Selective one-dimensional experiments

These assignments are confirmed by the HH TOCS Y diagram b and the selective one-dimensional experiment on top of b with the H NMR subspectrum of the 2-A/-acetylamino-2-deoxygluco-pyranosyl- residue. 

The application of SIMBA to cryptospirolepine (1) highlights another very important usage of selective one-dimensional experiments. While it... 

Figure 2.11. Proton-Proton shift correlations of a-pinene (1) [purity 99 %, CDCls, 5 % v/v, 25 °C, 500 MHz, 8 scans, 256 experiments], (a) HH COSY (b) HH TOCSY (c) selective one-dimensional HH TOCSY, soft pulse irradiation at Sh = 5.20 (signal not shown), compared with the NMR spectrum on top deviations of chemical shifts from those in other experiments (Fig. 2.14, 2.16) arise from solvent effects...

The idea of back transformation of a three-dimensional NMR experiment involving heteronuclear 3H/X/Y out-and-back coherence transfer can in principle be carried to the extreme by fixing the mixing time in both indirect domains. Even if one-dimensional experiments of this kind fall short of providing any information on heteronuclear chemical shifts, they may still serve to obtain isotope-filtered 3H NMR spectra. A potential application of this technique is the detection of appropriately labelled metabolites in metabolism studies, and a one dimensional variant of the double INEPT 111/X/Y sequence has in fact been applied to pharmacokinetics studies of doubly 13C, 15N labelled metabolites.46 Even if the pulse scheme relied exclusively on phase-cycling for coherence selection, a suppression of matrix signals by a factor of 104 proved feasible, and it is easily conceivable that the performance can still be improved by the application of pulsed field gradients. 

It is important to realize that double Fourier transformation is not an essential part of two-dimensional NMR spectroscopy. This was made clear by Ernst in his early article (26) and when the spin system is simple there may be no particular advantage in using it. This approach was adopted in studies of C-enriched methyl formate in which various selective H and/or pulses were applied to individual transitions and it was found possible to deduce an accurate value for v( C) and draw conclusions about relaxation behaviour. (164-166) Detailed analysis (167) also shows that the sensitivity of two-dimensional Fourier transform spectroscopy can be as good as half that achieved in ordinary one-dimensional experiments. In this connection we should note that the time-saving gain of Fourier transformation... 

Muns ENDOR mvolves observation of the stimulated echo intensity as a fimction of the frequency of an RE Ti-pulse applied between tlie second and third MW pulse. In contrast to the Davies ENDOR experiment, the Mims-ENDOR sequence does not require selective MW pulses. For a detailed description of the polarization transfer in a Mims-type experiment the reader is referred to the literature [43]. Just as with three-pulse ESEEM, blind spots can occur in ENDOR spectra measured using Muns method. To avoid the possibility of missing lines it is therefore essential to repeat the experiment with different values of the pulse spacing Detection of the echo intensity as a fimction of the RE frequency and x yields a real two-dimensional experiment. An FT of the x-domain will yield cross-peaks in the 2D-FT-ENDOR spectrum which correlate different ENDOR transitions belonging to the same nucleus. One advantage of Mims ENDOR over Davies ENDOR is its larger echo intensity because more spins due to the nonselective excitation are involved in the fomiation of the echo. 

Beeause of its emphasis on eonsistent thermodynamies, the csq eode does not permit the use of a P-a model for the erush-up behavior of the powder. Thus, it was neeessary to draw upon the experience in the one-dimensional simulation to select appropriate shock-compression materials behaviors. The... 

One-dimensional double-resonance or homonuclear spin-spin decoupling experiments can be used to furnish information about the spin network. However, we have to irradiate each proton signal sequentially and to record a larger number of ID H-NMR spectra if we wish to determine all the coupling interactions. Selective irradiation (saturation) of an individual proton signal is often difficult if there are protons with close chemical shifts. Such information, however, is readily obtainable through a single COSY experiment. 

For convenience, only one-dimensional random movement will be considered. In this case, an atom is constrained to jump from one stable site to the next in the x direction, the choice of +x or -x being selected in a random way.6 For example, imagine a diffusion experiment starting with a thin layer of N atoms on the surface of a crystal. 

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