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NUCLEAR MAGNETIC RESONANCE

NUCLEAR SPIN
The nuclei of some atoms have a property called “SPIN”.

These nuclei behave as if


they were spinning.
….. we don’t know if they actually do spin!

This is like the spin property


of an electron, which can have
two spins: +1/2 and -1/2 .

Each spin-active nucleus has a number of spins defined by


its spin quantum number, I.

The spin quantum numbers of some common nuclei follow …..


Spin Quantum Numbers of Some Common Nuclei
The most abundant isotopes of C and O do not have spin.

Element 1H 2H 12C 13C 14N 16O 17O 19F

Nuclear Spin
Quantum No 1/2 1 0 1/2 1 0 5/2 1/2
(I)
No. of Spin 2 3 0 2 3 0 6 2
States

Elements with either odd mass or odd atomic number


have the property of nuclear “spin”.

The number of spin states is 2I + 1,


where I is the spin quantum number.
THE PROTON

Although interest is increasing in other nuclei,


particulary C-13, the hydrogen nucleus (proton)
is studied most frequently, and we will devote
our attention to it first.
NUCLEAR SPIN STATES - HYDROGEN NUCLEUS
The spin of the positively
m charged nucleus generates
a magnetic moment vector, m.

+ +

The two states


m are equivalent
in energy in the
+ 1/2 - 1/2 absence of a
TWO SPIN STATES magnetic or an
electric field.
THE “RESONANCE” PHENOMENON

absorption of energy by the


spinning nucleus
Nuclear Spin Energy Levels
N

-1/2

In a strong magnetic
unaligned
field (Bo) the two
spin states differ in
energy.

+1/2
aligned
Bo S
Absorption of Energy
quantized
Opposed

-1/2 -1/2

DE

DE = hn
Radiofrequency

+1/2 +1/2
Applied
Field

Bo Aligned
THE ENERGY SEPARATION DEPENDS ON Bo

- 1/2

DE = kBo = hn
degenerate
at Bo = 0

+ 1/2

Bo
increasing magnetic field strength
The Larmor Equation!!!
DE = kBo = hn can be transformed into

gyromagnetic
ratio g
frequency of gBg0
the incoming
nn == Bo
radiation that
will cause a 2p
2p
transition strength of the
magnetic field

g is a constant which is different for


each atomic nucleus (H, C, N, etc)
A SECOND EFFECT OF A STRONG MAGNETIC FIELD

WHEN A SPIN-ACTIVE HYDROGEN ATOM IS


PLACED IN A STRONG MAGNETIC FIELD

….. IT BEGINS TO PRECESS

OPERATION OF AN NMR SPECTROMETER DEPENDS


ON THIS RESULT
N

w Nuclei precess at
frequency w when
RADIOFREQUENCY
placed in a strong
40 - 600 MHz magnetic field.

hn
NUCLEAR
MAGNETIC
If n = w then RESONANCE
energy will be
absorbed and NMR
the spin will
invert. S
Resonance Frequencies of Selected Nuclei
Isotope Abundance Bo (Tesla) Frequency(MHz) g(radians/Tesla)
1H 99.98% 1.00 42.6 267.53
1.41 60.0
2.35 100.0
7.05 300.0

2H 0.0156% 1.00 6.5 41.1 4:1


7.05 45.8

13C 1.108% 1.00 10.7 67.28


2.35 25.0
7.05 75.0

19F 100.0% 1.00 40.0 251.7


POPULATION AND SIGNAL STRENGTH
The strength of the NMR signal depends on the
Population Difference of the two spin states

Radiation
induces both
upward and
downward resonance
induced
transitions. emission

For a net positive signal excess


there must be an excess population
of spins in the lower state.

Saturation = equal populations = no signal


CLASSICAL INSTRUMENTATION
typical before 1960
field is scanned
A Simplified 60 MHz
NMR Spectrometer
RF (60 MHz) hn
Oscillator absorption RF
Recorder
signal Detector
Transmitter
Receiver

MAGNET MAGNET
~ 1.41 Tesla
N S (+/-) a few ppm

Probe
Fortunately, different types of protons precess at
different rates in the same magnetic field.

N Bo = 1.41 Tesla

EXAMPLE: 59.999995 MHz


59.999700 MHz
O
CH2 C CH3

hn
To cause absorption
60 MHz 59.999820 MHz of the incoming 60 MHz
the magnetic field strength,
Bo , must be increased to
S a different value for each
type of proton.
Differences are very small,
in the parts per million range.
IN THE CLASSICAL NMR EXPERIMENT THE INSTRUMENT
SCANS FROM “LOW FIELD” TO “HIGH FIELD”

LOW HIGH
FIELD FIELD
NMR CHART

DOWNFIELD UPFIELD
scan
NMR Spectrum of Phenylacetone

O
CH2 C CH3

NOTICE THAT EACH DIFFERENT TYPE OF PROTON COMES


AT A DIFFERENT PLACE - YOU CAN TELL HOW MANY
DIFFERENT TYPES OF HYDROGEN THERE ARE
MODERN INSTRUMENTATION

PULSED FOURIER TRANSFORM


TECHNOLOGY

FT-NMR
requires a computer
PULSED EXCITATION
N

n2
n1
O
BROADBAND
RF PULSE CH2 C CH3
contains a range
of frequencies n3
(n1 ..... nn)

S
All types of hydrogen are excited
simultaneously with the single RF pulse.
FREE INDUCTION DECAY
( relaxation )

n1

O
CH2 C CH3 n2

n3

n1, n2, n3 have different half lifes


COMPOSITE FID

“time domain“ spectrum

n1 + n2 + n3 + ......
time
FOURIER TRANSFORM
A mathematical technique that resolves a complex
FID signal into the individual frequencies that add
together to make it. ( Details not given here. )

converted to DOMAINS ARE


TIME DOMAIN FREQUENCY DOMAIN MATHEMATICAL
FID NMR SPECTRUM TERMS

FT-NMR
computer
COMPLEX
SIGNAL n1 + n2 + n3 + ......
Fourier
Transform

individual
a mixture of frequencies
frequencies
decaying (with time)
converted to a spectrum
The Composite FID is Transformed into
a classical NMR Spectrum :

O
CH2 C CH3

“frequency domain” spectrum


COMPARISON OF
CW AND FT TECHNIQUES
CONTINUOUS WAVE (CW) METHOD
THE OLDER, CLASSICAL METHOD

The magnetic field is “scanned” from a low field


strength to a higher field strength while a constant
beam of radiofrequency (continuous wave) is
supplied at a fixed frequency (say 100 MHz).

Using this method, it requires several minutes to plot


an NMR spectrum.

SLOW, HIGH NOISE LEVEL


PULSED FOURIER TRANSFORM
(FT) METHOD FAST
THE NEWER COMPUTER-BASED METHOD LOW NOISE

Most protons relax (decay) from their excited states


very quickly (within a second).

The excitation pulse, the data collection (FID), and


the computer-driven Fourier Transform (FT) take
only a few seconds.

The pulse and data collection cycles may be repeated


every few seconds.

Many repetitions can be performed in a


very short time, leading to improved signal …..
IMPROVED SIGNAL-TO-NOISE RATIO
By adding the signals from many pulses together, the
signal strength may be increased above the noise level.

signal enhanced
noise signal

1st pulse

2nd pulse
add many
pulses

noise is random
nth pulse etc. and cancels out