Effective chemical shift anisotropy

Fig. 13. (Upper) ip-NMR spectrum (121.5 MHz) of the purple membrane from Halobacterium cutirubrum obtained with high-power H decoupling at IS C spectral width 125 kHz acquisition time 6 ms recycle time 1 s pulse width 45° decoupler on 4 fts before acquisition and during acquisition but off during remainder of cycle Fourier transform of 16,384 data points after zero iilling. (Lower) Computer simulation of the above in terms of two axially symmetric powder patterns characterized by effective chemical-shift anisotropies of -I-61 and 4-18.5 ppm the angular-independent and -dependent linewidths were 300 and 200 Hz, and 350 and 250 Hz, for the phosphomonoester and phosphodiester, respectively. The broken curves are the powder patterns for the two types of phosphate ester present. From Ekiel et al. (1981).

Tjandra N, Szabo A and Bax A 1996 Protein backbone dynamics and N-15 chemical shift anisotropy from quantitative measurement of relaxation interference effected. Am. Chem. Soc. 118 6986-91... 

Figure 3 Characteristic solid state NMR line shapes, dominated by the chemical shift anisotropy. The spatial distribution of the chemical shift is assumed to be spherically symmetric (a), axially symmetric (b), and completely asymmetric (c). The top trace shows theoretical line shapes, while the bottom trace shows rear spectra influenced by broadening effects due to dipole-dipole couplings.

It can be seen that, in all cases, relaxation rates are directly proportional to (Aa). Because Aa reflects the anisotropy of the shielding tensor and because the chemical shift originates from the shielding effect, the terminology Chemical Shift Anisotropy is used for denoting this relaxation mechanism. Dispersion may be disconcerting because of the presence of Bq (proportional to cOq) in the numerator of and R2 (Eq. (49)). Imagine that molecular reorientation is sufficiently slow so that coo 1 for all considered values of coo from (49), it can be seen that R is constant whereas R2 increases when Bq increases, a somewhat unusual behavior. 

The magnitude of the chemical shift anisotropy depends on the bonding situation and the nucleus gyromagnetic ratio. Since the bonds formed by lithium in organolithium compounds or other lithiated systems are mainly ionic, the anisotropy of the lithium chemical shift is generally small. It is more pronounced for Li than for Li. Li spectra are dominated by the quadrupolar effect and the CSA contribution to the Li lineshape is often negligible. Exceptions are compounds with poly-hapto bound lithium, such as... 

Solids—Many polymers are either soluble or insoluble. NMR of solids generally give broad lines because of the effects of dipolar coupling between nuclei and the effect of chemical shift anisotropy (CSA). Both of these effects are greatly reduced for polymers in solution and allow for decent spectra of soluble polymers in solution. 

Hence, originally designed to eliminate dipolar interactions, MAS has the main effect on the removal of the chemical shift anisotropy, which is rather pronounced in 13C NMR spectroscopy. Since heteronuclear interactions could be viewed as a perturbation of abundant spins (I) on the energy states of rare spin system (S), a more convenient way of reducing HD to zero is high power decoupling of the I nuclei < u = 0). 

The carbon-proton dipolar interaction and the chemical shift anisotropies broaden the lines in solid state 13C NMR spectra. The major effect arises from the dipolar coupling of the carbon nuclei with neighboring protons homonuclear dipolar couplings between two adjacent 13C nuclei are neglegible because of their low natural abundance. The large magnitude of dipolar 13C— H coupling (up to 40 kHz) results in broad and structureless proton-coupled 13C NMR absorptions. 

The electrons modify the magnetic field experienced by the nucleus. Chemical shift is caused by simultaneous interactions of a nucleus with surrounding electrons and of the electrons with the static magnetic field B0. The latter induces, via electronic polarization and circulation, a secondary local magnetic field which opposes B0 and therefore shields the nucleus under observation. Considering the nature of distribution of electrons in molecules, particularly in double bonds, it is apparent that this shielding will be spatially anisotropic. This effect is known as chemical shift anisotropy. The chemical shift interaction is described by the Hamiltonian... 

The following strategy therefore emerges for the study of quadrupolar nuclei observe the central transition of nuclei with noninteger spin, use MAS (to remove dipolar coupling, chemical shift anisotropy, and first-order quadrupolar effects), and work at high fields (to minimize second-order effects). 

Trifluoromethyl-substituted517 and perfluorophenyl-substitutedcarbocations518,519 have also been prepared and studied. Because of the relatively large fluorine chemical shifts, anisotropy and ring current effects play a relatively much smaller role than they... 

Fig. 15 Effect of a phenyl ring yr-flip on the orientation of the chemical shift anisotropy tensor components for unprotonated and protonated aromatic carbons...

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