Nuclear Overhauser effect enhancements

Figure 4.2 Energy levels and populations for an IS system in which nuclei I and S are not directly coupled with each other. This forms the basis of the nuclear Overhauser enhancement effect. Nucleus S is subjected to irradiation, and nucleus I is observed, (a) Population at thermal equilibrium (Boltzmann population).

R. Mathur-De Vre, C. Maerschalk and C. Delporte, Spin-lattice relaxation times and nuclear Overhauser enhancement effect for P metabolites in model solutions at two... 

NOESY Nuclear Overhauser enhancement (effect) spectroscopy... 

Figure 1.2.13 (a) Partial 400 MHz IH-NMR spectrum of the methine protons of testosterone. A hopeless case for assignment, (b) Decoupling and nuclear Overhauser enhancement effects can be used to disect the multiline, one-dimensional spectrum into a variety of two-dimensional spectra. Assignment of signals to individual hydrogen atoms can thus be achieved. (From Sanders and Hunter, 1993.)... 

Figure 8.6.9 Diagram showing the eight intermolecular nuclear Overhauser enhancement effects between zinc bleomycin Aj and dfCGCTAGCG). ...

Such pulse programs are also used to enable other special ID experiments such as saturation or nonexcitation of a large solvent resonance (these are different in that the former method will also saturate NH or OH protons in the molecules under study through the mechanism of chemical exchange), or the measurement of nuclear Overhauser enhancement effects... 

Nuclear Overhauser enhancement effects again precluded quantitative enrichment determinations by integration of the peak areas of the carbon signals. The signal intensities of C-S and C-8 carbons, which probably have similar nuclear Overhauser enhancements, have a 3.9 1 ratio, which is identical with that obtained by the C-satellite method. 

More recent studies on the folded toxin structure by Norton and colleagues have utilized h- and C-NMR techniques (19,20). By using 2D-FT-NMR, it was possible to localize a four stranded, antiparallel )5-pleated sheet "backbone structure in As II, Ax I, and Sh I (21,22), In addition, Wemmer et al. (23) have observed an identical )5-pleated structure in Hp II. No a-helix was observed in these four variants. In the near future, calculated solution conformations of these toxins, utilizing distance measurements from extracted Nuclear Overhauser Enhancement (NOE) effects should greatly stimulate structure-activity investigations. 

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 ... 

T3C n.m.r. spectra were recorded for the oils produced at 400°, 450°, 550° and 600°C. As the temperature increased the aromatic carbon bands became much more intense compared to the aliphatic carbon bands (see Figure 8). Quantitative estimation of the peak areas was not attempted due to the effect of variations in spin-lattice relaxation times and nuclear Overhauser enhancement with different carbon atoms. Superimposed on the aliphatic carbon bands were sharp lines at 14, 23, 32, 29, and 29.5 ppm, which are due to the a, 8, y, 6, and e-carbons of long aliphatic chains (15). As the temperature increases, these lines... 

The relative stereochemistry of hyperaspine 93 was determined by 2-D NMR spectroscopic and mass spectrometry (MS) methods. It has a m-fused bicyclic conformation 93a <2001TL4621>. The trans-fused one is disfavored by an axial pentyl group at C-8 and by a destabilizing dipole-dipole interaction between the N- and O-atoms, which does not exist in the alternative //.(-conformation. The geminal coupling constant of C( 1 )H2 in 93 (11.0 Hz), and that of its 6-hydroxy derivative (11.2 Hz), indicates that they exist preferentially in / //-conformations, whereas their 6-epimers adopt trans-conformations (9.3 and 8.4 Hz, respectively) <2005EJ01378>. Nuclear Overhauser enhancement spectroscopy (NOESY) studies also confirmed the stereochemistry of 93 by the marked nuclear Overhauser effect (NOE) correlation between H-3 and H-4a <20030L5063>. 

The 13C NMR sensitivity can sometimes be a problem, but for the kind of samples studied here the effective concentration of monomer units is several molar which does not place excessive demands on present Fourier transform NMR spectrometers. In addition to the sensitivity of the chemical shift to structure (9), the relaxation of protonated carbons is dominated by dipole-dipole interaction with the attached proton (9). The dependence of the relaxation parameters T, or spin-lattice, and Tor spin-spin, on isotropic motional correlation time for a C-H unit is shown schematically in Figure 1. The T1 can be determined by standard pulse techniques (9), while the linewidth at half-height is often related to the T2. Another parameter which is related to the correlation time is the nuclear Overhauser enhancement factor, q. The value of this factor for 13C coupled to protons, varies from about 2 at short correlation times to 0.1 at long correlation... 

The stereochemistry of the double bond in 4-(a-arylethylidene)-2-phenyl-5(4//)-oxazolones can be determined by measurements of long-range heteronuclear selective carbon-13 proton nuclear Overhauser enhancements. In the (Z)-isomers 774, large nuclear Overhauser enhancements are observed for the carbonyl carbon atom upon presaturation of the methyl group (Fig. 7.65). These effects are much smaller for the ( ) isomers. ... 

However, one of the interesting aspects of NMR structural results is that they often suggest no discernible solution structure for small systems, such as a tri- or tetra-peptides. This is due to the flexibility and structural variance displayed by these sample systems. However, the lack of interactions between parts of the molecule, which normally are detected via Nuclear Overhauser enhancements and refined into molecular structures during NMR structural determinations, should not be interpreted as a lack of a solution structure. It is the slow time scale of NMR, coupled with the rapidly interconverting conformations, which weakens these effects to the point where they can no longer be detected with certainty, and structural techniques which operate on a much faster time scale (e.g., UV-CD spectroscopy, or forms of vibrational spectroscopy) demonstrate that there is a preferred class of solution conformers even in small peptide systems. 

A third type of information available from NMR comes from the nuclear Overhauser enhancement or NOE. This is a direct through-space interaction of two nuclei. Irradiation of one nucleus with a weak radio frequency signal at its resonant frequency will equalize the populations in its two energy levels. This perturbation of population levels disturbs the populations of nearby nuclei so as to enhance the intensity of absorbance at the resonant frequency of the nearby nuclei. This effect depends only on the distance between the two nuclei, even if they are far apart in the bonding network, and varies in intensity as the inverse sixth power of the distance. Generally the NOE can only be detected between protons (XH nuclei) that are separated by 5 A or less in distance. These measured distances are used to determine accurate three-dimensional structures of proteins and nucleic acids. 

The assignment of the H-3 and H-5 signals in several A-substituted nitropyrazoles was made by the use of NOE (Nuclear Overhauser Enhancement) difference spectroscopy [290], NMR spectroscopy was employed for the investigation of metallotropic transitions in nitropyrazole organomercury derivatives [291], By means of II NMR spectroscopy the solvation effects of 4-substituted-l,3,5-trimethylpyrazoles in binary solvents (CC14/C6H6, benzene molar fractions) were studied [292], The author of this... 

NMR experiments include COSY, TOCSY, Cheteronuclear NMR experiments, NOESY (nuclear overhauser enhancement spectroscopy) and ROESY (rotating frame overhauser effect spectroscopy) as well as other two- and three-dimensional methodologies (Fossen and Andersen, 2006). 

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