High field 17O solid-state NMR study of alanine tripeptides

(17)O chemical shifts of Ala-Ala-Ala, with parallel and anti-parallel beta-sheet structures, are observed using a 930-MHz high-resolution solid-state NMR spectrometer. Ala-Ala-Ala serves as a model sheet-forming peptide because it can be easily prepared as either a parallel or an anti-parallel beta-sheet structure. Spectral differences between the two samples are observed which arise from molecular packing differences between the two sheet structures. DFT chemical shift calculations are performed for the two samples, and the calculated spectra are in good agreement with the experimental spectra. The DFT calculations provide insight into the nature of the chemical shift differences observed between the two sheet structures.     

沸石^17O固体核磁共振研究进展

沸石作为一类最重要的固体氧化物材料,是17O固体核磁共振最早研究对象之一.近年来,随着核磁共振谱仪磁体场强的不断提高,以及新脉冲序列的发展,17O固体核磁共振被越来越多地应用于沸石的结构表征,在研究骨架氧结构以及测定Brnsted酸位的O-H键长等方面都提供了非常丰富的信息.本文将介绍17O固体核磁共振的特点,回顾20年来它在沸石研究方面的发展并着重介绍近期这一方面的研究突破.     

17O NMR studies of low silicate zeolites

Multiple-quantum magic-angle spinning and double-rotation NMR techniques were applied in the high field of 17.6 T to the study of oxygen-17-enriched zeolites A and LSX with the ratio Si/Al = 1. A monotonic correlation between the isotropic value of the chemical shift and the Si-O-Al bond angle alpha (taken from X-ray data) could be found. Hydration of the zeolites causes a downfield 17O NMR chemical shift of about 8 ppm with respect to the dehydrated zeolites. Ion exchange of the hydrated zeolites generates stronger chemical shift effects. The increase of the basicity of the oxygen framework of the zeolite LSX is reflected by a downfield shift of approx. 10 ppm going from the lithium to the cesium form, and the substitution of sodium by thallium in the zeolite A causes a shift of 34 ppm for the O3 signal. 17O DOR NMR spectra are superior to 17O 3QMAS NMR spectra, featuring a resolution increase by a factor of 2 and are about equal with respect to the sensitivity. The residual linewidths of the signals in the 17O DOR and 17O 5QMAS NMR spectra can be explained by a distribution of the Si-O-Al angles in the zeolites.     

Solid-state 17O NMR study of the electric-field-gradient and chemical shielding tensors in polycrystalline gamma-glycine

We report the first experimental determination of the carboxylate oxygen electric-field-gradient (EFG) and chemical shielding (CS) tensors in polycrystalline γ-glycine. Analysis of magic-angle spinning (MAS) and stationary ¹⁷O NMR spectra of [¹⁷O]-γ-glycine obtained at 9.4, 14.1, 16.4, and 18.8 T yields the magnitudes of the ¹⁷O EFG and CS tensors and the relative orientations between the two tensors. Extensive quantum chemical calculations at both the restricted Hartree–Fock and density functional levels have been performed to present the absolute tensor orientations in term of the molecular frame. We have demonstrated that ¹⁷O NMR tensor information could be unambiguously derived by the multiple field analyses of stationary ¹⁷O NMR spectra.     

17O and 13C NMR Studies of Isobenzopyrylium Salts

¹³C and ¹⁷O NMR chemical shifts for a series of isobenzopyrylium salts are reported. The oxygen signal range from 300 to 270 ppm as a double bonded carboxylic oxygen, From the ¹⁷O and ¹³C data valuable informations on the conjugative and substituent effects of isobenzopyrylium salts were obtained.     

93Nb and 17O NMR chemical shifts of niobiophosphate compounds

Niobiophosphate compounds with a large range of niobium and oxygen environments were studied with (93)Nb and (17)O solid-state NMR. (93)Nb isotropic chemical shift of pure niobate Nb(ONb)(6), pure phosphate Nb(OP)(6) and mixed phosphate-niobate Nb(OP)(x)(ONb)((6-x)) (1相似文献   

Natural Abudance 17O NMR Studies of Thiol Esters and Related Analogs

Natural abundance ¹⁷O NMR data for a series of thiol esters and related analogs are reported. The carbonyl signal of the thiol esters range from 463 ppm to 514 ppm; these values are downfield of their oxygen analogs by ca. 150 ppm. A linear relationship between the ¹⁷O NMR chemical shift of the thio-compounds and their oxo-analogs is observed.     

Natural-abundance 17O NMR spectra of some inorganic and biologically important phosphates

A number of optimization techniques were employed to obtain ¹⁷O NMR spectra at natural abundance for a variety of inorganic and orgnic phosphates and polyphosphates. ¹⁷O chemical shifts and some J_po coupling constants are reported for the orthophosphate series of ions from H₃PO₄ to PO₄³⁻, the pyrophosphate ion, P₂O₇⁴⁻, the linear tripolyphosphate ion, P₃O₁₀⁵⁻, and the cyclic trimetaphosphate ion, P₃O₉³⁻; and for disodium dl-α-glycerophosphate and monosodium adenosine monophosphate. ¹⁷O-depleted water enables much improved results to be obtained in acqueous solutions.     

Procedures for labeling the high-resolution axis of two-dimensional MQ-MAS NMR spectra of half-integer quadrupole spins

The increasing development and application of the multiple-quantum MAS NMR for half-integer quadrupole spins has led to various RF pulse sequences for improving the excitation of multiple-quantum coherences and their conversion to single-quantum coherences. As a result, several conventions for labeling the Fl dimension of a 2D MQ-MAS spectrum appear in the literature. The corresponding relations for extracting the isotropic chemical shift, the quadrupole coupling constant, and the asymmetry parameter from experimental data are not always provided. We analyze these various conventions systematically and propose a new one, similar to that introduced by J.-P. Amoureux and C. Fernandez (2000, Solid State NMR 10, 339-343). These various conventions are illustrated with 27Al (I = 5/2) nuclei in aluminum acetylacetonate Al(CH3COCHCOCH3)3. Another experimental problem often met, the aliasing of peaks in the 2D spectrum, is analyzed and illustrated with 27Al (I = 5/2) in NH4Y zeolite and 23Na (I = 3/2) in sodium pyrophosphate Na4P2O7.     

Combined 17O NMR and 11B-31P double resonance NMR studies of sodium borophosphate glasses

17O enriched sodium borophosphate glasses were prepared from isotopically enriched NaPO3 and H3BO3. These glasses have been studied by 17O, 11B and 31P NMR including 17O and 11B multiple quantum magic angle sample spinning (MQMAS), 11B-31P heteronuclear correlation (HETCOR) NMR and 11B{31P} rotational echo double resonance (REDOR). For comparison, the crystalline borophosphates BPO4 and Na5B2P3O13 were included in the investigations. The latter compound shows three sharp 31P resonances at -0.2, -2 and -8 ppm and two BO4 sites that can only be resolved by MQMAS. The 17O NMR spectra were recorded using both the static echo method at medium magnetic field (9.4 T) as well as MAS and MQMAS methods at high field (17.6 T). In total, five oxygen sites were identified in these borophosphate glasses: P-O-P, Na...O-P, P-O-B, B-O-B, Na...O-B. However, these five sites are not present simultaneously in any of the glasses. The 17O MQMAS spectra prove that P-O-B links play a major role in borophosphate glasses. These results are confirmed by the complementary 11B MAS spectra that show the presence of asymmetric and symmetric trigonal groups BO3a and BO3s and two tetrahedral BO4 units. 11B{31P} REDOR NMR is used to give independent information to assign the 11B lines to structural units present in the glasses. These REDOR measurements reveal that B-O-P bonds are present for each borate unit, including the BO3 groups. Particularly, a structural proposal for the two different BO4 resonances is given in terms of a different number of bonded phosphate tetrahedra. The 31P MAS spectra are usually broad and not well resolved. It is shown by 11B-31P HETCOR NMR that a possible structural assignment of a 31P signal at about -20 ppm to Q2 units as in binary sodium phosphate glasses is wrong and that the phosphate tetrahedron belonging to this resonance must be connected to borate groups.     

Both experimental and theoretical investigations of solid-state 17O NMR for L-valine and L-isoleucine

We have presented an experimental investigation of the carboxyl oxygen NMR parameters for four distinct sites in l-valine and l-isoleucine. The carboxyl (17)O quadrupolar coupling constant, C(Q), and isotropic chemical shift, delta(iso), for these compounds are obtained by analyzing two-dimensional (17)O multiple-quantum magic-angle spinning (MQMAS) and/or 1D MAS spectra. The values of C(Q) and delta(iso) found to be in the range of 7.00-7.85 MHz, and 264-314 ppm, respectively. Extensive quantum chemical calculations at the density functional levels have been performed for a full cluster of l-valine molecules and a few theoretical models. The calculated results indicated that there was a correlation between the (17)O NMR parameters and C-O bond lengths, which was helpful for the spectral assignment. They also demonstrated that the torsion angle of l-valine plays an important role in determining the magnitudes of (17)O NMR parameters.     

Comparison of the (17)O NMR spectra of zeolites LTA and LSX

¹⁷O NMR studies of various cation-exchanged LTA and LSX zeolites have shown similarities between the two systems. LSX samples containing divalent cations contain resonances with similar chemical shifts to those previously assigned to ‘bare’ framework oxygen atoms in Ca-LTA and Sr-LTA. The assignments are consistent with the trends seen in the spectra of monovalent cation-containing LSX and LTA zeolites, which show an increase in the average chemical shift with increasing cationic radius. The spectrum of Li-LSX, like Na-LSX, can be assigned based on the T–O–T bond angles. Gas sorption studies on Li-LSX are used to help identify the framework oxygen atoms that form the β-cages and demonstrate the sensitivity of the ¹⁷O shifts to gas loading.     

17O NMR studies of a triangular-lattice superconductor NaxCoO2 x yH(2)O

We report the first 17O NMR studies of a triangular-lattice superconductor Na(1/3)CoO2 x 4/3H(2)O and the host material Na(x)CoO2 (x=0.35 and 0.72). Knight shift measurements reveal that p-d hybridization induces sizable spin polarization in the O triangular-lattice layers. Water intercalation makes CoO2 planes homogeneous and enhances low frequency spin fluctuations near T(c)=4.5 K at some finite wave vectors different from both the ferromagnetic and "120 degree" modes.     

A combined NMR and microstructural study of the effect of high-pressure processing on strawberries

A combination of nuclear magnetic resonance water proton relaxometry and optical microscopy is used to investigate the effects of high pressure on parenchyma tissue of fresh strawberries (Elsanta variety). Although a low pressure of just 35 MPa induces no visible tissue damage, there are subtle changes in the water relaxation behavior suggesting subcellular water redistribution. Higher pressures of 100 MPa are shown to rupture membranes and cause major water redistribution. Cell wall damage is apparent at pressures of 300 MPa.     

A spectroscopic study of 18F: (I). The 17O(p,p)17O and 17O(p, α0)14N reactions

The ¹⁷O(p, p)¹⁷O and ¹⁷O(p, α₀)¹⁴N reactions have been studied in the energy range E_p = 0.5–1.33 MeV. Excitation functions for elastic scattering measured at several angles give l_p values for six resonances and J^π; T values of 3⁺; 1 and 2⁺; 1 for the states at 6.16 and 6.28 MeV, respectively. From both reactions, J^π limitations were found for six resonant levels. The ¹⁷O(p, α₀)¹⁴N reaction also yields information on T-assignments and level formation parameters. Experimental results are discussed in terms of shell-model configurations.     

Natural abundance (17)O NMR spectroscopy of rat brain in vivo

Oxygen is an abundant element that is present in almost all biologically relevant molecules. NMR observation of oxygen has been relatively limited since the NMR-active isotope, oxygen-17, is only present at a 0.037% natural abundance. Furthermore, as a spin 5/2 nucleus oxygen-17 has a moderately strong quadrupole moment which leads to fairly broad resonances (T(2)=1-4 ms). However, the similarly short T(1) relaxation constants allow substantial signal averaging, whereas the large chemical shift range (>300 ppm) improves the spectral resolution of (17)O NMR. Here it is shown that high-quality, natural abundance (17)O NMR spectra can be obtained from rat brain in vivo at 11.74 T. The chemical shifts and line widths of more than 20 oxygen-containing metabolites are established and the sensitivity and potential for (17)O-enriched NMR studies are estimated.