High-field QCPMG NMR of large quadrupolar patterns using resistive magnets

Spectroscopy in a high magnetic field reduces second-order quadrupolar shift while increasing chemical shift. It changes the scale between quadrupolar and chemical shift of half-integer quadrupolar spins. The application of QCPMG multiple echo for acquiring large quadrupolar pattern under the high magnetic field of a 25 T resistive magnet is presented for acquiring large quadrupolar patterns. It shows that temporal field fluctuations and spatial homogeneity of the Keck magnet at the NHMFL contribute about ±20 ppm in line broadening. NMR patterns which have breadths of hundreds to thousands of kilohertz can be efficiently recorded using a combination of QCPMG and magnetic field stepping with negligible hindrance from the inhomogeneity and field fluctuations of powered magnets.     

Solid state (47,49)Ti, (87)Sr and (137)Ba NMR characterisation of mixed barium/strontium titanate perovskites

Solid state ^47,49Ti, ¹³⁷Ba, ⁸⁷Sr NMR spectra have been recorded on Ba_xSr_1−xTiO₃ (0 x 1) perovskite samples prepared by the powder sintering method. Multinuclear solid state NMR shows great potential for characterising such systems since the quadrupolar parameters are very sensitive to any geometric deformation around the studied nucleus. ^47,49Ti NMR powder lineshapes appear strongly influenced by the presence of even a small amount of barium (or strontium) in the coordination second sphere of the probed titanium site: substitution of strontium by barium induces the broadening of the peaks, due to quadrupolar effects, while the isotropic chemical shift increases. ¹³⁷Ba NMR spectra exhibit a distribution of the quadrupolar interaction, that could be tentatively quantified, C_Q increasing with the amount of strontium. Preliminary results were also obtained on ⁸⁷Sr NMR showing behaviour comparable to ¹³⁷Ba NMR, i.e. a broadening of the peaks due to an increasing quadrupolar interaction with the amount of barium distorting the environment of the strontium sites.     

Solid-state 25Mg QCPMG NMR of bis(cyclopentadienyl)magnesium

Application of the "quadrupolar Carr-Purcell Meiboom-Gill" (QCPMG) sequence permits the first natural abundance solid-state 25Mg NMR study of an organometallic magnesium compound, bis(cyclopentadienyl)magnesium. Analytical and numerical simulations of both static and magic-angle spinning QCPMG NMR spectra beget an axially symmetric 25Mg electric field gradient (EFG) tensor (quadrupolar asymmetry parameter, eta(Q)=0.01(1)) with a nuclear quadrupole coupling constant of C(Q)=5.80(5)MHz. Restricted Hartree-Fock and hybrid density functional theory (B3LYP) calculations are in good agreement with experimental EFG values and predict a chemical shielding anisotropy of about 40-50 ppm, which we attempt to elucidate by numerical simulations. The parameters and orientation of the 25Mg EFG tensor are rationalized from examination of the crystal structure and molecular symmetry. The NMR properties of the cyclopentadienyl rings are examined by 13C[1H] CPMAS NMR, RHF and hybrid-DFT (B3LYP) calculations, and simulations of the effects of chemical exchange on the 13C powder pattern.     

Observation of "hidden" magnesium: first-principles calculations and 25Mg solid-state NMR of enstatite

²⁵Mg NMR parameters have been determined for two polymorphs of enstatite (MgSiO₃), an important magnesium silicate phase present as a major component of the Earth's upper mantle. The crystal structures of both polymorphs contain two crystallographically distinct magnesium sites; however, only a single resonance is observed in ²⁵Mg MAS NMR spectra recorded at 14.1 and 20.0 T. First-principles calculations performed on geometry-optimised crystal structures reveal that the quadrupolar interaction for the second site is expected to be very large, resulting in extensive broadening of the spectral resonance, explaining its apparent absence in the NMR spectrum. ²⁵Mg QCPMG NMR experiments employing variable offset cumulative spectroscopy (VOCS) are used to observe the broadened site and enable measurement of NMR parameters. The large difference in quadrupolar interaction between the two crystallographic magnesium sites is rationalised qualitatively in terms of the distortion of the local coordination environment as well as longer-range effects using a simple point charge model.     

A general strategy for the NMR observation of half-integer quadrupolar nuclei in dilute environments.

A general strategy for the observation of low gamma half-integer quadrupolar nuclides in biological systems is presented. The methodology combines low-temperature (4-100 K) techniques with cross-polarization (CP) experiments while employing a so-called Carr-Purcell-Meiboom-Gill spin-echo sequence (CPMG). This combined approach is termed CP/QCPMG. Also discussed are data processing issues that are unique to the induced signals that result from the QCPMG pulse sequence. Central to this strategy is the development of a stable low-temperature (4 to 250 K) NMR double-resonance probe. The probe is robust enough to handle multiple contact experiments and long acquisition periods with 1H decoupling. This approach is illustrated with low-temperature solid-state 67Zn and 25Mg NMR CP/QCPMG experiments on model compounds. The conclusion reached is that the strategy affords sufficient sensitivity to examine Zn2+ and/or Mg2+ binding sites in metalloproteins.     

Simulations of molecular dynamics in solid-state NMR spectra of spin-1 nuclei including effects of CSA- and EFG-terms up to second order

By numerical simulations MAS and QCPMG methods for acquiring spectra of spin-1 nuclei were compared in order to determine the most sensitive experiment for analysis of molecular dynamics. To comply with the large quadrupolar constants for 14N and the CSA reported for 6Li both of these interactions are included up to second order. For 2H and 6Li both QCPMG and single-pulse MAS experiments were suitable for dynamics studies whereas the single-pulse MAS experiment were the method of choice for investigation of 14N dynamics for C(Q)'s larger than 750kHz at 14.1T. This property prohibits excitation of the 14N lineshape using either single hard or softer composite rf-pulses. Focusing on 14N it was demonstrated that the centerband lineshape is sensitive toward both off-MAS and CSA effects. In addition, excitation by real-time pulses showed that proper lineshapes corresponding to a site with a C(Q) of 3MHz may be excited by a very short pulse.     

Molecular dynamics of half-integer quadrupolar nuclei studied by QCPMG solid-state NMR experiments on static and rotating samples. Theory and simulations

Simulations of QCPMG NMR type experiments have been used to explore dynamic processes of half-integer quadrupolar nuclei in solids. By setting up a theoretical approach that is well suited for efficient numerical simulations the QCPMG type experiments have been analyzed regarding the effect of the magnitude of the EFG- and CSA-tensors, the spin-quantum number, different dynamical processes and MAS. Compared to the QE experiment the QCPMG experiment offers not only intensity gain by an order of magnitude and changes in overall lineshape as a function of the kinetic rate constant but the lineshape of the individual spin-echo sidebands is also very sensitive towards dynamics. Hereby a visual identification of the dynamics is obtained. In common for all the simulations the spin-echo sidebands are narrow in the slow (k< or =10(2) Hz) and the fast (k> or =10(7) Hz) dynamic regime whereas they are broadened in the intermediate regime 10(3)< or =k< or =10(7) Hz. The maximum intensity of the spin-echo sidebands for two-site jumps is highly dependent on the type of anisotropic interactions involved and the type of QCPMG experiment. Hence, in the fast limit the maximum intensity was 140% of the initial intensity when significant CSA was present or under the QCPMG-MAS experiment compared to 89 or 71% for the static experiment influenced by the quadrupolar interaction only. For 3-, 4-, and 6-site jumps the maximum intensity in the fast limit reached up to 339% of the intensity in the static limit.     

87Sr/86Sr in Saxon Mineral and Spa Waters

Abstract

Understanding and preserving the genesis of natural mineral and spa waters is a matter of keen interest. Under a complex analysis programme, ⁸⁷Sr/⁸⁶Sr ratios (as well as other isotopes) were measured in such waters at various sites in Saxony, producing values ranging between 0.708 and 0.731. The strontium isotope ratio was found to be closely linked to the flow patterns and variations in the chemical composition of water. The ⁸⁷Sr/⁸⁶Sr ratio can thus be used as an indicator to characterize groundwater-rock interaction and hence the variation of flow paths. It is especially useful for differentiating waters in a lithologically heterogeneous aquifer system. However, it has to be applied together with other methods and different samples from the same area should be compared.     

Estimating groundwater mixing and origin in an overexploited aquifer in Guanajuato, Mexico, using stable isotopes (strontium-87, carbon-13, deuterium and oxygen-18)

Stable Isotopes (strontium-87, deuterium and oxygen-18, carbon-13) have been used to reveal different sources of groundwater and mixing processes in the aquifer of the Silao-Romita Valley in the state of Guanajuato, Mexico. Calcite dissolution appeared to be the main process of strontium release leading to relatively equal (87)Sr/(86)Sr ratios of 0.7042-0.7062 throughout the study area which could be confirmed by samples of carbonate rocks having similar Sr ratios (0.7041-0.7073). delta(13)C values (-11.91- -6.87 per thousand VPDB) of groundwaters confirmed the solution of carbonates but indicated furthermore influences of soil-CO(2). Deuterium and (18)O contents showed a relatively narrow range of-80.1- -70.0 per thousand VSMOW and -10.2- -8.8 per thousand, VSMOW, respectively but are affected by evaporation and mixing processes. The use of delta(13)C together with (87)Sr/(86)Sr revealed three possible sources: (i) carbonate-controlled waters showing generally higher Sr-concentrations, (ii) fissure waters with low-strontium contents and (iii) infiltrating water which is characterized by low delta(13)C and (87)Sr/(86)Sr ratios. The third component is affected by evaporation processes taking place before and during infiltration which might be increased by extraction and reinfiltration (irrigation return flow).     

Signal enhancement in solid-state NMR of quadrupolar nuclei

Recent progress in the development and application of signal enhancement methods for NMR of quadrupolar nuclei in solids is presented. First, various pulse schemes for manipulating the populations of the satellite transitions in order to increase the signal of the central transition (CT) in stationary and rotating solids are evaluated (e.g., double-frequency sweeps, hyperbolic secant pulses). Second, the utility of the quadrupolar Carr–Purcell–Meiboom–Gill (QCPMG) and WURST-QCPMG pulse sequences for the rapid and efficient acquisition of particularly broad CT powder patterns is discussed. Third, less frequently used experiments involving polarization transfer from abundant nuclear spins (cross-polarization) or from unpaired electrons (dynamic nuclear polarization) are assessed in the context of recent examples. Advantages and disadvantages of particular enhancement schemes are highlighted and an outlook on possible future directions for the signal enhancement of quadrupolar nuclei in solids is offered.     

Effect of strontium substitution on superconductivity in YBa 2 Cu 4 O 8

Superconducting powders with the composition Y(Ba 1 mx Sr x ) 2 Cu 4 O 8 ( x = 0.00-0.50) have been prepared by an aqueous sol-gel method. The effects of strontium substitution on the properties of compounds were studied by resistivity measurements, X-ray powder diffraction, thermogravimetric analysis, electron microscopy and elemental analysis. The data indicate that single-phase Y(Ba 1 mx Sr x ) 2 Cu 4 O 8 superconducting samples were obtained. They also show that doping with strontium has a strong effect on the superconducting properties of the YBa 2 Cu 4 O 8 phase. The critical temperature is enhanced from 78 K (for a non-substituted sample) to 88 K (for Y(Ba 1 mx Sr x ) 2 Cu 4 O 8 ). Elemental analysis data clearly indicate that small amounts of strontium enter the copper sites in the Y(Ba 1 mx Sr x ) 2 Cu 4 O 8 compounds. A point-defect chemistry approach, which explains the enhancement of T c by substituting strontium for barium, is presented.     

Flooding of lignite mines: isotope variations and processes in a system influenced by saline groundwater

The quality of both groundwaters and surface waters that arise during flooding of abandoned lignite open pits are influenced by regional and local factors. A typical regional factor is due to oxidised sedimentary sulfides. A more local factor is the interaction of shallow water with highly saline groundwater, which is important in Merseburg-Ost (Germany). Investigation of this system is aided by the use of many environmental isotope tracers but special problems can arise. In order to reveal processes in the mine environment (shallow groundwater, lake water) and to characterise mixtures with saline groundwater results are described using the tracers deltaD, delta18O, delta13C, delta34S, 87Sr/86Sr, 3H, 14C, 39Ar, and 222Rn. Deep highly saline groundwater had a radiocarbon concentration typically below 10 pMC. The values of delta13C(DIC) are around-5 per thousand. As delta13C of the aquifer rock samples (Permian, Zechstein carbonates) was in the range of-6...+5 per thousand, residence time corrections based on delta13C are questionable. Additional checks with 39Ar, as well as results from the variationof delta18O (or deltaD) with respect to the salinity, emphasise a Holocene age; as is also the case for most mineralised groundwaters and also for water having a low delta18O (and deltaD). For saline groundwater residing in the Zechstein aquifer the measured delta34S values of about 12 per thousand are close to those expected from the literature. In contrast, the 87Sr/86Sr ratio of dissolved strontium is far from the values anticipated for the aquifer rocks despite there being proportionality between the chloride concentration and the strontium concentration. Furthermore, the proportionality is not valid in lower mineralised water. The 87Sr/86Sr ratio can, therefore, hardly be used as a tracer for the distribution of ascending saline water. The amount of salt-water coming from below into the residual quarry basins is an essential contribution to the lake inventories. Therefore, 222Rn was used to assist in determining the renewal of salt-water layers that formed in deep lake locations. In the deep zones 222Rn concentrations up to 6 Bq/l were measured but were dominantly in equilibrium with 226Ra, which was found in all higher mineralised groundwater samples. Excess radon was limited to just a few decimetres above the lake sediment surface but does not appear to be caused by continuous groundwater discharge.Hydrochemical investigations of groundwater from the Quaternary aquifer were carried out over the last six years before flooding was complete. Apart from a slight downward shift of the average sulfate concentration, other changes showed virtually no trends. An increase of the sulfate concentration was mostly correlated with a decrease of delta34S for individual sites only, but not for the whole ensemble of sampling locations. Sulfate from pyrite oxidation plays an important role but cannot be attributed unequivocally to coal mining. There are hints that the conditions closer to the basin edges may differ from those remoter parts of the flood plain.     

2-photon ionization for efficient seeding and trapping of strontium ions

We describe an efficient way to photoionize strontium atoms in a linear radio-frequency trap. We use a 2-photon second order process to excite the autoionization resonance (4d²+5p²) ¹D₂ in neutral strontium (Sr). A doubled Ti:sapphire laser system is used at 431 nm to provide 100 fs pulses at 82 MHz. The fabrication of the laser systems for addressing the Sr⁺ transitions necessary for laser cooling and excitation of quantum jumps, vacuum system and ion trap structure are also described. With the current setup a easy and repeatable trapping of linear ion chains is readily achieved at very low Sr vapor pressures.     

States in86Sr,84Sr and87Y populated in the (p,t) reaction

The (p,t) reactions on⁸⁸Sr,⁸⁴Sr and⁸⁹Y have been carried out at a bombarding energy of 49.5 MeV. Some low-lying excitations in⁸⁶Sr and⁸⁴Sr associated with configurations of 1g _9/2 and 2p _1/2 neutrons have been identified. Levels populated to 4 MeV of excitation in the strontium nuclei and to 2.5 MeV in⁸⁷Y have been studied in the present experiment. In the case of⁸⁷Y most of the levels populated are of a complex nature.     

A combined 17O RAPT and MQ-MAS NMR study of L-leucine

We report the application of rotor-assisted population transfer (RAPT) to measure the quadrupolar coupling constant (C(q)) for spin 5/2 nuclei. Results from numerical simulations are presented on the magnitude of enhancement factor as a function of frequency offsets, i.e. the RAPT profile. Experimental O17 RAPT profile is traced for the amino acid L-leucine. In addition, results from MQ-MAS experiments are incorporated to determine the quadrupolar asymmetry parameter (eta(q)). Unlike previous reports, the O17 NMR parameters for an amino acid, L-leucine, is reported at a relatively low field of 9.4 T.     

87Sr/86Sr-Untersuchungen an Grundwässern des Berliner Urstromtales

From a sector within an extended Tertiary basin 21 groundwater samples as well as 3 rock samples of a Zechslein diapir were analysed for ⁸⁷Sr/⁸⁶Sr-ralio. As a tendency the isotope ratio of the dissolved strontium is decreasing with increasing depth and strontium content. Furthermore, strontium content and salinity are correlated. With two exceptions the isotope data are in the range between about 0.7080 and 0.7100. Significant differences in the strontium isotope composition were found between the Zechstein salts and the typical groundwaters. This shows, that the Zechstein diapir can not be the source of the higher salinity in parts of the groundwater system. The results are discussed.     

Increased strontium uptake in trabecular bone of ovariectomized calcium‐deficient rats treated with strontium ranelate or strontium chloride

Based on clinical trials showing the efficacy to reduce vertebral and non‐vertebral fractures, strontium ranelate (SrR) has been approved in several countries for the treatment of postmenopausal osteoporosis. Hence, it is of special clinical interest to elucidate how the Sr uptake is influenced by dietary Ca deficiency as well as by the formula of Sr administration, SrR versus strontium chloride (SrCl₂). Three‐month‐old ovariectomized rats were treated for 90 days with doses of 25 mg kg^?1 d^?1 and 150 mg kg^?1 d^?1 of SrR or SrCl₂ at low (0.1% Ca) or normal (1.19% Ca) Ca diet. Vertebral bone tissue was analysed by confocal synchrotron‐radiation‐induced micro X‐ray fluorescence and by backscattered electron imaging. Principal component analysis and k‐means clustering of the acquired elemental maps of Ca and Sr revealed that the newly formed bone exhibited the highest Sr fractions and that low Ca diet increased the Sr uptake by a factor of three to four. Furthermore, Sr uptake in bone of the SrCl₂‐treated animals was generally lower compared with SrR. The study clearly shows that inadequate nutritional calcium intake significantly increases uptake of Sr in serum as well as in trabecular bone matrix. This indicates that nutritional calcium intake as well as serum Ca levels are important regulators of any Sr treatment.     

Cation Radii and Oxygen Deficiency Effects on the Structural,Magnetic, and Electrical Properties in La 1− x Sr x MnO 3−δ □ δ Manganites ( x = 0.2-0.5 and δ = 0.1)

The series of non-stochiometric strontium substituted lanthanium manganites La 1 m x Sr x MnO 3 m i i ( i = 0.1, x = 0.2-0.5) has been studied and show the effect of oxygen deficiency on the structural transition, magnetic and electrical properties of these compounds. Polycrystalline samples La 1 m x Sr x MnO 3 m i i were synthesised by a new method at atmospheric pressure. In this series of manganites, the Mn 4+ content is systematically decreased due to increase in the non-stoichiometry. X-ray diffraction analysis shows a phase transition from orthorhombic to rhombohedral systems for 0.2 h x h 0.5. The material is ferromagnetic for 0.3 h x h 0.5 and antiferromagnetic for x = 0.2. The Curie temperature T C increases with increasing x . The resistivity as a function of temperature shows that samples with x = 0.3 and ferromagnetic metal between T CF and T P becomes ferromagnetic insulators below T CF where charge-ordering seems to appear.     

通过超宽139La固体核磁共振波谱研究层状La(OH)2NO3

层状稀土氢氧化物是一类新型的稀土功能材料，本文采用固体核磁共振（SSNMR）方法研究了同时具备离子交换能力和非线性光学特性的层状La（OH）₂NO₃化合物，探讨了通过四极核CPMG（QCPMG）脉冲序列和变频谱图采集获取超宽¹³⁹La SSNMR谱图的方法，并描述了适用于此类实验的滤波方程和谱图重建方法.重建谱图同时包含四极核中心跃迁和卫星跃迁信息，本文使用QUEST软件对超宽¹³⁹La NMR谱图进行了模拟，获取的四极耦合常数C_Q和非对称因子η_Q均与CASTEP密度泛函理论计算值高度吻合.SSNMR实验结果证实层状La（OH）₂NO₃化合物属于非中心对称结构（P2₁），解决了对其结构长期以来存在的争论.