Chemical shift definition

It is evident from Table 2 that the chemical shift data are very similar in both states of aggregation. Only the carbonyl carbon show a small but definite shifts, 2 ppm. In the solution state, in acetone -d6 solution the relaxation times T1 of the pyranose carbon atoms are very similar and only slightly smaller than those of the carbon atom of the methyl group in the acetyl substituent, while the T1-value of the carbon atom of the carbonyl group is considerably higher. 

Usually, a careful analysis of the combination of fluorine, proton, and carbon NMR chemical shifts and spin-spin coupling constants will provide definitive information regarding the structure of disubstituted fluoroaromatics. 

An example of the use of chemical shifts to delineate residual secondary structure is given in Figure 3 for the molten globule state of apomyo-globin (Eliezer et al., 1998 Eliezer et al., 2000). Combined use of 13C , H , 13C, and 13CO secondary shifts gives a more precise definition of secondary structure boundaries than use of 13C shifts alone (Eliezer et al., 2000). 

Rings incorporating [4 +2] rt-electrons are aromatic according to the Hiickel definition and on this basis 1,2,3-thiadiazoles can be considered as aromatic. This is supported by 13C and 111 NMR chemical shifts. In 1990, the aromaticities of some five- and six-membered ring heterocycles including 1,2,3-thiadiazole were studied by computational methods and found to correlate well with their chemical natures <1990JPR885>. 

J-splitting, when it exists, imposes the definition of new spin quantities. These quantities also evolve according to relaxation phenomena and may interfere (by relaxation) with the usual magnetization components. This latter interference stems precisely from cross-correlation rates, i.e., relaxation parameters which involve two different mechanisms, for instance the dipolar interaction and the so-called Chemical Shift Anisotropy (27,28) (csa)... 

The shielded chemical shift is in turn due to the strong magnetic anisotropy of the sp -hybridized carbons. All the above dications are definitively classical, nonbridged cations, as also shown by the chemical shift additivity criterion of Schleyer and coworkers. 

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