Nuclear Overhauser effect intensity

NMR Structure Determination of a 28-Nucleotide Signal Recognition Particle RNA with Complete Relaxation Matrix Methods Using Corrected Nuclear Overhauser Effect Intensities... 

NOE Nuclear Overhauser effect, change of signal intensities (integrals) dining decoupling experiments decreasing with spatial distance of nuclei... 

Methods of disturbing the Boltzmann distribution of nuclear spin states were known long before the phenomenon of CIDNP was recognized. All of these involve multiple resonance techniques (e.g. INDOR, the Nuclear Overhauser Effect) and all depend on spin-lattice relaxation processes for the development of polarization. The effect is referred to as dynamic nuclear polarization (DNP) (for a review, see Hausser and Stehlik, 1968). The observed changes in the intensity of lines in the n.m.r. spectrum are small, however, reflecting the small changes induced in the Boltzmann distribution. 

Nuclear Overhauser effect (nOe) The change in intensity in the signal of one nucleus when another nucleus lying spatially close to it is irradiated, with the two nuclei relaxing each other via the dipolar mechanism. Nuclear Overhauser effect correlation spectroscopy (NOESY) A 2D... 

Nuclear Overhauser effects (NOEs) cause changes in the intensity of NMR signals by through-space dipole iipole interactions [36]. The magnitude of an observed NOE between two magnetic nuclei gives useful information on the distances between them. The observed NOE is also related to Brownian... 

NOE Nuclear Overhauser effect/nuclear Overhauser enhancement. Enhancement of the intensity of a signal via augmented relaxation of the nucleus to other nearby nuclei that are undergoing saturation. See also ... 

When one resonance in an NMR spectrum is perturbed by saturation or inversion, the net intensities of other resonances in the spectrum may change. This phenomenon is called the nuclear Overhauser effect (NOE). The change in resonance intensities is caused by spins close in space to those directly affected by the perturbation. In an ideal NOE experiment, the target resonance is completely saturated by selected irradiation, while all other signals are completely unaffected. An NOE study of a rigid molecule or molecular residue often gives both structural and conformational information, whereas for highly flexible molecules or residues NOE studies are less useful. 

Exchange of magnetization due to cross-relaxation (NOE, nuclear Overhauser effect) does lead to intensity changes of individual resonances which provide valuable information about spatial and motional characteristics of the spins involved [4, 5]. It is currently mostly measured in two-dimensional NMR, where the NOE is measured as cross-peak intensity. Cross-relaxation is caused by mutual spin flips in dipolar coupled spin pairs. 

The basis for the determination of solution conformation from NMR data lies in the determination of cross relaxation rates between pairs of protons from cross peak intensities in two-dimensional nuclear Overhauser effect (NOE) experiments. In the event that pairs of protons may be assumed to be rigidly fixed in an isotopically tumbling sphere, a simple inverse sixth power relationship between interproton distances and cross relaxation rates permits the accurate determination of distances. Determination of a sufficient number of interproton distance constraints can lead to the unambiguous determination of solution conformation, as illustrated in the early work of Kuntz, et al. (25). While distance geometry algorithms remain the basis of much structural work done today (1-4), other approaches exist. For instance, those we intend to apply here represent NMR constraints as pseudoenergies for use in molecular dynamics or molecular mechanics programs (5-9). 

In most C spectra, nuclei which have directly attached protons receive a significant (but not easily predictable) signal enhancement when the protons are decoupled as a result of the Nuclear Overhauser Effect (see Section 7.3) and as a consequence, peak intensity does not necessarily reflect the number of nuclei giving rise to the signal. 

It is not usually possible to integrate routine C spectra directly unless specific precautions have been taken. However with proper controls, NMR spectroscopy can be used quantitatively and it is a valuable technique for the analysis of mixtures. To record C NMR spectra where the relative signal intensity can be reliably determined, the spectra must be recorded with techniques to suppress the Nuclear Overhauser Effect and with a long delay between the acquisition of successive spectra to ensure that all of the carbons in the molecule are completely relaxed between spectral acquisitions. 

The isotope N, with a natural abundance of 99.9%, has nuclear spin 7 = 1 and gives broad signals which are of little use for structural determinations. The N nucleus, with I = 1/2, is therefore preferred. However, the low natural abundance of about 0.4% and the extremely low relative sensitivity (Table 1) make measurements so difficult that N NMR spectroscopy was slow to become an accepted analytical tool. A further peculiarity is the negative magnetogyric ratio since, in proton decoupled spectra, the nuclear Overhauser effect can strongly reduce the signal intensity. DEPT and INEPT pulse techniques are therefore particularly important for N NMR spectroscopy. 

This phenomenon should not be confused with the interaction through distance between two nuclei that exchange magnetisation because the structure of the molecule is such that they are close in space, although a great number of bonds separates them. This is the Nuclear Overhauser Effect that causes modifications in signal intensities. 

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