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2071 atoms
2175 bonds
NMR Structure Determination
What is NMR?
How does NMR work?
How is a three dimensional structure
elucidated?
Nuclear Magnetic Resonance
Nuclear spin
I is a property of the nucleus
=Ih
-magnetic moment Mass # Atomic # I
- gyromagnetic ratio
Odd Even or odd 1/2, 3/2, 5/2,
I - spin quantum number
h - Plancks constant Even Even 0
Even Odd 1, 2, 3
z
= Bo = /2
- resonance frequency
in radians per second,
also called Larmor frequency
Bo - resonance frequency
in cycles per second, Hz
- gyromagnetic ratio
Bo - external magnetic
field (the magnet)
Spin 1/2 nuclei will have two
orientations in a magnetic field
+1/2 and -1/2.
Net magnetic moment
z
+1/2
Bo
-1/2
Ensemble of Nuclear Spins
Bo
Bo = 0 Bo > 0
Randomly oriented Highly oriented
N
Each nucleus behaves like
S a bar magnet.
The net magnetization vector
z
one nucleus
x
Mo - net magnetization
vector allows us to
many nuclei z
look at system as a whole
z
y y
x
x
Allowed Energy States for a
Spin 1/2 System
E = h Bo = h
-1/2 antiparallel
E E
+1/2 parallel
Bo = 0 Bo > 0
Therefore, the nuclei will absorb light with energy E resulting in
a change of the spin states.
Energy of Interaction
E = h Bo = h
The frequency, , corresponds to light in the
radiofrequency range when Bo is in the Teslas.
Mo
Mo
z z z
Mo
y y y
x x x
RF on
RF off RF off
z z z
Mo
y y
y
x x x
Mo
x
RF receivers pick up
the signals I Time
y
Free Induction Decay
FT
Frequency
Time
Spin Relaxation
lattice
N N
S S
Nuclear Overhauser Effect
The intensity of the interaction is a function of the distance
between the nuclei according to the following equation.
I - intensity
I = A (1/r6) A - scaling constant
r - internuclear distance
r1,2
1
H 1
H Arrows denote cross relaxation pathways
r1,2 - distance between protons 1 and 2
1 2
r2,3 - distance between protons 2 and 3
r1,3 r2,3
The NOE provides a link between an
1
H
experimentally measurable quantity, I, and
3 internuclear distance.
NOE is only observed up to ~5.
Scalar J Coupling
Electrons have a magnetic moment and are spin 1/2 particles.
Multiplet = 2nI + 1
1
H 1
H
n - number of identical adjacent nuclei
I - spin quantum number
12
C 12
C
Scalar J Coupling
10
C H 8
J
6
C
3
electronegativity.
Torsion Angles
1
H, 13C, 15N, 31P
= ( - o)/o * 106
Biomolecular NMR Experiments
J Correlated Based Experiments
COSY - Correlated Spectroscopy
2QF-COSY - Double Quantum Filtered Spectroscopy
HETCOR - Heteronuclear Correlated Spectroscopy
E.COSY - Exclusive COSY
HOHAHA - Homonuclear Hartmann Hahn (TOCSY)