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Chemical Shift Differences (chemical + shift_difference)
Selected AbstractsThe First Fulleropyrrolidine Derivative of Sc3N@C80: Pronounced Chemical Shift Differences of the Geminal Protons on the Pyrrolidine Ring.CHEMINFORM, Issue 41 2005Claudia M. Cardona No abstract is available for this article. [source] NMR diffusion measurements under chemical exchange between sites involving a large chemical shift differenceCONCEPTS IN MAGNETIC RESONANCE, Issue 2 2010S. Leclerc Abstract This study concerns the thallium-205 cation in aqueous solution in the presence of a calixarene molecule. Although the measurement of the self-diffusion coefficient of pure thallium (without calixarene in the aqueous solution) does not pose any particular problem, major difficulties are encountered with the standard method using gradient strength increment as soon as thallium is partly complexed by calixarene. With static magnetic field gradients, the NMR signal is so weak that it prevents any reliable measurement, whereas radio frequency (rf) field gradients lead to an unrealistic value of the diffusion coefficient. This failure is explained by the fact that thallium is in fast exchange between two sites (complexed and free thallium) thus exhibiting a single NMR signal although, in the course of the experiment, two signals, with an important difference in resonance frequencies (due to the large thallium chemical shift range), are effectively involved. With the objective to understand these quite unexpected observations, the theory underlying NMR diffusion experiments is first reviewed, and criteria of fast exchange are discussed for three parameters: chemical shifts, relaxation rates, and diffusion coefficients. It turns out that off-resonance effects are responsible for unwanted defocusing due to rf pulses in the static magnetic field gradient method and for time-dependent gradients in the rf field gradient method. Concerning the latter, a remedy is proposed which consists in applying the stronger gradient and incrementing the gradient pulse durations. After correction for relaxation, the expected value of the diffusion coefficient is retrieved. © 2010 Wiley Periodicals, Inc. Concepts Magn Reson Part A 36A: 127,137, 2010. [source] Solid-state NMR studies of the molecular structure of TaxolMAGNETIC RESONANCE IN CHEMISTRY, Issue 6 2006Yu Ho Abstract Solid-state 13C{1H} cross-polarization/magic angle spinning spectroscopy (CP/MAS) has been utilized to extract the molecular structure information of Taxol, which is an anti-tumor therapeutic medicine extracted from the yew bark. The 13C signals have chemical shift values quite consistent with those measured in solution phase, and the overall chemical shift range is over 200 ppm. Notably, most of the 13C resonances of the taxane ring have two clearly resolved spectral components except the resonance peaks of C-15, C-16 and C-17, which are located at the central part of the taxane ring. On the basis of our NMR data, we propose that these doublets originate from two slightly different molecular conformations of the taxane ring and still the central part of the ring remains structurally similar. Furthermore, it is demonstrated that the 13C chemical shift difference deduced from the doublet splittings can serve as a direct measure of the structural difference between the two conformations, which could possibly correlate with the anti-tumor activity of Taxol. Copyright © 2006 John Wiley & Sons, Ltd. [source] Natural Abundance 43Ca NMR Spectroscopy of Tobermorite and Jennite: Model Compounds for C,S,HJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 2 2009Geoffrey M. Bowers There are few effective methods for characterizing the molecular scale structural environments of Ca2+ in hydrated cements, which has limited our ability to understand the structure of, for example, Ca,silicate hydrate (C,S,H). 43Ca nuclear magnetic resonance (NMR) spectroscopy has long been considered too insensitive to provide useful data in this regard, but 43Ca magic angle spinning (MAS) NMR spectra reported here for synthetic tobermorite and jennite with naturally abundant levels of 43Ca demonstrate that this is a viable approach. We show that spectra with useful signal/noise ratios can be obtained in a reasonable acquisition period (,2 days) using an H0 field strength of 21.1 T, 5 mm rotors spinning at a frequency of 5 kHz, and a double frequency sweep preparatory pulse sequence. Tobermorite and jennite produce relatively broad resonances due to their complex structures and structural disorder, however, the chemical shift differences between six-coordinate 43Ca in jennite and seven-coordinate 43Ca in 11 Å tobermorite are large enough that the signals are entirely resolved at this field. These data suggest that signal from ideal tobermorite-like and jennite-like sites in cement C,S,H can most likely be distinguished by 43Ca NMR and that this method will be a powerful approach for studying cement-based ceramic materials in the coming decade. [source] DFT-GIAO1H NMR chemical shifts prediction for the spectral assignment and conformational analysis of the anticholinergic drugs (,)-scopolamine and (,)-hyoscyamineMAGNETIC RESONANCE IN CHEMISTRY, Issue 6 2010Marcelo A. Muñoz Abstract The relatively large chemical shift differences observed in the 1H NMR spectra of the anticholinergic drugs (,)-scopolamine 1 and (,)-hyoscyamine 2 measured in CDCl3 are explained using a combination of systematic/molecular mechanics force field (MMFF) conformational searches and gas-phase density functional theory (DFT) single point calculations, geometry optimizations and chemical shift calculations within the gauge including/invariant atomic orbital (GIAO) approximation. These calculations show that both molecules prefer a compact conformation in which the phenyl ring of the tropic ester is positioned under the tropane bicycle, clearly suggesting that the chemical shift differences are produced by the anisotropic effect of the aromatic ring. As the calculations fairly well predict these experimental differences, diastereotopic NMR signal assignments for the two studied molecules are proposed. In addition, a cursory inspection of the published 1H and 13C NMR spectra of different forms of 1 and 2 in solution reveals that most of them show these diastereotopic chemical shift differences, strongly suggesting a preference for the compact conformation quite independent of the organic or aqueous nature of the solvent. Copyright © 2010 John Wiley & Sons, Ltd. [source] DFT-GIAO 1H and 13C NMR prediction of chemical shifts for the configurational assignment of 6,-hydroxyhyoscyamine diastereoisomersMAGNETIC RESONANCE IN CHEMISTRY, Issue 7 2009Marcelo A. Muñoz Abstract 1H and 13C NMR chemical shift calculations using the density functional theory,gauge including/invariant atomic orbitals (DFT,GIAO) approximation at the B3LYP/6-311G++(d,p) level of theory have been used to assign both natural diastereoisomers of 6,-hydroxyhyoscyamine. The theoretical chemical shifts of the 1H and 13C atoms in both isomers were calculated using a previously determined conformational distribution, and the theoretical and experimental values were cross-compared. For protons, the obtained average absolute differences and root mean square (rms) errors for each comparison showed that the experimental chemical shifts of dextrorotatory and levorotatory 6,-hydroxyhyoscyamines correlated well with the theoretical values calculated for the (3R,6R,2,S) and (3S,6S,2,S) configurations, respectively, whereas for 13C atoms the calculations were unable to differentiate between isomers. The nature of the relatively large chemical shift differences observed in nuclei that share similar chemical environments between isomers was asserted from the same calculations. It is shown that the anisotropic effect of the phenyl group in the tropic ester moiety, positioned under the tropane ring, has a larger shielding effect over one ring side than over the other one. Copyright © 2009 John Wiley & Sons, Ltd. [source] | ||||||||||