Proton chemical shift anisotropy

Tjandra N and Bax A 1997 Solution NMR measurement of amide proton chemical shift anisotropy in N-15-enriched proteins. Correlation with hydrogen bond length J. Am. Chem. Soc. 119 8076-82... 

A new NMR method for the determination of the anomeric configuration in mono- and disaccharides has been described.18 The protocol is based on the different cross-correlated relaxation between proton chemical shift anisotropy (CSA) and dipolar relaxation for the a and (3 anomers of sugars. Only the ot-anomers show the presence of CSA (HI or Hl )-proton dipole (H1-H2 or Hl -H2 ) in the longitudinal relaxation of the anomeric protons. The method is of special interest for cases in which vicinal coupling constants between HI and H2 in both anomers a and (3 are similar and small, such as D-mannose, and the non-ambiguous description of the anomeric configuration needs additional measurements. 

Using time-dependent perturbation theory and taking full account of the symmetry and commutation relations for the high-order dipolar Hamiltonians, Hohwy et al.61 69 gave a systematic analysis of homonuclear decoupling under sample rotation and proposed a novel approach to the design of multiple-pulse experiments. Based on the theoretical analysis, they proposed a pulse sequence that can average dipolar interaction up to the fifth order. One example of these pulse sequences is shown at the top of Fig. 3. This sequence is sufficiently powerful that it is possible to obtain precise measurement of proton chemical shift anisotropies, as shown in Fig. 3. 

Only the anisotropy of the magnetic susceptibility influences the isotropic mean value, whereas the complete susceptibility tensor contributes to the chemical shift anisotropy [see Eq. (36)]. The influence of the susceptibility of a spherical symmetric charge distribution on the isotropic chemical shift of a nearby nucleus will be zero, but there is a contribution to the chemical shift tensor. Especially in solid state proton chemical shift investigations this effect is quite remarkable and can be observed when studying proton chemical shift anisotropies. 

Tjandra N, Bax A (1997) Solution NMR measurement of amide proton chemical shift anisotropy in N-ebmiched proteins. Corrrelation with hydrogen bond length. J Am Chem Soc 119 8076-8082 Tossell JA (1984) Correlation of Si NMR chemical shifts in sihcates with orbital energy differences obtained from x-ray spectra. Phys Chem Mineral 10 137-141 Tossell JA (1992) Calculation of the Si NMR shielding tensor in forsterite. Phys Chem Mineral 19 338-342... 

The process of spin-lattice relaxation involves the transfer of magnetization between the magnetic nuclei (spins) and their environment (the lattice). The rate at which this transfer of energy occurs is the spin-lattice relaxation-rate (/ , in s ). The inverse of this quantity is the spin-lattice relaxation-time (Ti, in s), which is the experimentally determinable parameter. In principle, this energy interchange can be mediated by several different mechanisms, including dipole-dipole interactions, chemical-shift anisotropy, and spin-rotation interactions. For protons, as will be seen later, the dominant relaxation-mechanism for energy transfer is usually the intramolecular dipole-dipole interaction. 

Molecular anisotropy affects proton chemical shifts to a far greater extent than 13C chemical shifts. This is because the protons occupy the outer extremities of a molecule whilst the carbon framework is far more internal and to a large extent, removed from the influences of anisotropy. 

Despite having been the earliest attempted prediction, proton prediction remains relatively poor. The reasons for this have been alluded to earlier but to summarise the proton chemical shift is often highly dependant on through-space effects (anisotropy) and has a very small distribution. There are four main commercial approaches to proton prediction currently Incremental parameters, HOSE code databases, semi-empirical and cib initio methods. 

Here, ojr is the rate of spinner rotation. I is the proton spin number, 8 is the chemical shift anisotropy (CSA) and q is the asymmetric parameter of the CSA tensor. Thus, the line broadening occurs when an incoherent fluctuation frequency is very close to the coherent amplitude of proton decoupling monotonously decreased values without such interference in Figure 1. 

French workers have studied the 1H- and 13C-NMR parameters of disubstituted selenophenes.37 38 The proton chemical shifts are discussed in terms of magnetic anisotropy and electric field effects of the substituents in order to study the conformational equilibrium of the carbonyl group. The relationship between the H- and 13C-chemical shifts and 7t-electron distribution calculated by the PPP method are examined. Shifts and coupling constants are discussed in additivity terms. 

In an organic solid representative broadenings are 150 ppm for aromatic carbon chemical shift anisotropy and 25 kHz (full width at half-height) for a rather strong carbon-proton dipolar interaction. At a carbon Larmor frequency of 15 MHz, the shift anisotropy corresponds to 2.25 kHz. In high magnetic fields the forms of the respective Hamiltonians are... 

A single proton species can be irradiated exactly on resonance in general the spread in Larmor frequencies is determined by the breadth of the chemical shift spectrum Ao- (liQifi. Chemical shift anisotropy must be included, even if the sample is spun. If the... 

---