Nuclear Overhauser effect

Nuclear Overhauser effect

Irradiation at the resonance frequency of one nucleus in the molecule may cause changes in the intensity of a signal at a different frequency corresponding to another nucleus - this is called the Nuclear Overhauser effect (Noe). Nuclear overhauser effect is due to dipole-dipole interactions between the magnetic moments of the pair of nuclei. Unlike J-coupling, this interaction is not mediated through bonds and hence it may be possible to observe the Nuclear Overhauser effect between pairs of nuclei separated by many bonds provided that they are in spatial proximity. The strength of the observable Nuclear overhauser effect for molecules in solution is proportional to the inverse of the sixth power of the distance between the two nuclei due to averaging caused by rotational motion. Both the magnitude as well as the sign of the nuclear overhauser effect depend on the rotational frequencies of the pair of nuclei with respect to the applied magnetic field. The Noe enhancement is quantitatively defined as $\eta$

$\eta ={\frac {S_{z}-S_{z,equil}}{S_{z,equil}}}$

In the steady state, when the resonance frequency of spin I is irradiated and the intensity of spin S is monitored, the equations for cross relaxation shown above indicate that

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \eta = \frac{<S_z> - <S_{z,equil}>}{<S_{z,equil}> = \frac{\sigma}{\rho_S} \frac{\gamma_I}{\gamma_S} }

This indicates that considerable enhancement in the intensity of the S signal can be obtained by irradiation at the frequency of the I spin, provided that ${\frac {\gamma _{I}}{\gamma _{S}}}>1$, because ${\frac {\sigma }{\rho _{S}}}=1/2$ when $w\tau _{c}<<1$. However, when $w\tau _{c}>>1$ ${\frac {\sigma }{\rho _{S}}}=-1$ and negative Noe enhancements are obtained. The sign of $\eta$ changes from positive to negative when $w\tau _{c}$ is close to one and under such conditions the Noe effect may not be observable. This happens for rigid molecules with relative molecular mass about 500 at room temperature e.g. many hexapeptides.