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NOE is the change in the intensity during

decoupling experiments. This is similar to signal
enhancement by polarization transfer. When 13C
NMR spectrum is recorded under BB
THE  decoupling conditions, spin populations
NUCLEAR OVERHAUSER redistribute on the 13C energy levels. The
difference in the Zeamen levels is greater that
EFFECT
those under equilibrium conditions.

THE ENHANCEMENT

NOE is defined by the quotient Mx/Mo where:

Mx = 13C magnetization with proton decoupling

Mo = 13C magnetization without proton decoupling.



Thus:


NOE = Mx (13C)/Mo(13C)

= 1 + γ(1H)/2γ(13C) ♠ 3

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THEORETICAL BACKGROUND OF NOE

This is an AX system.
This diagram represents the

Assume there is no scalar
Spin-spin relaxation transitions.

coupling J(A,X) = 0



W2 (4 1) and w0 (3 2)

1  3 & 2 4 A transitions
with double (∆ m = 2) and

1 2 & 3
4 X transitions
zero (∆m = 0) quantum

∆m = ±1
transitions become allowed

Respectively.

Line intensities are determined


by population difference in

energy levels according to the

equilibrium conditions.

W2 tries to increase N1’ at

the expense of N4’. Thus,

signal is amplified in

N1’ to N2’ and N3’ to N4’

transitions.



W0 tries to increase N2’ at

the expense of N3’. Thus,

signal reduction is seen in

the same transitions.

J(A,X) ≠ 0, When A nuclei are saturated (A) , population in

In small molecules with short Tc W2 predominates over Wo

levels 1 & 3, and 2 & 4 become equal (B).

and positive NOE effect is observed.

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OVERALL RESULT

TC is the correlation time which corresponds roughly

to the interval between two successive reorientation.



In small molecule with short Tc, w2 predominates and

positive NOE is observed.



In large molecules, with long Tc, wo predominates and

negative NOE is observed.

MAGNITUDE OF NOE EFFECT

MULTIPLE SPIN
In heteronuclear cases (1H & 13C) the enhancement

in 13C signal is about 200%.

SYSTEM

In homonuclear cases (1H & 1H), the enhancement

is about 50%.

In multi-spin systems, negative contributions to NOE

can occur.
1.  Assume a three spin system:

2.  If HA is transition is radiated, HB populations will be


altered and signal will increase.

Thus, NOE experiments can be used to estimate
3.  Due to dipolar interaction between HB and HC, HC populations
internuclear distance by

will be altered and HC signals will decrease.

measuring the fractional increase or decrease in signal
4.  Thus indirect NOE is negative.

intensities.

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EXAMPLES OF NOE

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Radiated protons

Radiated protons

HOW FAR DOES NOE FELT?

Assignment of methyl signals (A) and (B) is difficult.  The effect of a radiated (saturated) proton

Saturating signal at δ = 1.7 gives an enhancement at on the neighboring atoms is proportional

signal at δ = 4.25 (H-3), the difference spectrum. to r-6. The effect disappears beyond 0.35 nm

The negative signal at the NOE difference spectrum is Or about 5 Å.

the irradiating frequency. Sometimes strong signals like
CH3 groups may not exactly cancelled to zero.

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Chloroprothixene:

After metabolism, a

hydroxyl group is

introduced either C5 or C8.

Irradiation of resonance of proton H’ on carbon C1’ at

δ = 5.84 should have no NOE if OH is on C8.

The doublet of doublet at δ = 7.02 assigned to H8 proton

has a positive NOE effect. Also confirms that the exocyclic

double bond has Z configuration.

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When the E isomer of this

compound is synthesized

and H1 signal is saturated,

enhancement is observed

on the proton at C1.

To distinguish between two natural products I or II, the

readily available compound III is radiated at C5 methyl

group. Enhancement is observed on both H4 and H6. When

C3 methyl group is radiated, only H4 is enhanced.

Geraniol (E-isomer)

Difference spectrum

when CH3 on C3 is

irradiated.



Nerol (Z-isomer)

Difference spectrum

when CH3 on C5 is

irradiated.

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Nerol

Geraniol

Short range: up to 2.8 A

Medium range; Up to 3.4 A

Long range: Up to 4.2 A

Beyond 5-6 A, no detectable NOE.

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NOESY: Nuclear Overhouse Enhancement SpectroscopY

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