Fourier transform to produce a proper spectrum, it requires true real and imaginary inputs. When the inputs are equal in amplitude, there are no negative frequency artifacts in the spectrum. If the two inputs are different, the negative frequency components of a signal do not cancel. You can tell a negative frequency artifact because it appears to be the mirror image (but smaller) of a peak from the opposite sign end of the spectrum.

Negative frequency artifacts can be removed by recording an FID with Mx or the real signal (My or the imaginary signal) from channel 1 (2) of the quadrature detector. Another FID is recorded with Mx or the real signal (My or the imaginary signal) from channel 2 (1) of the quadrature detector. The two FIDs are then averaged. As a result, the amplitude of the real and imaginary inputs to the FT are equal, so when the FIDs are Fourier transformed, there are no negative frequency artifacts. The averaging described above can be achieved by applying a 90 degree pulse about +X and a 90 degree pulse about +Y, and adding the two resulting FIDs together. To eliminate all possible errors from different combinations of these types of pulses, phase cycling is applied. Phase cycling adds together eight FIDs recorded with the following phases to eliminate all the possible quadrature artifacts.

1-D Hydrogen Spectra

There are several parameters, in addition to the ones already discussed in this chapter, which must be set before a spectrum can be recorded. These include the width of the spectrum, number of data points in the spectrum, and the receiver gain. Some of these are automatically set to default values on some spectrometers. You are encouraged to refer to Chapter 5 for a deeper appreciation of the significance of these parameters. Once an FID is recorded and Fourier transformed, the resultant spectrum must be phased so that all the absorption lines are positive. You are encouraged to review Chapter 5 for an explanation of the need to phase correcting a spectrum. There are various automatic and manual phase correction algorithms on most NMR spectrometers. Here are a few examples of simple hydrogen NMR spectra to demonstrate the capabilities of NMR spectroscopy. As you become more knowledgeable about NMR, you will learn the relationship between peak locations, peak splitting, and molecular structure in NMR spectra. Molecule cyclohexane benzene toluene ethyl benzene acetone methyl ethyl ketone water ethanol ethanol 1-propanol Formula C6H12 C6H6 C6H5CH3 C6H5CH2CH3 CH3(C=O)CH3 CH3(C=O)CH2CH3 H2O CH3CH2OH CH3CH2OH CH3CH2CH2OH Solvent Spectrum CDCl3 CDCl3 CDCl3 CDCl3 CDCl3 CDCl3 D2O CDCl3 D2O CDCl3

2-propanol t-butanol 2-butanol pyridine

(CH3)2CHOH (CH3)3COH CH3CH2CH(OH)CH3 C5H5N

CDCl3 CDCl3 CDCl3 CDCl3

Integration
In addition to chemical shift and spin-spin coupling information, there is one additional piece of information which the chemist can use in determining the structure of a molecule from an NMR spectrum. This information is the relative area of absorption peaks in the spectrum. Here an absorption peak is defined as the family of peaks centered at a particular chemical shift. For example, if there is a triplet of peaks at a specific chemical shift, the number is the sum of the area of the three. The rule is that peak area is proportional to the number of a given type of spins in the molecule and in the sample. An example should help you understand this relationship. Consider the methyl ethyl ketone (CH3CH2(C=O)CH3) molecule and its hydrogen NMR spectrum. When the -CH2- ( = 2.25 ppm), -CH3 ( = 2.0 ppm), and CH3- ( = 0.9 ppm) peaks are integrated we get the following spectrum. The areas under the three types of peaks on this spectrometer are 26:39:39. Dividing each number by 13, we obtain a 2:3:3 ratio which is proportional to the number of -CH2- to -CH3 to CH3- hydrogens. There are a few assumptions which were made in presenting this rule.

The T1 and T2 values of all the spins are equal. There is no spin decoupling being performed. The signal-to-noise ratio is good. There is no sloping baseline in the spectrum.

Spin decoupling will be discussed in Chapter 9. You may correct for a sloping baseline by performing a baseline correction to the spectrum. A poor signal-to-noise ratio may be improved by performing signal averaging, discussed next.

SNR Improvement
The signal-to-noise ratio (SNR) of a spectral peak is the ratio of the average height of the peak to the standard deviation of the noise height in the baseline. Often spectroscopists approximate this quantity as the average peak height divided by the amplitude of the noise in the baseline. The signal to noise ratio may be improved by performing signal averaging. Signal averaging is the collection and averaging together of several spectra. The signals are present in each of the averaged spectra so their contribution to the resultant spectrum add. Noise is random so it does not add, but begins to cancel as the number of spectra averaged

increases. The signal-to-noise improvement from signal averaging is proportional to the square root of the number of spectra (N) averaged. SNR N1/2 Because of the need to perform phase cycling, you will need to have the number of averages equal to a multiple of the minimum number of phase cycling steps. Compare the results of averaging together the following number of spectra of a very dilute solution of methyl ethyl ketone. 1.00 1/2 N Spectrum N 8 1 2.83 16 4.00 80 8.94 800 28.28

Variable Temperature
Many NMR spectrometers have the ability to control the temperature of the sample in the probe. A schematic representation of the variable temperature hardware on an NMR spectrometer is depicted in the animation window. All of these spectrometers permit you to set the temperature to values above room temperature by just entering the desired temperature. You should be careful not to exceed the maximum temperature allowable for your probe because doing so will melt adhesives and components in the probe. Controlling the temperature below room temperature requires the use of hardware to cool the gas flowing over the sample. If this gas is air, it must be dry air to avoid condensation of water on the sample. Once the sample and probe have been cooled or heated, you should slowly return the probe to room temperature. Do not expose a cold probe to the moist atmosphere; condensation will result.

Troubleshooting
By now you may realize that an NMR spectrometer is a complex piece of instrumentation with many sub systems which must be functioning properly in order to record a useable NRM spectrum. The intent of this section is to provide you with a systematic method of identifying a problem with the spectrometer. Once a problem is identified, you are not necessarily expected to be able to solve it, but you will at least be able to describe the steps you took to diagnose the problem when speaking to a system administrator or a service representative from the manufacturer of your spectrometer. Click on this icon to start the diagnosis process in the animation window.

Cryogen Fills

Superconducting magnets require liquid nitrogen (N2) and liquid Helium (He). Because it is difficult to make a perfect dewar to hold these cryogens, they need to be periodically replenished. Liquid nitrogen is typically filled every 7 to 10 days and liquid helium every 200 to 300 days. Cryogen fills must be performed correctly to avoid injury to you and the magnet. The injuries to you from cryogenic liquids were described in Chapter 7. Injury to a magnet could include breaking a seal on a dewar or quenching a magnet. Both forms of magnet injuries are repairable, but at the least entail recharging the magnet; at the most, they can entail replacing the magnet. When filling the magnet with liquid nitrogen, you must be sure not to exceed the recommended fill pressure and rate for your magnet. If your magnet has two liquid nitrogen ports, one should be used for filling and the other for venting the boil-off gaseous nitrogen and overfill liquid nitrogen. A piece of tubing is typically placed on the vent port to direct the overfill liquid nitrogen away from the magnet seals, probe, and electronics. It is highly recommended that your liquid nitrogen tanks be made of non-magnetic stainless steel. Liquid helium fills are typically a two-person operation. Because they are done so infrequently, it is good to review the process before each fill. The fill requires a supply dewar of liquid helium, a special liquid helium transfer line, and a tank of pure compressed helium gas. Liquid helium is transferred from the liquid helium supply dewar up through the transfer line, into the helium dewar of the magnet. The transfer line goes into the top of the liquid helium supply dewar, but should never rest on the bottom of the dewar. The bottom of the dewar may contain frozen water, oxygen, and nitrogen which will be forced into your magnet if the transfer line touches the bottom during the transfer process. The compressed helium gas, mentioned earlier, is for pressurizing the liquid helium supply dewar with about 2 to 4 psi of pressure. Gauges on helium supply dewars can be very inaccurate, so do not count on them to give you an accurate reading. A helium pressure above the liquid forces the Helium into the magnet dewar. The transfer line is usually inserted into the magnet until it contacts a transfer flange in the bottom of the magnet. The nitrogen ports on the magnet should be plugged with a check valve during filling of the helium dewar of the magnet. This step prevents cryopumping, a process whereby nitrogen, water, and oxygen are condensed out of the atmosphere into the nitrogen dewar due to the magnet stacks being cooled by the helium. Many labs loosely plug the helium vents with tissue during the fill. This cuts down on cryopumping should the flow of the venting He drop. The best way to determine if the magnet is full is to look for a change in the gas cloud coming out of the magnet vents. When the magnet is full the cloud becomes very thick with a deep white center plume with a slight blue tint. The helium vents on the magnet should be closed promptly after the magnet is full.

Unix Primer

Most NMR spectrometers are controlled by a computer workstation. The NMR program which gives your spectrometer the look and feel you are used to is running on this computer. This computer is most likely running a UNIX operating system. The operating system is equivalent to DOS on a Microsoft system or OS-5 on a Macintosh system. Although you may be able to perform all the file transfer and manipulation commands from your NMR program, you may find it useful to know a few UNIX commands. This chapter is intended to give you enough information about UNIX to perform simple tasks in the UNIX operating system. The UNIX file system is divided into directories, which are equivalent to folders in some operating systems. Because UNIX is a multi-user system, there must be a way to keep your directories separate (and safe) from someone else's. To achieve this, there are accounts with passwords and ownership of directories. For example, you have an account which has a password. Logging on under your account gives you access to your directories and to other directories for which you have access (permission). The most useful, but least used command in UNIX is man. This is short for manual and gives you on-line help on every UNIX command. The more you use it, the easier it is to use. The animation window contains a table of a few simple UNIX commands. Entries in italics are examples and can be any string of characters or numbers.

The Basics of NMR

Chapter 9 CARBON-13 NMR
Introduction Decoupling NOE Population Inversion 1-D C-13 Spectra

Introduction
Many of the molecules studied by NMR contain carbon. Unfortunately, the carbon-12 nucleus does not have a nuclear spin, but the carbon-13 (C-13) nucleus does due to the presence of an unpaired neutron. Carbon-13 nuclei make up approximately one percent of the carbon nuclei on earth. Therefore, carbon-13 NMR spectroscopy will be less sensitive (have a poorer SNR) than hydrogen NMR spectroscopy. With the appropriate

concentration, field strength, and pulse sequences, however, carbon-13 NMR spectroscopy can be used to supplement the previously described hydrogen NMR information. Advances in superconducting magnet design and RF sample coil efficiency have helped make carbon13 spectroscopy routine on most NMR spectrometers. The sensitivity of an NMR spectrometer is a measure of the minimum number of spins detectable by the spectrometer. Since the NMR signal increases as the population difference between the energy levels increases, the sensitivity improves as the field strength increases. The sensitivity of carbon-13 spectroscopy can be increased by any technique which increases the population difference between the lower and upper energy levels, or increases the density of spins in the sample. The population difference can be increased by decreasing the sample temperature or by increasing the field strength. Several techniques for increasing the carbon-13 signal have been reported in the NMR literature. Unfortunately, or fortunately, depending on your perspective, the presence of spin-spin coupling between a carbon-13 nucleus and the nuclei of the hydrogen atoms bonded to the carbon-13, splits the carbon-13 peaks and causes an even poorer signal-to-noise ratio. This problem can be addressed by the use of a technique known as decoupling, addressed in the next section.

Decoupling
The signal-to-noise ratio in an NMR spectrometer is related to the population difference between the lower and upper spin state. The larger this difference the larger the signal. We know from chapter 3 that this difference is proportional to the strength of the Bo magnetic field. To understand decoupling, consider the familiar hydrogen NMR spectrum of HC(CH2CH3)3. The HC hydrogen peaks are difficult to see in the spectrum due to the splitting from the 6 -CH2- hydrogens. If the effect of the 6 -CH2- hydrogens could be removed, we would lose the 1:6:15:20:15:6:1 splitting for the HC hydrogen and get one peak. We would also lose the 1:3:1 splitting for the CH3 hydrogens and get one peak. The process of removing the spin-spin splitting between spins is called decoupling. Decoupling is achieved with the aid of a saturation pulse. If the affect of the HC hydrogen is removed, we see the following spectrum. Similarly, if the affect of the -CH3 hydrogens is removed, we see this spectrum. A saturation pulse is a relatively low power B1 field left on long enough for all magnetization to disappear. A saturation pulse applied along X' rotates magnetization clockwise about X' several times. As the magnetization is rotating, T2 processes cause the magnetization to dephase. At the end of the pulse there is no net Z, X, or Y magnetization. It is easier to see this behavior with the use of plots of MZ, MX', and MY' as a function of time. Since the B1 pulse is long, its frequency content is small. It therefore can be set to coincide with the location of the -CH2- quartet and saturate the -CH2- spin system. By saturating the -CH2- spins, the -CH2- peaks and the splittings disappear, causing the height of the now unsplit HC- and -CH3 peaks to be enhanced.

Now that the concept of decoupling has been introduced, consider the carbon-13 spectrum from CH3I. The NMR spectrum from the carbon-13 nucleus will yield one absorption peak in the spectrum. Adding the nuclear spin from one hydrogen will split the carbon-13 peak into two peaks. Adding one more hydrogen will split each of the two carbon-13 peaks into two, giving a 1:2:1 ratio. The final hydrogen will split each of the previous peaks, giving a 1:3:3:1 ratio. If the hydrogen spin system is saturated, the four lines collapse into a single line having an intensity which is eight times greater than the outer peak in the 1:3:3:1 quartet since 1+3+3+1=8 . In reality, we see a single line with a relative intensity of 24. Where did the extra factor of three come from?

NOE
The answer to the question raised in the previous paragraph is the nuclear Overhauser effect (NOE). To understand the NOE, consider a set of coupled hydrogen and carbon-13 nuclei. Assume that the red-green nuclei are carbon-13 and the blue-pink nuclei are hydrogen. T1CC is T1 relaxation due to interactions between carbon-13 nuclei. T1HH is T1 relaxation due to interactions between hydrogen nuclei. T1CH is T1 relaxation due to interactions between carbon-13 and hydrogen nuclei. MZ(C) is the magnetization due to carbon-13 nuclei. Mo(C) is the equilibrium magnetization of carbon-13. MZ(H) is the magnetization due to hydrogen nuclei. Mo(H) is the equilibrium magnetization of hydrogen. The equations governing the change in the Z magnetization with time are:

If we saturate the hydrogen spins, MZ(H) = 0.

Letting the system equilibrate, d MZ(C) /dt = 0 .

Rearranging the previous equation, we obtain an equation for MZ(C) . . Note that MZ(C) has increased by Mo(H) T1CC / T1CH which is approximately 2 Mo(C), giving a total increase of a factor of 3 relative to the total area of the undecoupled peaks. This explains the extra factor of three (for a total intensity increase of 24) for the carbon-13 peak when hydrogen decoupling is used in the carbon-13 spectrum of CH3I.

The following spin-echo sequence has been modified to decouple the hydrogen spins from the carbon-13 spins. The signal is recorded as the second half of the echo.

Population Inversion
Another method of improving the NMR signal in systems with spin-spin coupling is population inversion. To understand the concept of a population inversion, recall from Chapter 3 that Boltzmann statistics tell us that there are more spins in the lower spin state than the upper one of a two spin state system. Population inversion is the interchange of the populations of these two spin states so that there are more spins in the upper state then the lower one. To understand how a population inversion improves the signal-to-noise ratio in a spectrum, consider the CHI3 molecule. CHI3 will have four energy levels (L1, L2, L3, and L4) due to C-H spin-spin coupling. There are two carbon-13 absorption frequencies f1 and f2 and two hydrogen absorption frequencies f3 and f4. The population distribution between the four levels is such that the lowest state has the greatest population and the highest the lowest population. The two intermediate states will have populations between the outer two as indicated by the thickness of the levels in the accompanying diagram. The four lines in the spectrum will have intensities related to the population difference between the two levels spanned by the frequency. The two carbon-13 absorption lines (f1 and f2) will have a lower intensity than the hydrogen lines (f3 and f4) due to the smaller population difference between the two states joined by f1 and f2. If the populations of L3 and L1 are inverted or interchanged with a frequency selective 180 degree pulse at f3, the signal at f2 will be enhanced because of the greater population difference between the states joined by f2. It should be noted that the signal at f1 will be inverted because the upper state of the two joined by f1 has a greater population than the lower one. An example of a population inverting pulse sequence designed to enhance the carbon-13 spectral lines is depicted in the animation window. The 180 degree pulse at f3 has a narrow band of frequencies centered on f3 that selectively rotates only the magnetization at f3 by 180 degrees.

1-D C-13 Spectra

The following table of compounds contains links to their corresponding one-dimensional carbon-13 NMR spectra. The spectra were recorded on a 300 MHz NMR spectrometer with a delay time between successive scans of two seconds. This relatively short delay time may cause differences in the peak heights due to variations in T1 values. Other differences may be caused by variations in the nuclear Overhauser effect. In spectra recorded with deuterated chloroform (CDCl3) as the lock solvent, the three peaks at = 75 are due to splitting of the CDCl3 carbon-13 peak by the nuclear spin = 1 deuterium nucleus. S Molecule o l v

e n t S p e c t r u m C6H6 CDCl3 toluene C6H5CH3 CDCl3 C6H12 cyclohexane Formula CH3(C=O)CH3 CDCl3 methyl ethyl ketone C6H5CH2CH3 CH3(C=O)CH2CH3 CDCl3 ethyl benzene benzene Iethanol n f o r m a t i o n C D C l
3

CDCl3

CDCl3

e t h a n

o l C H
3

C H
2

O H D
2

O 1 p r o p a n o l C H
3

C H
2

C H
2

O H C D C l
3

p r o p a n o l ( C H
3

)
2

C H O H C D C l
3

t b u t n o l ( C H
3

)
3

C O H

C D C l
3

2 b u t a n o l C H
3

C H
2

C H ( O H ) C H
3

C D C l
3

p y r i d i n e

C
5

H
5

N C D C l
3

T h e B a s i c s o f N M R a c e t o n e

C 2

I J C E

I
I n C h a p t e r 6 w e s a w t h e m e c h a n

i c s o f t h e s p i n e c h o s e q u e n c e . R e c a l l t h a t a 9 0

d e g r e e p u l s e r o t a t e s m a g n e t i z a t i o n f r o m a s i n

g l e t y p e o f s p i n i n t o t h e X Y p l a n e . T h e m a g n e t i

z a t i o n d e p h a s e s , a n d t h e n a 1 8 0 d e g r e e p u l s e i s

a p p l i e d w h i c h r e f o c u s s e s t h e m a g n e t i z a t i o n . W

h e n a m o l e c u l e w i t h J c o u p l i n g ( s p i n s p i n c o u

p l i n g ) i s s u b j e c t e d t o a s p i n e c h o s e q u e n c e , s

o m e t h i n g u n i q u e b u t p r e d i c t a b l e o c c u r s . L o o k a

t w h a t h a p p e n s t o t h e m o l e c u l e A
2

C C B w h e r e

A a n d B a r e s p i n 1 / 2 n u c l e i e x p e r i e n c i n g r e s

o n a n c e . T h e N M R s p e c t r u m f r o m a 9 0 F I D s e q u e n c

e l o o k s l i k e t h i s . W i t h a s p i n e c h o s e q u e n c e

t h i s s a m e m o l e c u l e g i v e s a r a t h e r p e c u l i a r s p

e c t r u m o n c e t h e e c h o i s F o u r i e r t r a n s f o r m e d . H

e r e i s a s e r i e s o f s p e c t r a r e c o r d e d a t d i f f e r

e n t T E t i m e s . T h e a m p l i t u d e o f t h e p e a k s h a v e

b e e n s t a n d a r d i z e d t o b e a l l p o s i t i v e w h e n T E =

0 m s . T o u n d e r s t a n d w h a t i s h a p p e n i n g , c o n s i d e

r t h e m a g n e t i z a t i o n v e c t o r s f r o m t h e A n u c l e i

. T h e r e a r e t w o a b s o r p t i o n s l i n e s i n t h e s p e c t

r u m f r o m t h e A n u c l e i , o n e a t + J / 2 a n d o n e a t

J / 2 . A t e q u i l i b r i u m , t h e m a g n e t i z a t i o n v e c t o r s

f r o m t h e + J / 2 a n d J / 2 l i n e s i n t h e s p e c t r u m

a r e b o t h a l o n g + Z . A 9 0 d e g r e e p u l s e r o t a t e s

b o t h m a g n e t i z a t i o n v e c t o r s i n t o t h e X Y p l a n e

. A s s u m i n g a r o t a t i n g f r a m e o f r e f e r e n c e a t
o

= , t h e v e c t o r s p r e c e s s a c c o r d i n g t o t h e i r L a r

m o r f r e q u e n c y a n d d e p h a s e d u e t o T
2

* . W h e n t h e

1 8 0 d e g r e e p u l s e i s a p p l i e d , i t r o t a t e s t h e m

a g n e t i z a t i o n v e c t o r s b y 1 8 0 d e g r e e s a b o u t t h e

X ' a x i s . I n a d d i t i o n t h e + J / 2 a n d J / 2 m a g n e t

i z a t i o n v e c t o r s c h a n g e p l a c e s b e c a u s e t h e 1 8 0

d e g r e e p u l s e a l s o f l i p s t h e s p i n s t a t e o f t h

e B n u c l e u s w h i c h i s c a u s i n g t h e s p l i t t i n g o f

t h e A s p e c t r a l l i n e s . T h e t w o g r o u p s o f v e c t

o r s w i l l r e f o c u s a s t h e y e v o l v e a t t h e i r o w n

L a r m o r f r e q u e n c y . I n t h i s e x a m p l e t h e p r e c e s s i

o n i n t h e X Y p l a n e h a s b e e n s t o p p e d w h e n t h e

v e c t o r s h a v e r e f o c u s s e d . Y o u w i l l n o t i c e t h a t

t h e t w o g r o u p s o f v e c o t r s d o n o t r e f o c u s o n t

h e Y a x i s . T h e p h a s e o f t h e t w o v e c t o r s o n r e

f o c u s s i n g v a r i e s a s a f u n c t i o n o f T E . T h i s p h a

s e v a r i e s a s a f u n c t i o n o f T E a t a r a t e e q u a l

t o t h e s i z e o f t h e s p i n s p i n c o u p l i n g f r e q u e

n c y . T h e r e f o r e , m e a s u r i n g t h i s r a t e o f c h a n g e o

f p h a s e w i l l g i v e u s t h e s i z e o f t h e s p i n s p i

n c o u p l i n g c o n s t a n t . T h i s i s t h e b a s i s o f o n e

t y p e o f t w o d i m e n s i o n a l ( 2 D ) N M R s p e c t r o s c o p

y .

J
I n a 2 D J r e s o l v e d N M R e x p e r i m e n t , t i m e

d o m a i n d a t a i s r e c o r d e d a s a f u n c t i o n o f T E a

n d t i m e . T h e s e t w o t i m e d i m e n s i o n s w i l l r e f e r r e

d t o a s t
1

a n d t
2

. F o r t h e A
2

C C B m o l e c u l e , t h

e c o m p l e t e t i m e d o m a i n s i g n a l s l o o k l i k e t h i s .

T h i s d a t a i s F o u r i e r t r a n s f o r m e d f i r s t i n t h e

t
2

d i r e c t i o n t o g i v e a n f
2

d i m e n s i o n , a n d t h e

n i n t h e t
1

d i r e c t i o n t o g i v e a n f
1

d i m e n s i o n

. D i s p l a y i n g t h e d a t a a s s h a d e d c o n t o u r s , w e h

a v e t h e f o l l o w i n g t w o d i m e n s i o n a l d a t a s e t . R o

t a t i n g t h e d a t a b y 4 5 d e g r e e s m a k e s t h e p r e s e

n t a t i o n c l e a r e r . T h e f
1

d i m e n s i o n g i v e s u s J c

o u p l i n g i n f o r m a t i o n w h i l e t h e f
2

d i m e n s i o n g i

v e s c h e m i c a l s h i f t i n f o r m a t i o n . T h i s t y p e o f e

x p e r i m e n t i s c a l l e d h o m o n u c l e a r J R e s o l v e d 2 -

D N M R . T h e r e i s a l s o h e t e r o n u c l e a r J r e s o l v e d

2 D N M R w h i c h u s e s a s p i n e c h o s e q u e n c e a n d t

e c h n i q u e s s i m i l a r t o t h o s e d e s c r i b e d i n C h a p t

e r 9 .

C
T h e a p p l i c a t i o n o f t w o 9 0 d e g r e e p u l

s e s t o a s p i n s y s t e m w i l l g i v e a s i g n a l w h i c h

v a r i e s w i t h t i m e t
1

w h e r e t
1

i s t h e t i m e b e t w e

e n t h e t w o p u l s e s . T h e F o u r i e r t r a n s f o r m o f b o t

h t h e t
1

a n d t
2

d i m e n s i o n s g i v e s u s c h e m i c a l s

h i f t i n f o r m a t i o n . T h e 2 D h y d r o g e n c o r r e l a t e d c

h e m i c a l s h i f t s p e c t r u m o f e t h a n o l w i l l l o o k l i

k e t h i s . T h e r e i s a w e a l t h o f i n f o r m a t i o n f o u n d

i n a C O S Y s p e c t r u m . A n o r m a l ( c h e m i c a l s h i f t )

1 D N M R s p e c t r u m c a n b e f o u n d a l o n g t h e t o p a n

d l e f t s i d e s o f t h e 2 D s p e c t r u m . C r o s s p e a k s e

x i s t i n t h e 2 D C O S Y s p e c t r u m w h e r e t h e r e i s s

p i n s p i n c o u p l i n g b e t w e e n h y d r o g e n s . T h e r e a r e

c r o s s p e a k s b e t w e e n O H a n d C H
2

h y d r o g e n s , a n d

a l s o b e t w e e n C H
3

a n d C H
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h y d r o g e n s h y d r o g e n s . T

h e r e a r e n o c r o s s p e a k s b e t w e e n t h e C H
3

a n d O H

h y d r o g e n s b e c a u s e t h e r e i s n o c o u p l i n g b e t w e e

n t h e C H
3

a n d O H h y d r o g e n s . H e t e r o n u c l e a r c o r r

e l a t e d 2 D N M R i s a l s o p o s s i b l e a n d u s e f u l .

T h e f o l l o w i n g t a b l e p r e s e n t s s o m e o f t h e h u

n d r e d s o f p o s s i b l e 2 D N M R e x p e r i m e n t s a n d t h e

d a t a r e p r e s e n t e d b y t h e t w o d i m e n s i o n s . T h e i n

t e r e s t e d r e a d e r i s d i r e c t e d t o t h e N M R l i t e r t u

r e f o r m o r e i n f o r m a t i o n . 2 D E x p e r i m e n t ( A c r o n y

m ) CH3CH2OH f1 Homonuclear J resolved Heteronuclear J resolved J JAX Homoculclear correlated spectroscopy (COSY) A Heteronuclear correlated spectroscopy (HETCOR) A Nuclear Overhauser Effect (2D-NOE) H, JHH Type Spectrum 2D- A + X X INADEQUATE f2
X A X H

, JHH The follo wing table of molec ules conta ins links to their corre spond ing twodime nsion al NMR spect ra. The spect ra were recor ded on a 300 MHz NMR spect romet er

with CDCl as 3 the lock solve nt. Molec ule methyl ethyl ketone D e f i n i t i o n C O S Y e t h a n o l C H
3

C H
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y l b e n z e n e C
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5

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T h e B a s i c s o f N M R F o r m u l a

C A

I D S S M

S F

I
N u c l e a r m a g n e t i c r e s o n a n c e s p e c t r o s

c o p y i s o n e o f t h e r i c h e s t s p e c t r o s c o p i e s a v a i

l a b l e . I n p r e v i o u s c h a p t e r s y o u h a v e s e e n h o w i

t c a n b e u s e d t o e l u c i d a t e c h e m i c a l s t r u c t u r e .

I n t h i s c h a p t e r y o u w i l l s e e s o m e o f t h e o t h e r

m o r e a d v a n c e d a p p l i c a t i o n s o f N M R . T w o o f t h e s

e t e c h n i q u e s , s o l i d s t a t e N M R a n d g r a d i e n t e n h a

n c e d s p e c t r o s c o p y , w i l l a s s i s t u s f u r t h e r i n t h

e d e t e r m i n a t i o n o f m o l e c u l a r s t r u c t u r e . T w o a d d

i t i o n a l t e c h n i q u e s w i l l a s s i s t u s i n s t u d y i n g

m o l e c u l a r d y n a m i c s , o r t h e r o t a t i o n a l a n d t r a n s

l a t i o n a l m o t i o n s o f m o l e c u l e s . T h e l a s t t e c h n i q

u e , N M R m i c r o s c o p y , w i l l e n a b l e u s t o d e t e r m i n e

t h e s p a t i a l d i s t r i b u t i o n o f n u c l e a r s p i n s i n a

s a m p l e .

D
D i f f u s i o n i s t h e m o t i o n o f p a r t i c l

e s d u e t o B r o w n i a n m o t i o n . T h e d i f f u s i o n c o e f f i

c i e n t , D , i s a m e a s u r e o f t h e d i f f u s i o n . T h e p u l s

e d g r a d i e n t s p i n e c h o s e q u e n c e p e r m i t s u s t o m

e a s u r e t h e d i f f u s i o n c o e f f i c i e n t . T h e s e q u e n c e

i s i n t h e o r y c a p a b l e o f m e a s u r i n g b o t h t h e r o t

a t i o n a l a n d t r a n s l a t i o n a l d i f f u s i o n c o e f f i c i e n

t s , b u t i s u s e d p r i m a r i l y f o r s t u d y i n g t r a n s l a t

i o n a l d i f f u s i o n . T o u n d e r s t a n d h o w t h e p u l s e d -

g r a d i e n t s p i n e c h o s e q u e n c e a l l o w s u s t o m e a s

u r e d i f f u s i o n , c o n s i d e r t h e t i m i n g d i a g r a m f o r

t h e s e q u e n c e . T h i s s e q u e n c e i s v e r y s i m i l a r t

o t h e s p i n e c h o s e q u e n c e i n t r o d u c e d i n C h a p t e

r 6 , e x c e p t t h a t t w o g r a d i e n t p u l s e s h a v e b e e n

a p p l i e d . T h e s e t w o g r a d i e n t p u l s e s a r e i d e n t i

c a l i n a m p l i t u d e , G , a n d w i d t h , . T h e t w o g r a d i e n

t p u l s e s a r e s e p a r a t e d b y a t i m e a n d a r e p l a c

e d s y m m e t r i c a l l y a b o u t t h e 1 8 0 d e g r e e p u l s e .

T h e f u n c t i o n o f t h e g r a d i e n t p u l s e s i s t o d e p

h a s e m a g n e t i z a t i o n f r o m s p i n s w h i c h h a v e d i f f

u s e d t o a n e w l o c a t i o n i n t h e p e r i o d . T h e s e p

u l s e s h a v e n o e f f e c t o n s t a t i o n a r y s p i n s . F o r

e x a m p l e , a s t a t i o n a r y s p i n e x p o s e d t o t h e f i r s

t g r a d i e n t p u l s e , a p p l i e d a l o n g t h e Z a x i s , w i l

l a c q u i r e a p h a s e i n r a d i a n s g i v e n b y

= 2 z

G
z

d t . T h e s p i n w i l l a c q u i r e a n e q u a l b u t o p p o

s i t e p h a s e f r o m t h e s e c o n d p u l s e s i n c e t h e p u l

s e s a r e o n d i f f e r e n t s i d e s o f t h e 1 8 0 d e g r e e R

F p u l s e . T h u s , t h e i r e f f e c t s c a n c e l e a c h o t h e r o

u t . C o n s i d e r t h e f o l l o w i n g i l l u s t r a t i o n o f t h e

e f f e c t o f t h e g r a d i e n t p u l s e s o n t h e p h a s e o

f s t a t i o n a r y a n d m o v i n g s p i n s . T h e i l l u s t r a t i o

n p r e s e n t s t h e p h a s e o f a d i f f u s i n g s p i n r e l a

t i v e t o t h a t o f a r e f e r e n c e s p i n a n d a s t a t i o

n a r y s p i n . T h e r e f e r e n c e s p i n i s o n e w h i c h e x p

e r i e n c e s n o g r a d i e n t p u l s e s . T h e s t a t i o n a r y s p

i n i s n o t d i f f u s i n g d u r i n g t h e t i m e i l l u s t r a t

e d b y t h e s e q u e n c e . T h e d i f f u s i n g s p i n m o v e s a

l o n g Z d u r i n g t h e s e q u e n c e . T h e b l u e l i n e i n t

h e t i m i n g d i a g r a m r e p r e s e n t s t h e t i m e o f t h e

1 8 0 d e g r e e p u l s e i n t h e s p i n e c h o s e q u e n c e . W h

e n y o u p u t t h e i l l u s t r a t i o n i n t o m o t i o n , t h e s

t a t i o n a r y s p i n c o m e s b a c k i n t o p h a s e w i t h t h e

r e f e r e n c e o n e , i n d i c a t i n g a p o s i t i v e c o n t r i b u

t i o n t o t h e e c h o . T h e d i f f u s i n g s p i n d o e s n o t

c o m e b a c k i n t o p h a s e w i t h t h e r e f e r e n c e s p i n

s o i t d i m i n i s h e s t h e e c h o h e i g h t . T h e r e l a t i o

n s h i p b e t w e e n t h e s i g n a l ( S ) o b t a i n e d i n t h e

p r e s e n c e o f a g r a d i e n t a m p l i t u d e G
i

i n t h e i d

i r e c t i o n a n d t h e d i f f u s i o n c o e f f i c i e n t i n t h e

s a m e d i r e c t i o n i s g i v e n b y t h e f o l l o w i n g e q u

a t i o n w h e r e S
o

i s t h e s i g n a l a t z e r o g r a d i e n t

. S / S
o

= e x p [ ( G
i

)
2

D
i

( / 3 ) ] T h e d i f f u s i o n

c o e f f i c i e n t i s t y p i c a l l y c a l c u l a t e d f r o m a p

l o t o f l n ( S / S
o

) v e r s u s ( G )
2

( / 3 ) . D i f f u s i o

n i n t h e x , y , o r z d i r e c t i o n m a y b e m e a s u r e d b

y a p p l y i n g t h e g r a d i e n t r e s p e c t i v e l y i n t h e x

, y , o r z d i r e c t i o n .

S
T h e s p i n l a t t i c e a n d s p

i n s p i n r e l a x a t i o n t i m e s , T
1

a n d T
2

r e s p e c t i v e l

y , o f t h e c o m p o n e n t s o f a s o l u t i o n a r e v a l u a b l e

t o o l s f o r s t u d y i n g m o l e c u l a r d y n a m i c s . Y o u s a w

i n C h a p t e r 3 t h a t T
1 1

i s p r o p o r t i o n a l t o t h e

n u m b e r o f m o l e c u l a r m o t i o n s a t t h e L a r m o r f r e

q u e n c y , w h i l e T
2 1

i s p r o p o r t i o n a l t o t h e n u m b e

r o f m o l e c u l a r m o t i o n s a t f r e q u e n c i e s l e s s t h a

n o r e q u a l t o t h e L a r m o r f r e q u e n c y . W h e n w e a r e

d e a l i n g w i t h s o l u t i o n s t h e s e m o t i o n s a r e p r e d

o m i n a n t l y r o t a t i o n a l m o t i o n s . T h e r e a r e m a n y p

u l s e s e q u e n c e s w h i c h m a y b e u s e d t o m e a s u r e T

a n d T
2

. T h e i n v e r s i o n r e c o v e r y , 9 0 F I D , a n d s p

i n e c h o s e q u e n c e s m a y b e u s e d t o m e a s u r e T
1

. E

a c h t e c h n i q u e h a s i t s o w n a d v a n t a g e s a n d d i s a

d v a n t a g e s . T h e s p i n e c h o s e q u e n c e m a y b e u s e d

t o m e a s u r e T
2

. T
1

M e a s u r e m e n t R e c a l l t h e t i m i

n g d i a g r a m f o r a n i n v e r s i o n r e c o v e r y s e q u e n c e

f i r s t p r e s e n t e d i n C h a p t e r 6 . T h e s i g n a l a s

a f u n c t i o n o f T I w h e n t h e s e q u e n c e i s n o t r e p

e a t e d i s S = k ( 1 2 e
T I / T 1

) . I f t h e c u r v

e i s w e l l d e f i n e d ( i . e . i f t h e r e i s a h i g h d e

n s i t y o f d a t a p o i n t s r e c o r d e d a t d i f f e r e n t T I

t i m e s ) , t h e T
1

v a l u e c a n b e d e t e r m i n e d f r o m t

h e z e r o c r o s s i n g o f t h e c u r v e w h i c h i s T
1

l n 2

. A l t e r n a t i v e l y t h e r e l a x a t i o n c u r v e a s a f u n

c t i o n o f T I m a y b e f i t u s i n g t h e e q u a t i o n S

= S
o

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T I / T 1

) . T h i s a p p r o a c h i s f a v o r e d

w h e n t h e r e a r e f e w e r d a t a p o i n t s a s a f u n c t i o

n o f T I . T
1

m a y a l s o b e d e t e r m i n e d f r o m a 9 0 -

F I D o r s p i n e c h o s e q u e n c e w h i c h i s r e p e a t e d a

t v a r i o u s r e p e t i t i o n t i m e s ( T R ) . F o r e x a m p l e , i

f t h e 9 0 F I D s e q u e n c e i s r e p e a t e d m a n y t i m e s

a t T R
1

a n d t h e n m a n y t i m e s a t T R
2

, T R
3

, e t c , t h e

p l o t o f s i g n a l a s a f u n c t i o n o f T R w i l l b e a

n e x p o n e n t i a l g r o w t h o f t h e f o r m S = k ( 1 -

e
T R / T 1

) . T h i s d a t a m a y b e f i t t o o b t a i n T
1

. T h e d i f f i c u l t y w i t h f i t t i n g t h i s d a t a a n d t

h e i n v e r s i o n r e c o v e r y d a t a i s a l a c k o f k n o w l

e d g e o f t h e v a l u e o f t h e e q u i l i b r i u m m a g n e t i z

a t i o n o r s i g n a l S
o

. O t h e r t e c h n i q u e s h a v e b e e n

p r o p o s e d w h i c h d o n o t r e q u i r e k n o w l e d g e o f t

h e e q u i l i b r i u m m a g n e t i z a t i o n o r s i g n a l . T
2

e a s u r e m e n t M e a s u r e m e n t o f t h e s p i n s p i n r e l a x

a t i o n t i m e r e q u i r e s t h e u s e o f a s p i n e c h o p u

l s e s e q u e n c e . T h e e c h o a m p l i t u d e , S , a s a f u n c t i

o n o f e c h o t i m e , T E , i s e x p o n e n t i a l l y d e c a y i n g .

P l o t t i n g l n ( S / S
o

) v e r s u s T E y i e l d s a s t r a i g h t

l i n e , t h e s l o p e o f w h i c h i s 1 / T
2

. A l i n e a r l e

a s t s q u a r e s a l g o r i t h m i s o f t e n u s e d t o f i n d t

h e s l o p e a n d h e n c e T
2

v a l u e . T h i s a p p r o a c h c a n

r e s u l t i n l e a d t o l a r g e e r r o r s i n t h e c a l c u l

a t e d T
2

v a l u e s w h e n t h e d a t a h a s n o i s e . T h e l a

t e r p o i n t s i n t h e d e c a y c u r v e h a v e p o o r e r s i g

n a l t o n o i s e r a t i o t h a n t h e e a r l i e r p o i n t s , b u

t a r e g i v e n e q u a l w e i g h t b y t h e l i n e a r l e a s t

s q u a r e s a l g o r i t h m . T h e s o l u t i o n t o t h i s p r o b l e

m i s t o u s e a n o n l i n e a r l e a s t s q u a r e s p r o c e d

u r e .

S
W e s a w i n C h a p t e r 4 t h a t t h e m a g n i t u d

e o f t h e c h e m i c a l s h i f t i s r e l a t e d t o t h e e x t e

n t t o w h i c h t h e e l e c t r o n c a n s h i e l d t h e n u c l e u

s f r o m t h e a p p l i e d m a g n e t i c f i e l d . I n a s p h e r i c

a l l y s y m m e t r i c m o l e c u l e , t h e c h e m i c a l s h i f t i s

i n d e p e n d e n t o f m o l e c u l a r o r i e n t a t i o n . I n a n a s y

m m e t r i c m o l e c u l e , t h e c h e m i c a l s h i f t i s d e p e n d e

n t o n t h e o r i e n t a t i o n . T h e m a g n e t i c f i e l d e x p e r

i e n c e d b y t h e n u c l e u s v a r i e s a s a f u n c t i o n o f

t h e o r i e n t a t i o n o f t h e m o l e c u l e i n t h e m a g n e t i

c f i e l d . T h e N M R s p e c t r u m f r o m a r a n d o m d i s t r i b

u t i o n o f f i x e d o r i e n t a t i o n s , s u c h a s i n a s o l i d

, w o u l d l o o k l i k e t h i s . T h e l a r g e r s i g n a l a t l o w

e r f i e l d s t r e n g t h i s d u e t o t h e f a c t t h a t t h e r

e a r e m o r e p e r p e n d i c u l a r o r i e n t a t i o n s . I n a n o n

v i s c o u s l i q u i d , t h e f i e l d s a t t h e v a r i o u s o r i e n

t a t i o n s a v e r a g e o u t d u e t o t h e t u m b l i n g o f t h e

m o l e c u l e . T h e a n i s o t r o p i c c h e m i c a l s h i f t i s o

n e r e a s o n w h y t h e N M R s p e c t r a o f s o l i d s a m p l e

s d i s p l a y b r o a d s p e c t r a l l i n e s . A n o t h e r r e a s o n

f o r b r o a d s p e c t r a l l i n e s i s d i p o l a r b r o a d e n i

n g . A d i p o l a r i n t e r a c t i o n i s o n e b e t w e e n t w o s

p i n 1 / 2 n u c l e i . T h e m a g n i t u d e o f t h e i n t e r a c t i

o n v a r i e s w i t h a n g l e a n d d i s t a n c e r . A s a f u n c

t i o n o f , t h e m a g n e t i c f i e l d B e x p e r i e n c e d b y

t h e r e d n u c l e u s i s ( 3 c o s
2

1 ) . A g r o u p o f d

i p o l e s w i t h a r a n d o m d i s t r i b u t i o n o f o r i e n t a t

i o n s , a s i n a s o l i d , g i v e s t h i s s p e c t r u m . T h e h i

g h e r s i g n a l a t m i d f i e l d s t r e n g t h i s d u e t o t

h e l a r g e r p r e s e n c e o f o r i e n t a t i o n s p e r p e n d i c u

l a r t o t h e d i r e c t i o n o f t h e B
o

f i e l d . T h i s s i g

n a l i s m a d e u p o f c o m p o n e n t s f r o m t h e r e d a n d

b l u e n u c l e i i n t h e d i p o l e . I n a n o n v i s c o u s l i

q u i d , t h e i n t e r a c t i o n a v e r a g e s o u t d u e t o t h e

p r e s e n c e o f r a p i d t u m b l i n g o f t h e m o l e c u l e . W

h e n t h e a n g l e i n t h e a b o v e e q u a t i o n i s 5 4 . 7
o

1 2 5 . 3
o

, 2 3 4 . 7
o

, o r 3 0 5 . 3
o

, t h e d i p o l e i n t e r a c t i o

n v a n i s h e s . T h e a n g l e 5 4 . 7
o

i s c a l l e d t h e m a g i

c a n g l e ,
m

. I f a l l t h e m o l e c u l e s c o u l d b e p o s i

t i o n e d a t
m

, t h e s p e c t r u m w o u l d n a r r o w t o t h e

f a s t t u m b l i n g l i m i t . S i n c e t h i s i s n o t p o s s i b

l e , t h e n e x t b e s t t h i n g i s t o c a u s e t h e a v e r a g

e o r i e n t a t i o n o f t h e m o l e c u l e s t o b e
m

. E v e n

t h i s i s n o t e x a c t l y p o s s i b l e , b u t t h e c l o s e s t

a p p r o x i m a t i o n i s t o r a p i d l y s p i n t h e e n t i r e s

a m p l e a t a n a n g l e
m

r e l a t i v e t o B
o

. I n s o l i d s

t a t e N M R , s a m p l e s a r e p l a c e d i n a s p e c i a l s a m p

l e t u b e a n d t h e t u b e i s p l a c e d i n s i d e a r o t o r

. T h e r o t o r , a n d h e n c e t h e s a m p l e , a r e o r i e n t e d

a t a n a n g l e
m

w i t h r e s p e c t t o t h e B
o

m a g n e t i c

f i e l d . T h e s a m p l e i s t h e n s p u n a t a r a t e o f t

h o u s a n d s o f r e v o l u t i o n s p e r s e c o n d . T h e s p i n n

i n g r a t e m u s t b e c o m p a r a b l e t o t h e s o l i d s t a t

e l i n e w i d t h . T h e c e n t r i f i g a l f o r c e c r e a t e d b y

s p i n n i n g t h e s a m p l e t u b e a t a r a t e o f s e v e r a

l t h o u s a n d s o f r e v o l u t i o n s p e r s e c o n d i s e n o u

g h t o d e s t r o y a t y p i c a l g l a s s N M R s a m p l e t u b e

. S p e c i a l l y e n g i n e e r e d s a m p l e t u b e s a n d r o t o r s

a r e n e e d e d .

M
N M R m i c r o s c o p y i s t h e a p p l i c a

t i o n o f m a g n e t i c r e s o n a n c e i m a g i n g ( M R I ) p r i n c

i p l e s t o t h e s t u d y o f s m a l l o b j e c t s . O b j e c t s w h

i c h a r e s t u d i e d a r e t y p i c a l l y l e s s t h a n 5 m m i

n d i a m e t e r . N M R m i c r o s c o p y r e q u i r e s s p e c i a l h a r

d w a r e n o t f o u n d o n c o n v e n t i o n a l N M R s p e c t r o m e t

e r s . T h i s i n c l u d e s g r a d i e n t c o i l s t o p r o d u c e a

g r a d i e n t i n t h e m a g n e t i c f i e l d a l o n g t h e X , Y , a

n d Z a x e s ; g r a d i e n t c o i l d r i v e r s ; R F p u l s e s h a

p i n g s o f t w a r e ; a n d i m a g e p r o c e s s i n g s o f t w a r e . R

e s u l t a n t i m a g e s c a n h a v e 2 0 t o 5 0 m r e s o l u t i o n

. T h e r e a d e r i n t e r e s t e d i n m o r e i n f o r m a t i o n o n

N M R m i c r o s c o p y i s e n c o u r a g e d t o r e a d t h e a u t h o

r ' s h y p e r t e x t b o o k o n M R I e n t i t l e d T h e B a s i c s

o f M R I l o c a t e d a t h t t p : / / w w w . c i s . r i t . e d u / h t b o o

k s / m r i / .

S
O c c a s i o n a l l y , i t b e c o m e s n e c e s s a r y

t o e l i m i n a t e t h e s i g n a l f r o m o n e c o n s t i t u e n t o

f a s a m p l e . A n e x a m p l e i s a n u n w a n t e d w a t e r s i g

n a l w h i c h o v e r w h e l m s t h e s i g n a l f r o m t h e d e s i r

e d c o n s t i t u e n t . I f T
1

o f t h e t w o c o m p o n e n t s d i f

f e r , t h i s m a y b e a c c o m p l i s h e d b y u s i n g a n i n v e r

s i o n r e c o v e r y s e q u e n c e , p r e s e n t e d i n C h a p t e r 6 .

T o e l i m i n a t e t h e w a t e r s i g n a l , c h o o s e t h e T I t o

b e t h e t i m e w h e n t h e w a t e r s i g n a l p a s s e s t h r o

u g h z e r o . T I = T
1

l n 2 I n t h i s e x a m p l e , a T I = 1

s w o u l d e l i m i n a t e t h e w a t e r s i g n a l . A n o t h e r m

e t h o d o f e l i m i n a t i n g a s o l v e n t a b s o r p t i o n s i g

n a l i s t o s a t u r a t e i t . I n t h i s p r o c e d u r e , a s a t

u r a t i o n p u l s e s i m i l a r t o t h a t e m p l o y e d i n C 1

3 N M R ( S e e C h a p t e r 9 ) i s u s e d t o d e c o u p l e h y d

r o g e n c o u p l i n g . T h e f r e q u e n c y o f t h e s a t u r a t i o

n p u l s e i s s e t t o t h e s o l v e n t r e s o n a n c e . T h e w

i d t h o f t h e s a t u r a t i o n p u l s e i s v e r y l o n g , s o

i t s b a n d w i d t h i s v e r y s m a l l c a u s i n g i t t o a f f

e c t o n l y t h e s o l v e n t r e s o n a n c e .

F
F i e l d c y c l

i n g N M R s p e c t r o s c o p y i s u s e d t o o b t a i n s p i n l a

t t i c e r e l a x a t i o n r a t e s , R
1

, w h e r e R
1

= 1 / T
1

a s a

f u n c t i o n o f m a g n e t i c f i e l d o r L a r m o r f r e q u e n c

y . T h e r e f o r e , f i e l d c y c l i n g N M R f i n d s a p p l i c a t i

o n s i n t h e s t u d y o f m o l e c u l a r d y n a m i c s . T h e a n

i m a t i o n w i n d o w c o n t a i n s a n e x a m p l e o f r e s u l t s

f r o m a f i e l d c y c l i n g N M R s p e c t r o m e t e r . T h e p l

o t r e p r e s e n t s t h e R
1

v a l u e o f t h e h y d r o g e n n u c

l e i i n v a r i o u s c o n c e n t r a t i o n a q u e o u s s o l u t i o n

s o f M n
+ 2

a t 2 5
o

a s a f u n c t i o n o f t h e p r o t o n L a r

m o r f r e q u e n c y . M a n y d i f f e r e n t t e c h n i q u e s h a v e

b e e n u s e d t o o b t a i n R
1

a s a f u n c t i o n o f m a g n e

t i c f i e l d . S o m e t e c h n i q u e s m o v e t h e s a m p l e r a p

i d l y b e t w e e n d i f f e r e n t m a g n e t i c f i e l d s t r e n g t

h s . O n e o f t h e m o r e p o p u l a r t e c h n i q u e s k e e p s t

h e s a m p l e a t a f i x e d l o c a t i o n a n d r a p i d l y v a r

i e s t h e m a g n e t i c f i e l d t h e s a m p l e e x p e r i e n c e s

. T h i s t e c h n i q u e i s r e f e r r e d t o a s r a p i d f i e l d

c y c l i n g N M R s p e c t r o s c o p y . T h e p r i n c i p l e b e h i

n d a r a p i d f i e l d c y c l i n g N M R s p e c t r o m e t e r i s

t o p o l a r i z e t h e s p i n s i n t h e s a m p l e u s i n g a h

i g h m a g n e t i c f i e l d , B
p

. T h e m a g n e t i c f i e l d i s r

a p i d l y c h a n g e d t o t h e v a l u e a t w h i c h r e l a x a t i

o n o c c u r s , B
r

. B
r

i s t h e v a l u e a t w h i c h R
1

i s t o b

e d e t e r m i n e d . A f t e r a p e r i o d o f t i m e , , t h e m a g

n e t i c f i e l d i s s w i t c h e d t o a v a l u e , B
d

, a t w h i c

h d e t e c t i o n o f a s i g n a l o c c u r s . B
d

i s f i x e d s o

t h a t t h e o p e r a t i n g f r e q u e n c y o f t h e d e t e c t i o n

c i r c u i t r y d o e s n o t n e e d t o b e c h a n g e d . T h e s i

g n a l , a n F I D , i s c r e a t e d b y t h e a p p l i c a t i o n o f

a 9 0
o

R F p u l s e . T h e t i m i n g d i a g r a m f o r t h i s s e q

u e n c e c a n b e f o u n d i n t h e a n i m a t i o n w i n d o w . T

h e F T o f t h e F I D r e p r e s e n t s t h e a m o u n t o f m a g

n e t i z a t i o n p r e s e n t i n t h e s a m p l e a f t e r r e l a x i

n g f o r a p e r i o d i n B
r

. A p l o t o f t h i s m a g n e t

i z a t i o n a s a f u n c t i o n o f i s a n e x p o n e n t i a l l

y d e c a y i n g f u n c t i o n , s t a r t i n g f r o m t h e e q u i l i b

r i u m m a g n e t i z a t i o n a t B
p

a n d g o i n g t o t h e v a l u

e a t B
r

. W h e n a s i n g l e t y p e o f s p i n i s p r e s e n t

, t h e r e l a x a t i o n i s m o n o e x p o n e n t i a l w i t h r a t e

c o n s t a n t R
1

a t B
r

. W h e n B
r

i s v e r y l a r g e c o m p a r e

d t o B
d

, B
p

i s o f t e n s e t t o z e r o a n d t h e p l o t o f

t h i s m a g n e t i z a t i o n a s a f u n c t i o n o f i s a n

e x p o n e n t i a l l y g r o w i n g f u n c t i o n .

T
C A

I D S S M S F

I
N u c l e a r m a g n e t i c r e s o n a n

c e s p e c t r o s c o p y i s o n e o f t h e r i c h e s t s p e c t r o s

c o p i e s a v a i l a b l e . I n p r e v i o u s c h a p t e r s y o u h a v e

s e e n h o w i t c a n b e u s e d t o e l u c i d a t e c h e m i c a l

s t r u c t u r e . I n t h i s c h a p t e r y o u w i l l s e e s o m e o

f t h e o t h e r m o r e a d v a n c e d a p p l i c a t i o n s o f N M R .

T w o o f t h e s e t e c h n i q u e s , s o l i d s t a t e N M R a n d g r

a d i e n t e n h a n c e d s p e c t r o s c o p y , w i l l a s s i s t u s f u

r t h e r i n t h e d e t e r m i n a t i o n o f m o l e c u l a r s t r u c t

u r e . T w o a d d i t i o n a l t e c h n i q u e s w i l l a s s i s t u s i

n s t u d y i n g m o l e c u l a r d y n a m i c s , o r t h e r o t a t i o n a

l a n d t r a n s l a t i o n a l m o t i o n s o f m o l e c u l e s . T h e l

a s t t e c h n i q u e , N M R m i c r o s c o p y , w i l l e n a b l e u s t o

d e t e r m i n e t h e s p a t i a l d i s t r i b u t i o n o f n u c l e a r

s p i n s i n a s a m p l e .

D
D i f f u s i o n i s t h e m o t i o n

o f p a r t i c l e s d u e t o B r o w n i a n m o t i o n . T h e d i f f u

s i o n c o e f f i c i e n t , D , i s a m e a s u r e o f t h e d i f f u s i

o n . T h e p u l s e d g r a d i e n t s p i n e c h o s e q u e n c e p e r m

i t s u s t o m e a s u r e t h e d i f f u s i o n c o e f f i c i e n t . T h

e s e q u e n c e i s i n t h e o r y c a p a b l e o f m e a s u r i n g b

o t h t h e r o t a t i o n a l a n d t r a n s l a t i o n a l d i f f u s i o n

c o e f f i c i e n t s , b u t i s u s e d p r i m a r i l y f o r s t u d y i

n g t r a n s l a t i o n a l d i f f u s i o n . T o u n d e r s t a n d h o w

t h e p u l s e d g r a d i e n t s p i n e c h o s e q u e n c e a l l o w s

u s t o m e a s u r e d i f f u s i o n , c o n s i d e r t h e t i m i n g

d i a g r a m f o r t h e s e q u e n c e . T h i s s e q u e n c e i s v e r

y s i m i l a r t o t h e s p i n e c h o s e q u e n c e i n t r o d u c e

d i n C h a p t e r 6 , e x c e p t t h a t t w o g r a d i e n t p u l s e

s h a v e b e e n a p p l i e d . T h e s e t w o g r a d i e n t p u l s e s

a r e i d e n t i c a l i n a m p l i t u d e , G , a n d w i d t h , . T h e

t w o g r a d i e n t p u l s e s a r e s e p a r a t e d b y a t i m e a

n d a r e p l a c e d s y m m e t r i c a l l y a b o u t t h e 1 8 0 d e g

r e e p u l s e . T h e f u n c t i o n o f t h e g r a d i e n t p u l s e

s i s t o d e p h a s e m a g n e t i z a t i o n f r o m s p i n s w h i c

h h a v e d i f f u s e d t o a n e w l o c a t i o n i n t h e p e r i

o d . T h e s e p u l s e s h a v e n o e f f e c t o n s t a t i o n a r y

s p i n s . F o r e x a m p l e , a s t a t i o n a r y s p i n e x p o s e d

t o t h e f i r s t g r a d i e n t p u l s e , a p p l i e d a l o n g t h e

Z a x i s , w i l l a c q u i r e a p h a s e i n r a d i a n s g i v e n

b y

= 2 z G
z

d t . T h e s p i n w i l l a c q u i r e a n e q

u a l b u t o p p o s i t e p h a s e f r o m t h e s e c o n d p u l s e s

i n c e t h e p u l s e s a r e o n d i f f e r e n t s i d e s o f t h e

1 8 0 d e g r e e R F p u l s e . T h u s , t h e i r e f f e c t s c a n c e l

e a c h o t h e r o u t . C o n s i d e r t h e f o l l o w i n g i l l u s t r

a t i o n o f t h e e f f e c t o f t h e g r a d i e n t p u l s e s o n

t h e p h a s e o f s t a t i o n a r y a n d m o v i n g s p i n s . T h e

i l l u s t r a t i o n p r e s e n t s t h e p h a s e o f a d i f f u s i

n g s p i n r e l a t i v e t o t h a t o f a r e f e r e n c e s p i n

a n d a s t a t i o n a r y s p i n . T h e r e f e r e n c e s p i n i s o

n e w h i c h e x p e r i e n c e s n o g r a d i e n t p u l s e s . T h e s

t a t i o n a r y s p i n i s n o t d i f f u s i n g d u r i n g t h e t i

m e i l l u s t r a t e d b y t h e s e q u e n c e . T h e d i f f u s i n g

s p i n m o v e s a l o n g Z d u r i n g t h e s e q u e n c e . T h e b l

u e l i n e i n t h e t i m i n g d i a g r a m r e p r e s e n t s t h e

t i m e o f t h e 1 8 0 d e g r e e p u l s e i n t h e s p i n e c h o

s e q u e n c e . W h e n y o u p u t t h e i l l u s t r a t i o n i n t o

m o t i o n , t h e s t a t i o n a r y s p i n c o m e s b a c k i n t o p h

a s e w i t h t h e r e f e r e n c e o n e , i n d i c a t i n g a p o s i t

i v e c o n t r i b u t i o n t o t h e e c h o . T h e d i f f u s i n g s p

i n d o e s n o t c o m e b a c k i n t o p h a s e w i t h t h e r e f

e r e n c e s p i n s o i t d i m i n i s h e s t h e e c h o h e i g h t .

T h e r e l a t i o n s h i p b e t w e e n t h e s i g n a l ( S ) o b t a i

n e d i n t h e p r e s e n c e o f a g r a d i e n t a m p l i t u d e G

i n t h e i d i r e c t i o n a n d t h e d i f f u s i o n c o e f f i c

i e n t i n t h e s a m e d i r e c t i o n i s g i v e n b y t h e f o

l l o w i n g e q u a t i o n w h e r e S
o

i s t h e s i g n a l a t z e

r o g r a d i e n t . S / S
o

= e x p [ ( G
i

)
2

D
i

( / 3 ) ] T h

e d i f f u s i o n c o e f f i c i e n t i s t y p i c a l l y c a l c u l a t

e d f r o m a p l o t o f l n ( S / S
o

) v e r s u s ( G )
2

( /

3 ) . D i f f u s i o n i n t h e x , y , o r z d i r e c t i o n m a y b e

m e a s u r e d b y a p p l y i n g t h e g r a d i e n t r e s p e c t i v e

l y i n t h e x , y , o r z d i r e c t i o n .

S
T h e s p i n l a t

t i c e a n d s p i n s p i n r e l a x a t i o n t i m e s , T
1

a n d T
2

r e s p e c t i v e l y , o f t h e c o m p o n e n t s o f a s o l u t i o n a

r e v a l u a b l e t o o l s f o r s t u d y i n g m o l e c u l a r d y n a m

i c s . Y o u s a w i n C h a p t e r 3 t h a t T
1 1

i s p r o p o r t i

o n a l t o t h e n u m b e r o f m o l e c u l a r m o t i o n s a t t h e

L a r m o r f r e q u e n c y , w h i l e T
2 1

i s p r o p o r t i o n a l t

o t h e n u m b e r o f m o l e c u l a r m o t i o n s a t f r e q u e n c i

e s l e s s t h a n o r e q u a l t o t h e L a r m o r f r e q u e n c y .

W h e n w e a r e d e a l i n g w i t h s o l u t i o n s t h e s e m o t i o

n s a r e p r e d o m i n a n t l y r o t a t i o n a l m o t i o n s . T h e r e

a r e m a n y p u l s e s e q u e n c e s w h i c h m a y b e u s e d t

o m e a s u r e T
1

a n d T
2

. T h e i n v e r s i o n r e c o v e r y , 9 0

F I D , a n d s p i n e c h o s e q u e n c e s m a y b e u s e d t o m

e a s u r e T
1

. E a c h t e c h n i q u e h a s i t s o w n a d v a n t a g

e s a n d d i s a d v a n t a g e s . T h e s p i n e c h o s e q u e n c e m

a y b e u s e d t o m e a s u r e T
2

. T
1

M e a s u r e m e n t R e c a

l l t h e t i m i n g d i a g r a m f o r a n i n v e r s i o n r e c o v e

r y s e q u e n c e f i r s t p r e s e n t e d i n C h a p t e r 6 . T h e

s i g n a l a s a f u n c t i o n o f T I w h e n t h e s e q u e n c e

i s n o t r e p e a t e d i s S = k ( 1 2 e
T I / T 1

) .

I f t h e c u r v e i s w e l l d e f i n e d ( i . e . i f t h e r e i

s a h i g h d e n s i t y o f d a t a p o i n t s r e c o r d e d a t d

i f f e r e n t T I t i m e s ) , t h e T
1

v a l u e c a n b e d e t e r m

i n e d f r o m t h e z e r o c r o s s i n g o f t h e c u r v e w h i c

h i s T
1

l n 2 . A l t e r n a t i v e l y t h e r e l a x a t i o n c u r v

e a s a f u n c t i o n o f T I m a y b e f i t u s i n g t h e e q

u a t i o n S = S
o

( 1 2 e
T I / T 1

) . T h i s a p p r o a c h

i s f a v o r e d w h e n t h e r e a r e f e w e r d a t a p o i n t s a

s a f u n c t i o n o f T I . T
1

m a y a l s o b e d e t e r m i n e d

f r o m a 9 0 F I D o r s p i n e c h o s e q u e n c e w h i c h i s

r e p e a t e d a t v a r i o u s r e p e t i t i o n t i m e s ( T R ) . F o

r e x a m p l e , i f t h e 9 0 F I D s e q u e n c e i s r e p e a t e d

m a n y t i m e s a t T R
1

a n d t h e n m a n y t i m e s a t T R
2

T R
3

, e t c , t h e p l o t o f s i g n a l a s a f u n c t i o n o f T

R w i l l b e a n e x p o n e n t i a l g r o w t h o f t h e f o r m

S = k ( 1 e
T R / T 1

) . T h i s d a t a m a y b e f i t t o

o b t a i n T
1

. T h e d i f f i c u l t y w i t h f i t t i n g t h i s

d a t a a n d t h e i n v e r s i o n r e c o v e r y d a t a i s a l a c

k o f k n o w l e d g e o f t h e v a l u e o f t h e e q u i l i b r i u

m m a g n e t i z a t i o n o r s i g n a l S
o

. O t h e r t e c h n i q u e s

h a v e b e e n p r o p o s e d w h i c h d o n o t r e q u i r e k n o w

l e d g e o f t h e e q u i l i b r i u m m a g n e t i z a t i o n o r s i g

n a l . T
2

M e a s u r e m e n t M e a s u r e m e n t o f t h e s p i n -

s p i n r e l a x a t i o n t i m e r e q u i r e s t h e u s e o f a s p

i n e c h o p u l s e s e q u e n c e . T h e e c h o a m p l i t u d e , S , a

s a f u n c t i o n o f e c h o t i m e , T E , i s e x p o n e n t i a l l y

d e c a y i n g . P l o t t i n g l n ( S / S
o

) v e r s u s T E y i e l d s

a s t r a i g h t l i n e , t h e s l o p e o f w h i c h i s 1 / T
2

. A

l i n e a r l e a s t s q u a r e s a l g o r i t h m i s o f t e n u s e d

t o f i n d t h e s l o p e a n d h e n c e T
2

v a l u e . T h i s a p

p r o a c h c a n r e s u l t i n l e a d t o l a r g e e r r o r s i n

t h e c a l c u l a t e d T
2

v a l u e s w h e n t h e d a t a h a s n o

i s e . T h e l a t e r p o i n t s i n t h e d e c a y c u r v e h a v e

p o o r e r s i g n a l t o n o i s e r a t i o t h a n t h e e a r l i e r

p o i n t s , b u t a r e g i v e n e q u a l w e i g h t b y t h e l i n

e a r l e a s t s q u a r e s a l g o r i t h m . T h e s o l u t i o n t o t

h i s p r o b l e m i s t o u s e a n o n l i n e a r l e a s t s q u a

r e s p r o c e d u r e .

S
W e s a w i n C h a p t e r 4 t h a t t h

e m a g n i t u d e o f t h e c h e m i c a l s h i f t i s r e l a t e d t

o t h e e x t e n t t o w h i c h t h e e l e c t r o n c a n s h i e l d

t h e n u c l e u s f r o m t h e a p p l i e d m a g n e t i c f i e l d . I n

a s p h e r i c a l l y s y m m e t r i c m o l e c u l e , t h e c h e m i c a l

s h i f t i s i n d e p e n d e n t o f m o l e c u l a r o r i e n t a t i o n

. I n a n a s y m m e t r i c m o l e c u l e , t h e c h e m i c a l s h i f t

i s d e p e n d e n t o n t h e o r i e n t a t i o n . T h e m a g n e t i c f

i e l d e x p e r i e n c e d b y t h e n u c l e u s v a r i e s a s a f u

n c t i o n o f t h e o r i e n t a t i o n o f t h e m o l e c u l e i n t

h e m a g n e t i c f i e l d . T h e N M R s p e c t r u m f r o m a r a n d

o m d i s t r i b u t i o n o f f i x e d o r i e n t a t i o n s , s u c h a s

i n a s o l i d , w o u l d l o o k l i k e t h i s . T h e l a r g e r s i g

n a l a t l o w e r f i e l d s t r e n g t h i s d u e t o t h e f a c t

t h a t t h e r e a r e m o r e p e r p e n d i c u l a r o r i e n t a t i o n

s . I n a n o n v i s c o u s l i q u i d , t h e f i e l d s a t t h e v a r

i o u s o r i e n t a t i o n s a v e r a g e o u t d u e t o t h e t u m b l

i n g o f t h e m o l e c u l e . T h e a n i s o t r o p i c c h e m i c a l

s h i f t i s o n e r e a s o n w h y t h e N M R s p e c t r a o f s o

l i d s a m p l e s d i s p l a y b r o a d s p e c t r a l l i n e s . A n o t

h e r r e a s o n f o r b r o a d s p e c t r a l l i n e s i s d i p o l a

r b r o a d e n i n g . A d i p o l a r i n t e r a c t i o n i s o n e b e t

w e e n t w o s p i n 1 / 2 n u c l e i . T h e m a g n i t u d e o f t h e

i n t e r a c t i o n v a r i e s w i t h a n g l e a n d d i s t a n c e r

. A s a f u n c t i o n o f , t h e m a g n e t i c f i e l d B e x p e r

i e n c e d b y t h e r e d n u c l e u s i s ( 3 c o s
2

1 ) . A

g r o u p o f d i p o l e s w i t h a r a n d o m d i s t r i b u t i o n o

f o r i e n t a t i o n s , a s i n a s o l i d , g i v e s t h i s s p e c t

r u m . T h e h i g h e r s i g n a l a t m i d f i e l d s t r e n g t h i

s d u e t o t h e l a r g e r p r e s e n c e o f o r i e n t a t i o n s

p e r p e n d i c u l a r t o t h e d i r e c t i o n o f t h e B
o

f i e l

d . T h i s s i g n a l i s m a d e u p o f c o m p o n e n t s f r o m t

h e r e d a n d b l u e n u c l e i i n t h e d i p o l e . I n a n o n

v i s c o u s l i q u i d , t h e i n t e r a c t i o n a v e r a g e s o u t d

u e t o t h e p r e s e n c e o f r a p i d t u m b l i n g o f t h e m

o l e c u l e . W h e n t h e a n g l e i n t h e a b o v e e q u a t i o n

i s 5 4 . 7
o

, 1 2 5 . 3
o

, 2 3 4 . 7
o

, o r 3 0 5 . 3
o

, t h e d i p o l e

i n t e r a c t i o n v a n i s h e s . T h e a n g l e 5 4 . 7
o

i s c a l l e

d t h e m a g i c a n g l e ,
m

. I f a l l t h e m o l e c u l e s c o u

l d b e p o s i t i o n e d a t
m

, t h e s p e c t r u m w o u l d n a r r

o w t o t h e f a s t t u m b l i n g l i m i t . S i n c e t h i s i s

n o t p o s s i b l e , t h e n e x t b e s t t h i n g i s t o c a u s e

t h e a v e r a g e o r i e n t a t i o n o f t h e m o l e c u l e s t o b

e
m

. E v e n t h i s i s n o t e x a c t l y p o s s i b l e , b u t t h

e c l o s e s t a p p r o x i m a t i o n i s t o r a p i d l y s p i n t h

e e n t i r e s a m p l e a t a n a n g l e
m

r e l a t i v e t o B
o

I n s o l i d s t a t e N M R , s a m p l e s a r e p l a c e d i n a s p

e c i a l s a m p l e t u b e a n d t h e t u b e i s p l a c e d i n s i

d e a r o t o r . T h e r o t o r , a n d h e n c e t h e s a m p l e , a r e

o r i e n t e d a t a n a n g l e
m

w i t h r e s p e c t t o t h e B

m a g n e t i c f i e l d . T h e s a m p l e i s t h e n s p u n a t a

r a t e o f t h o u s a n d s o f r e v o l u t i o n s p e r s e c o n d

. T h e s p i n n i n g r a t e m u s t b e c o m p a r a b l e t o t h e

s o l i d s t a t e l i n e w i d t h . T h e c e n t r i f i g a l f o r c e

c r e a t e d b y s p i n n i n g t h e s a m p l e t u b e a t a r a t

e o f s e v e r a l t h o u s a n d s o f r e v o l u t i o n s p e r s e c

o n d i s e n o u g h t o d e s t r o y a t y p i c a l g l a s s N M R

s a m p l e t u b e . S p e c i a l l y e n g i n e e r e d s a m p l e t u b e s

a n d r o t o r s a r e n e e d e d .

M
N M R m i c r o s c o p y i s

t h e a p p l i c a t i o n o f m a g n e t i c r e s o n a n c e i m a g i n g

( M R I ) p r i n c i p l e s t o t h e s t u d y o f s m a l l o b j e c t s

. O b j e c t s w h i c h a r e s t u d i e d a r e t y p i c a l l y l e s s

t h a n 5 m m i n d i a m e t e r . N M R m i c r o s c o p y r e q u i r e s

s p e c i a l h a r d w a r e n o t f o u n d o n c o n v e n t i o n a l N M R

s p e c t r o m e t e r s . T h i s i n c l u d e s g r a d i e n t c o i l s t o

p r o d u c e a g r a d i e n t i n t h e m a g n e t i c f i e l d a l o n

g t h e X , Y , a n d Z a x e s ; g r a d i e n t c o i l d r i v e r s ; R

F p u l s e s h a p i n g s o f t w a r e ; a n d i m a g e p r o c e s s i n g

s o f t w a r e . R e s u l t a n t i m a g e s c a n h a v e 2 0 t o 5 0 m

r e s o l u t i o n . T h e r e a d e r i n t e r e s t e d i n m o r e i n f o

r m a t i o n o n N M R m i c r o s c o p y i s e n c o u r a g e d t o r e a

d t h e a u t h o r ' s h y p e r t e x t b o o k o n M R I e n t i t l e d

T h e B a s i c s o f M R I l o c a t e d a t h t t p : / / w w w . c i s . r i

t . e d u / h t b o o k s / m r i / .

S
O c c a s i o n a l l y , i t b e c o m e s

n e c e s s a r y t o e l i m i n a t e t h e s i g n a l f r o m o n e c o

n s t i t u e n t o f a s a m p l e . A n e x a m p l e i s a n u n w a n t e

d w a t e r s i g n a l w h i c h o v e r w h e l m s t h e s i g n a l f r o

m t h e d e s i r e d c o n s t i t u e n t . I f T
1

o f t h e t w o c o m

p o n e n t s d i f f e r , t h i s m a y b e a c c o m p l i s h e d b y u s i

n g a n i n v e r s i o n r e c o v e r y s e q u e n c e , p r e s e n t e d i n

C h a p t e r 6 . T o e l i m i n a t e t h e w a t e r s i g n a l , c h o o s

e t h e T I t o b e t h e t i m e w h e n t h e w a t e r s i g n a l

p a s s e s t h r o u g h z e r o . T I = T
1

l n 2 I n t h i s e x a m p l

e , a T I = 1 s w o u l d e l i m i n a t e t h e w a t e r s i g n a l

. A n o t h e r m e t h o d o f e l i m i n a t i n g a s o l v e n t a b s

o r p t i o n s i g n a l i s t o s a t u r a t e i t . I n t h i s p r o c

e d u r e , a s a t u r a t i o n p u l s e s i m i l a r t o t h a t e m p l

o y e d i n C 1 3 N M R ( S e e C h a p t e r 9 ) i s u s e d t o d

e c o u p l e h y d r o g e n c o u p l i n g . T h e f r e q u e n c y o f t h

e s a t u r a t i o n p u l s e i s s e t t o t h e s o l v e n t r e s o

n a n c e . T h e w i d t h o f t h e s a t u r a t i o n p u l s e i s v e

r y l o n g , s o i t s b a n d w i d t h i s v e r y s m a l l c a u s i n

g i t t o a f f e c t o n l y t h e s o l v e n t r e s o n a n c e .

F i e l d c y c l i n g N M R s p e c t r o s c o p y i s u s e d t o o

b t a i n s p i n l a t t i c e r e l a x a t i o n r a t e s , R
1

, w h e r e R
1

= 1 / T
1

a s a f u n c t i o n o f m a g n e t i c f i e l d o r L a r m

o r f r e q u e n c y . T h e r e f o r e , f i e l d c y c l i n g N M R f i n d

s a p p l i c a t i o n s i n t h e s t u d y o f m o l e c u l a r d y n a

m i c s . T h e a n i m a t i o n w i n d o w c o n t a i n s a n e x a m p l e

o f r e s u l t s f r o m a f i e l d c y c l i n g N M R s p e c t r o m

e t e r . T h e p l o t r e p r e s e n t s t h e R
1

v a l u e o f t h e h

y d r o g e n n u c l e i i n v a r i o u s c o n c e n t r a t i o n a q u e o

u s s o l u t i o n s o f M n
+ 2

a t 2 5
o

a s a f u n c t i o n o f t h e

p r o t o n L a r m o r f r e q u e n c y . M a n y d i f f e r e n t t e c h

n i q u e s h a v e b e e n u s e d t o o b t a i n R
1

a s a f u n c t i

o n o f m a g n e t i c f i e l d . S o m e t e c h n i q u e s m o v e t h e

s a m p l e r a p i d l y b e t w e e n d i f f e r e n t m a g n e t i c f i

e l d s t r e n g t h s . O n e o f t h e m o r e p o p u l a r t e c h n i q

u e s k e e p s t h e s a m p l e a t a f i x e d l o c a t i o n a n d

r a p i d l y v a r i e s t h e m a g n e t i c f i e l d t h e s a m p l e

e x p e r i e n c e s . T h i s t e c h n i q u e i s r e f e r r e d t o a s

r a p i d f i e l d c y c l i n g N M R s p e c t r o s c o p y . T h e p r i

n c i p l e b e h i n d a r a p i d f i e l d c y c l i n g N M R s p e c t

r o m e t e r i s t o p o l a r i z e t h e s p i n s i n t h e s a m p l

e u s i n g a h i g h m a g n e t i c f i e l d , B
p

. T h e m a g n e t i c

f i e l d i s r a p i d l y c h a n g e d t o t h e v a l u e a t w h i

c h r e l a x a t i o n o c c u r s , B
r

. B
r

i s t h e v a l u e a t w h i c

h R
1

i s t o b e d e t e r m i n e d . A f t e r a p e r i o d o f t i m

e , , t h e m a g n e t i c f i e l d i s s w i t c h e d t o a v a l u e

, B
d

, a t w h i c h d e t e c t i o n o f a s i g n a l o c c u r s . B
d

i s

f i x e d s o t h a t t h e o p e r a t i n g f r e q u e n c y o f t h e

d e t e c t i o n c i r c u i t r y d o e s n o t n e e d t o b e c h a n

g e d . T h e s i g n a l , a n F I D , i s c r e a t e d b y t h e a p p l i

c a t i o n o f a 9 0
o

R F p u l s e . T h e t i m i n g d i a g r a m f o

r t h i s s e q u e n c e c a n b e f o u n d i n t h e a n i m a t i o n

w i n d o w . T h e F T o f t h e F I D r e p r e s e n t s t h e a m o

u n t o f m a g n e t i z a t i o n p r e s e n t i n t h e s a m p l e a f

t e r r e l a x i n g f o r a p e r i o d i n B
r

. A p l o t o f t

h i s m a g n e t i z a t i o n a s a f u n c t i o n o f i s a n e x

p o n e n t i a l l y d e c a y i n g f u n c t i o n , s t a r t i n g f r o m t

h e e q u i l i b r i u m m a g n e t i z a t i o n a t B
p

a n d g o i n g t

o t h e v a l u e a t B
r

. W h e n a s i n g l e t y p e o f s p i n

i s p r e s e n t , t h e r e l a x a t i o n i s m o n o e x p o n e n t i a l

w i t h r a t e c o n s t a n t R
1

a t B
r

. W h e n B
r

i s v e r y l a r

g e c o m p a r e d t o B
d

, B
p

i s o f t e n s e t t o z e r o a n d t

h e p l o t o f t h i s m a g n e t i z a t i o n a s a f u n c t i o n o

f i s a n e x p o n e n t i a l l y g r o w i n g f u n c t i o n .

A r t i f a c t
A feature which appear s in an NMR spectru m of a molecu le which should not be present based on the chemic al structu re and pulse sequen ce used. [ er 7

C h e m i c a l

S c r e e n i n g
The screeni ng of an applied magnet ic field experie nced by a nucleu s due to the electro n cloud around an atom or molecu le. [ er 4

C h e m i c a l S

h i f t
A variati on in the resona nce freque ncy of a nuclear spin due to the chemic al enviro nment around the nucleu s. Chemi cal shift is reporte d in ppm. [ er 4

C o i l
One or more loops of a conduc tor

used to create a magnet ic field. In NMR, the term general ly refers to the radiofr equenc y coil. [ er 7

C o n v o l u t i o n
A mathe matical operati on betwee n two functio ns. [ er 2

C o

m p l e x D a t a
Numer ical data with a real and an imagin ary compo nent. [ er 2

C o n t i n u o u s W a v e ( C W )

A form of spectro scopy in which a consta nt amplit ude electro magnet ic wave is applied . [ er 3

C o o r d i n a t e T r a n s f o r m a t

i o n
A change in the axes used to represe nt some spatial quantit y. [ er 2

C r y o p u m p i n g
The conden sation of air onto a surface cooled by a cryoge nic liquid . [ er 8

D e

p h a s i n g G r a d i e n t
A magnet ic field gradien t used to dephas e transve rse magnet ization. [ er 11

D i g i t a l F i l t

e r i n g
A feature found on may newer spectro meters which elimina tes wrapar ound artifact s by filterin g out the higher freque ncy compo nents in the time domain spectru m. [ er 7

D o u b l y b a

l a n c e d m i x e r
An electric al device, often referre d to as a produc t detecto r, which is used in NMR to convert signals from the laborat ory frame of referen ce to the rotatin g frame of

referen ce. [ er 7

E c h o
A form of magnet ic resona nce signal from the refocus ing of transve rse magnet ization. [ er 6

E c h o T i m e ( T E )
The

time betwee n the 90 degree pulse and the maxim um in the echo in a spinecho sequen ce. [ er 6

E x c h a n g e , C h e m i c a l
The interch ange of chemic ally equival ent compo

nents on a molecu le. [ er 3

E x c h a n g e , S p i n
The interch ange of spin state betwee n two nuclei. [ er 3

F i g u r e 8 C o i

l
A magnet ic field gradien t coil shaped like the numbe r eight. [ er 7

F r e e i n d u c t i o n d e c a y ( F I D )

A form of magnet ic resona nce signal from the decay of transve rse magnet ization. [ er 4

F o u r i e r t r a n s f o r m ( F T )
A

mathe matical techniq ue capabl e of convert ing a time domain signal to a freque ncy domain signal and vice versa. [ er 5

G r a d i e n t ( G )
A variati on in some quantit y with respect to another

. In the context of NMR, a magnet ic field gradien t is a variati on in the magnet ic field with respect to distanc e. [ er 7

G y r o m a g n e t i c R a t i o
The ratio of the resona

nce freque ncy to the magnet ic field strengt h for a given nucleu s. [ er 3

I m a g i n a r y C o m p o n e n t
The compo nent of a signal perpen dicular to the real signal. [

er 5

I m a g i n g S e q u e n c e
A specifi c set of RF pulses and magnet ic field gradien ts used to produc e an image. [ er 11

I n v e r s i o n

R e c o v e r y S e q u e n c e
A pulse sequen ce produc ing signals which represe nt the longitu dinal magnet ization present after the applica tion of a 180 inversi on RF pulse. [ er 6

I n v e r s i o n T i m e ( T I )
The time betwee n the inversi on pulse and the sampli ng pulse(s ) in an inversi on recover y sequen ce. [ er 6

K S p

a c e
That image space represe nted by the time and phase raw data. The Fourier transfo rm of kspace is the magnet ic resona nce image. [ er 5

L a r m o r f r e q u e n c

y
The resona nce freque ncy of a spin in a magnet ic field. The rate of precess ion of a spin packet in a magnet ic field. The freque ncy which will cause a transiti on betwee n the two spin energy levels of a nucleu s. [ er 3

L o n g i

t u d i n a l M a g n e t i z a t i o n
The Z compo nent of magnet ization. [ er 3

L o r e n t z i a n L i

n e s h a p e
A functio n obtaine d from the Fourier transfo rm of an expone ntial functio n. [ er 5

M a g n i t u d e
The length of a magnet ization vector. In NMR, the square

root of the sum of the squares of the M and M compo nents, i.e. magnit ude of the transve rse magnet ization. [ er 2

M a g n e t i c R e s o n a n c e I m a g

i n g ( M R I )
An imagin g techniq ue based on the princip les of NMR. [ er 11

N e g a t i v e F r e q u e n c y A r

t i f a c t
The appear ance of smaller in amplit ude peaks in one half of the spectru m which are the mirror image of ones in the opposit e half. [ er 8

N e t M a g n e t i z a t

i o n V e c t o r
A vector represe nting the sum of the magnet ization from a spin system . [ er 3

N u c l e a r M a g n e t i c

R e s o n a n c e ( N M R )
A spectro scopic techniq ue used by scientis ts to elucida te chemic al structu re and molecu lar dynami cs. [ er 1

P i x e l
Picture

elemen t. [ er 1

P r e c e s s
A rotatio nal motion of a vector about the axis of a coordi nate system where the polar angle is fixed and the azmuth al angle change s steadil y. [ er 3

P r o p o

r t i o n a l i t y C o n s t a n t
A consta nt used to convert one set of units to another . [ er 8

P u l s e S e q u e

n c e
A series of RF pulses and/or magnet ic field gradien ts applied to a spin system to produc e a signal whose behavi or gives inform ation about some propert y of the spin system . [ er 4

Q u a d r a t u

r e D e t e c t i o n
Detecti on of M and M simulta neousl y as a functio n of time. [ er 9

R a d i o F r e q u e n c y
A

freque ncy band in the electro magnet ic spectru m with freque ncies in the millons of cycles per second . [ er 3

R a w d a t a
The M and M data as a functio n of time and/or other parame ters in an NMR pulse

sequen ce. This is also called kspace data. [ er 10

R e a l
The compo nent of a signal perpen dicular to the imagin ary signal. [ er 2

R e p e t i t i o n T i m e

The time betwee n repetiti ons of the basic sequen ce in a pulse sequen ce. [ er 6

R e s o n a n c e
An exchan ge of energy betwee n two system s at a specifi c freque ncy. [ er 3

R F C o

i l
An inducto rcapacit or resona nt circuit used to set up B magnet ic fields in the sample and to detect the signal from the sample . [ er 7

R F P u l s e
A short burst of RF energy which has a specifi

c shape.

R o t a t i o n M a t r i x
A matrix used to describ e the rotatio n of a vector. [ er 3

S a m p l e P r o b e
That portion

of the NMR spectro meter contain ing the RF coils and into which the sample is placed. [ er 7

S a d d l e C o i l
A coil geomet ry which has two loops of a conduc tor wrappe d around opposit e sides of a

cylinde r. [RF: Chapte r7

S p i n
A funda mental propert y of matter respon sible for NMR and MRI. [ er 3

S p i n D e n s i t y
The concen tration of spins. [ er 6

p i n E c h o
An NMR sequen ce whose signal is an echo resultin g from the refocus ing of magnet ization after the applica tion of 90 180 RF pulses. [ er 6

S p i n L a t t i

c e R e l a x a t i o n
The return of the longitu dinal magnit ization to its equilib rium value along the +Z axis. [ er 3

S p i n L a t t i c e

R e l a x a t i o n T i m e ( T
1

)
The time to reduce the differe nce betwee n the longitu dinal magnit ization and its equilib rium value by a factor of e. [ er 3

p i n P a c k e t
A group of spins experie ncing the same magnet ic field. [ er 3

S p i n S p i n R e l a x a t i o

n
The return of the transve rse magnit ization to its equilib rium value (zero). [ er 3

S p i n S p i n R e l a x a t i o n T i m e
The

time to reduce the transve rse magnet ization by a factor of e. [ er 3

S i n c P u l s e
An RF pulse shaped like Sin(x)/ x. [ er 5

S u p e r c o n d u c t

To have no resista nce. A perfect superc onduct or can carry an electric al current withou t losses. [ er 7

T
2

*
Pronou nced T-2star. The spinspin relaxati on time compo sed of contrib utions from molecu lar interact ions and inhom ogeneit ies in

the magnet ic field. [ er 3

T i m i n g D i a g r a m
A multia xis plot of some aspects of a pulse sequen ce as a functio n of time. [ er 6

T r a n s v e r

s e m a g n e t i z a t i o n
The XY compo nent of the net magnet ization. [ er 3

S y m b o l
Angstrom (10-10 meters) CH3(C=O

)CH2CH3

B1

C The radio frequency Contrast magnetic field

CW

C D o n t i n u o u s w a v e

Chemical shift Magneti c field gradient Magnetic field gradient pulse separation pulse width

E Chemical shift f FID FT

Energy Frequency Free induction decay Fourier transform

Gyromagnetic ratio

Hydrogen

IFT

IM Inverse Imaginary part of a complex number Fourier transform J Joule J Spin-spin coupling constant k Boltzmann constant k kilo (103) k Proportionality constant K Kelvin temperature L

Mo MX MX' MY MY' MZ MXY MRI

micro (10-6) Equilibrium magnetization X component of magnetization X' component of magnetization Y component of magnetization Y' component of magnetization Z component of magnetization Transverse component of magnetization Magnetic resonance imaging

N+ N u m b e r o f a v e r a g e s S N p i n p o p u l a t i o n i n l o w e n e r

g y s t a t e NMR Spin populatio Nuclear magnetic resonance n in high energy state

3.14159... Ohm, impedance Phase angle ppm Parts per million

Radio frequency Real part of a complex number RE

SAR

S Sinc p e c i f i c a b s o r p t i o n r a t e

SNR Signal-to-noise ratio Sin(x)/x T Temperature Spinlattice relaxation time T2 Spin-spin relaxation time T2* Tesla T2 star T2inhomo Inhomog eneous T2 Rotation angle T TE T1 Echo Time TI Inversion Time TR Repetition Time X X axis in laboratory coordinate system X' Rotating frame X axis Y Y axis in laboratory coordinate system Y' Z Rotating Z axis in laboratory coordinate system frame Y axis 1-D One-dimensional 2-D Two-dimensional

References

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A. Carrington and A.D. McLachlan, Introduction To Magnetic Resonance, Chapman and Hall, London 1967. B. Noble and J.W. Daniel, Applied Linear Algebra, Prentice-Hall Englewood Cliffs, NJ. G.B. Thomas, Calculus, Addison-Wesley, Reading, MA 1969. H. Gunther, "Modern pulse methods in high-resolution NMR spectroscopy." Angew. Chem.. Int. Ed. Engl.22:350-380 (1983). R.K. Harris, Nuclear Magnetic Resonance Spectroscopy, Pitman, London 1983. T.C. Farrar, An Introduction to Pulse NMR Spectroscopy, Farragut Press, Chicago 1987. T.C. Farrar and E.D. Becker, Pulse And Fourier Transform NMR, Academic Press, 1971. D. Shaw, Fourier Transform NMR Spectroscopy, Elsevier, NY 1976. J.W.Akitt, NMR and Chemistry, An Introduction to the Fourier Transform Multinuclear Era. Chapman and Hall, London, 1983. R. Freeman, A Handbook of Nuclear Magnetic Resonance, Longman Scientific & Technical, Essex, England, 1988. Woodrow W. Conover, "Magnet Shimming," Technical Report, Nicolet Magnetics Corporation C.E. Hayes, W.A. Edelstein, J.F. Schenck, "Radio Frequency Resonators." in Magnetic Resonance Imaging, ed. by C.L. Partain, R.R. Price, J.A. Patton, M.V. Kulkarni, A.E. James, Saunders, Philadelphia, 1988. G.M. Bydder, "Clinical Applications of Gadolinium-DTPA." in in Magnetic Resonance Imaging, ed. by D.D. Stark and W.G. Bradley, C.V. Mosby Co., St. Louis, MO 1988. J. Granot, J. Magn. Reson. 70:488-492 (1986). S.R. Thomas, L.J. Busse, J.F. Schenck, "Gradient Coil Technology." in Magnetic Resonance Imaging, ed. by C.L. Partain, R.R. Price, J.A. Patton, M.V. Kulkarni, A.E. James, Saunders, Philadelphia, 1988. J. Gong and J.P. Hornak, "A Fast T1 Algorithm." Magn. Reson. Imaging 10:623626 (1992). X. Li and J.P. Hornak, "T2 Calculations in MRI: Linear versus Nonlinear Methods." J. Imag. Sci. & Technol. 38:154-157 (1994). Peter Stilbs, "Fourier transform pulsed-gradient spin-echo studies of molecular diffusion." Progress in NMR Spectroscopy 19:1-45 (1987). J.R. Dyer, Applications of Absorption Spectroscopy by Organic Compounds, Prentice-Hall, Englewood Cliffs, NJ 1965. D.A. Skoog, F.J. Holler, T.A. Nieman, Principles of Instrumental Analysis, 5th ed., Saunders College Publishing, New York, 1992. D.E. Leyden, R.H. Cox, Analytical Applications of NMR, Wiley, NY 1977. A.E. Derome, NMR Techniques for Chemistry Research, Pergamon Press, NY 1987. Atta-ur-Rahman, Nuclear Magnetic Resonance, Basic Principles, Springer-Verlag, NY 1986.

F. Noack, "NMR field-cycling spectroscopy: principles and applications." Progress in NMR Spectroscopy, 18171-276 (1986). Field Cycling NMR Relaxometry: Review of Technical Issues and Applications, STELAR s.r.l., via E. Fermi 4, 27035 Mede (PV), Italy. 2001, (http://www.stelar.it/) E. Anoardo, G. Galli, G. Ferrante, "Fast Field Cycling NMR: Applications and Instrumentation." Appl. Magn. Reson. 20:365-404 (2001) F.A. Bovey, L. Jelinski, P.A. Mirau, Nuclear Magnetic Resonance Spectroscopy, Academic Press, NY, 1988.