Na and H NMR Microimaging of Intact Plants

²³Na NMR microimaging is described to map, for the first time, the sodium distribution in living plants. As an example, the response of 6-day-old seedlings of Ricinus communis to exposure to sodium chloride concentrations from 5 to 300 mM was observed in vivo using ²³Na as well as ¹H NMR microimaging. Experiments were performed at 11.75 T with a double resonant ²³Na–¹H probehead. The probehead was homebuilt and equipped with a climate chamber. T₁ and T₂ of ²³Na were measured in the cross section of the hypocotyl. Within 85 min ²³Na images with an in-plane resolution of 156 × 156 μm were acquired. With this spatial information, the different types of tissue in the hypocotyl can be discerned. The measurement time appears to be short compared to the time scale of sodium uptake and accumulation in the plant so that the kinetics of salt stress can be followed. In conclusion, ²³Na NMR microimaging promises great potential for physiological studies of the consequences of salt stress on the macroscopic level and thus may become a unique tool for characterizing plants with respect to salt tolerance and salt sensitivity.     

Hardware modification of a 7 mm MAS NMR probe to a single-crystal goniometer

Tensorial terms of the Hamiltonian can be measured by solid-state single-crystal nuclear magnetic resonance (NMR) spectroscopy which requires a goniometer NMR probehead. Goniometer probes; however, are not standard parts of solid NMR spectrometers and are available only at a much higher price than magic-angle spinning (MAS) probeheads widely used in research. Due to requirements of MAS experiments, modern probeheads are designed for small ceramic rotors, which are 1-4 mm in diameter, to reach very high angular frequencies, so there are several older 7 mm MAS probeheads used rarely todays in NMR laboratories. In this paper, a simple method is presented how to rebuild step-by-step a 7 mm Bruker MAS probehead to be suitable for single-crystal spectroscopy. In the second part (31)P chemical shift tensors of Na(4)P(2)O(7) x 10H(2)O are determined to demonstrate the functionality of the rebuilt probehead.     

<Superscript>23</Superscript>Na spin-lattice relaxation in powder Rochelle salt

The temperature dependence of ²³Na spin-lattice relaxation in the polycrystalline Rochelle salt was studied by NMR within the range from 235 to 320 K covering both Curie points. The spin-relaxation time t ₁ versus temperature curve showed noticeable dips near the phase transitions against the background of the regular decrease in the relaxation time upon increasing temperature. The dips observed were ascribed to critical contributions to sodium spin-lattice relaxation caused by the slowdown of the correlation time for one of two relaxation modes in the Rochelle salt. The ²³Na NMR parameters were also measured for the melted Rochelle salt. This article was submitted by the authors in English.     

Noninvasive (1)H and (23)Na nuclear magnetic resonance imaging of ancient Egyptian human mummified tissue

Historic mummies are a unique example of the human desire for immortality. Therefore, it is not surprising that modern diagnostic imaging has been widely applied to study them. Yet, magnetic resonance imaging (MRI) of such old remains has never been successfully achieved in a noninvasive way without rehydration. Furthermore, the impact of artificial mummification as done in ancient Egypt by natron (a blend of NaCl, Na(2)CO(3), NaHCO(3) and NaP(2)SO(4)) on human tissue with a particular focus on the sodium spatial distribution has never been addressed. Here, we show for the very first time completely noninvasive (1)H and (23)Na imaging of an ancient Egyptian mummified finger by nuclear magnetic resonance (NMR). Protons could be visualized by NMR only in the tissue close to surface and sodium primarily in the bone, while computer tomography images both, soft tissue and bone but does not distinguish between different chemical elements. The selective enrichment of sodium in the bone may by due to postmortem incorporation of (23)Na into the tissue by natron-based mummification because our reference measurement of a historical finger not subjected to artificial mummification showed no sodium signal at all. Our results demonstrate not only the general feasibility of nonclinical MRI to visualize historic dry human tissues but also shows the specific (1)H and (23)Na spatial distributions in such mummy tissue, which is particularly interesting for archeology and may open up a new application for MRI.     

利用原子吸收光谱法分析盐胁迫对野生披碱草矿质元素吸收和积累的影响

应用原子吸收光谱法测定了两份耐盐性不同的野生披碱草种质材料在不同盐浓度胁迫条件下根组织和叶组织中的大量元素(Na,K,Ca,Mg)和微量元素(Cu,Fe,Mn,Zn)含量,并对野生披碱草种质材料矿质元素吸收和积累的选择性与耐盐性的关系进行了分析,结果表明：随着盐胁迫浓度的升高,野生披碱草种质材料叶和根组织中Na含量不断增加,耐盐材料HS叶组织中的Na含量显著低于敏盐材料LS(P<0.05);而K和Ca含量呈下降的趋势,在高浓度盐胁迫下,耐盐材料HS中两种元素的含量显著高于敏盐材料LS(P<0.05);微量元素Fe和Zn在野生披碱草材料根、叶组织中的含量升高,Cu在根组织中的含量没有变化,但是在叶组织中升高,而Mn在根、叶组织中的含量都呈下降的趋势,耐盐材料HS叶组织和根组织中Zn和Fe含量低于敏盐材料LS,Mn含量显著高于敏盐材料LS(P<0.05)。     

Dynamics of NaHSeO3 and NaHSeO4 single crystals by observation of 1H and 23Na spin-lattice relaxation

The 1H and 23Na spin-lattice relaxation times of NaHSeO3 and NaHSeO4 single crystals grown by the slow evaporation method were measured. The phase transitions of the two crystals were studied using differential scanning calorimetry (DSC), and the environments of the 1H and 23Na nuclei in these crystals were investigated by means of 1H and 23Na NMR spectroscopy. The DSC results show that NaHSeO3 crystals do not undergo phase transitions, whereas for NaHSeO4 crystals there is a small endothermic peak at 419 K. The dimers in NaHSeO3 stabilize its structure to the extent that there are no phase transitions even in the presence of disordered hydrogen bonds. In addition, the NMR results indicate that the temperature dependencies of T1 for the 1H and 23Na nuclei in the two hydrogen-bonded crystals-the NaHSeO3 crystal with 3-coordinated SeO3 and the NaHSeO4 crystal with 4-coordinated SeO4--are significantly different. The different trends in T1 for Na in the two crystals are accompanied by different shifts of the oxygen atoms from the 3-coordinated SeO3 and the 4-coordinated SeO4 species around the Na+ ions. Thus, although the two crystals have hydrogen-bonded structures, the differences between the hydrogen bonding of the 3-coordinated SeO3 in NaHSeO3 and the hydrogen bonding of the 4-coordinated SeO4 in NaHSeO4 result in different T1 temperature dependences and different phase transitions.     

Multinuclear NMR study of silica fiberglass modified with zirconia

Silica fiberglass textiles are emerging as uniquely suited supports in catalysis, which offer unprecedented flexibility in designing advanced catalytic systems for chemical and auto industries. During manufacturing fiberglass materials are often modified with additives of various nature to improve glass properties. Glass network formers, such as zirconia and alumina, are known to provide the glass fibers with higher strength and to slow down undesirable devitrification processes. In this work multinuclear (1)H, (23)Na, (29)Si, and (91)Zr NMR spectroscopy was used to characterize the effect of zirconia on the molecular-level fiberglass structure. (29)Si NMR results help in understanding why zirconia-modified fiberglass is more stable towards devitrification comparing with pure silica glass. Internal void spaces formed in zirconia-silica glass fibers after acidic leaching correlate with sodium and water distributions in the starting bulk glass as probed by (23)Na and (1)H NMR. These voids spaces are important for stabilization of catalytically active species in the supported catalysts. Potentials of high-field (91)Zr NMR spectroscopy to study zirconia-containing glasses and similarly disordered systems are illustrated.     

Strategies for extracting NMR parameters from 23Na MAS, DOR and MQMAS spectra. A case study for Na4P2O7

The 23Na magic-angle spinning (MAS), double rotation (DOR) and multiple-quantum magic-angle spinning (MQMAS) NMR spectra of anhydrous sodium pyrophosphate, Na4P2O7, measured at five different Larmor frequencies (nuL) ranging from 105.8 MHz (corresponding to 400 MHz 1H frequency) to 211.6 MHz (800 MHz) are analysed and the complete set of NMR parameters (C(qcc), etaQ and delta(iso)) of the four crystallographically inequivalent sodium sites were determined with high accuracy. Different approaches of spectra evaluation are discussed and their results are compared. The most reliable results are obtained from a combined evaluation of five DOR and three MQMAS spectra but also from two DOR and one MAS spectra or even from a single MQMAS spectrum all data can be derived. It is shown that Na4P2O7 may serve as a useful reference material for experimental set-up and reliability tests of the various NMR experiments.     

Periodic ab initio calculation of nuclear quadrupole parameters as an assignment tool in solid-state NMR spectroscopy: applications to 23Na NMR spectra of crystalline materials

Periodic ab initio HF calculations using the CRYSTAL code have been used to calculate (23)Na NMR quadrupole parameters for a wide range of crystalline sodium compounds including Na(3)OCl. An approach is developed that can be used routinely as an alternative to point-charge modelling schemes for the assignment of distinct lines in (23)Na NMR spectra to specific crystallographic sodium sites. The calculations are based on standard 3-21 G and 6-21 G molecular basis sets and in each case the same modified basis set for sodium is used for all compounds. The general approach is extendable to other quadrupolar nuclei. For the 3-21 G calculations a 1:1 linear correlation between experimental and calculated values of C(Q)((23)Na) is obtained. The 6-21 G calculations, including the addition of d-polarisation functions, give better accuracy in the calculation of eta((23)Na). The sensitivity of eta((23)Na) to hydrogen atom location is shown to be useful in testing the reported hydrogen-bonded structure of Na(2)HPO(4).     

A 125Te and 23Na NMR investigation of the structure and crystallisation of sodium tellurite glasses

125Te static nuclear magnetic resonance (NMR) and 23Na and 125Te magic angle spinning (MAS) NMR have been used, in conjunction with X-ray diffraction, to examine the structure and crystallisation behaviour of glasses of composition xNa2O.(1-x)TeO2 (0.075 x 0.4). The MAS NMR 23Na spectra from the glasses are broad and featureless but shift by approximately +5 ppm with increased x, i.e. as the system becomes more ionic. The static 125Te NMR spectra show an increase in axial symmetry with increasing x, indicating a shift from predominantly [TeO4] to [TeO3] structural units. The 23Na and 125Te spectra from the crystallised samples have been fitted to obtain information on the sites in the metastable crystal phases, which are the first to form on heating and which are therefore more closely related to the glass structure than thermodynamically stable crystal phases. New sodium tellurite phases are reported, including a sodium stabilised, face centred cubic phase related to delta-TeO2; a metastable form of Na2Te4O9 containing 3 sodium and 4 tellurium sites; and a metastable form of Na2Te2O5 containing 2 sodium sites. There is evidence of oxidation of TeIV to TeVI occurring in glasses with high values of x and, at x=0.40 and 0.50 (outside the glass forming range), some sodium metatellurate (Na2TeO4) is formed at the same time as sodium metatellurite (Na2TeO3). The 125Te shift is very sensitive to environment within the sodium tellurite system, covering more than 320 ppm, with anisotropies varying from 640 to 1540 ppm. The lack of features in the 125Te spectra of the glass phases, combined with the large shift range and high but variable anisotropy, means than it is not possible to obtain a unique fit to any presumed species present. Furthermore, the chemical shift anisotropy parameters for three of the four Te sites in the Na2Te4O9 phase are found to lie outside the range used for previous simulations of glass spectra.     

Reaction of layered sodium disilicate SKS-6 with calcium chloride solution as revealed by solid state NMR spectroscopy: exploring the calcium ion extracting mechanism of SKS-6

Solid-state 1H, 29Si NMR and 23Na MQMAS NMR spectroscopy combined with X-ray powder diffraction (XRD) technique was used to study the reaction between layered sodium disilicate SKS-6 and calcium chloride solution with different concentrations. Based on the experimental results the calcium ion extracting mechanism of SKS-6 was demonstrated to be via ion replacement, during which calcium ions replace sodium ions and combine with the non-bridging oxygen in SKS-6 for charge compensation, and simultaneously sodium ions leave the interlayer. This ion-replacement process was greatly influenced by the substitution of sodium ions by protons as well as the calcium ions concentration. Increasing calcium ions concentration favors the replacement of sodium ions by calcium ions, but prevents sodium ions from being substituted by protons.     

Practical design of a 4 Tesla double-tuned RF surface coil for interleaved 1H and 23Na MRI of rat brain

MRI is proving to be a very useful tool for sodium quantification in animal models of stroke, ischemia, and cancer. In this work, we present the practical design of a dual-frequency RF surface coil that provides (1)H and (23)Na images of the rat head at 4 T. The dual-frequency RF surface coil comprised of a large loop tuned to the (1)H frequency and a smaller co-planar loop tuned to the (23)Na frequency. The mutual coupling between the two loops was eliminated by the use of a trap circuit inserted in the smaller coil. This independent-loop design was versatile since it enabled a separate optimisation of the sensitivity and RF field distributions of the two coils. To allow for an easy extension of this simple double-tuned coil design to other frequencies (nuclei) and dimensions, we describe in detail the practical aspects of the workbench design and MRI testing using a phantom that mimics in vivo conditions. A comparison between our independent-loop, double-tuned coil and a single-tuned (23)Na coil of equal size obtained with a phantom matching in vivo conditions, showed a reduction of the (23)Na sensitivity (about 28 %) because of signal losses in the trap inductance. Typical congruent (1)H and (23)Na rat brain images showing good SNR ((23)Na: brain 7, ventricular cerebrospinal fluid 11) and spatial resolution ((23)Na: 1.25 x 1.25 x 5mm(3)) are also reported. The in vivo SNR values obtained with this coil were comparable to, if not better than, other contemporary designs in the literature.     

Sodium T2*-weighted MR imaging of acute focal cerebral ischemia in rabbits

Changes in T2*-weighted tissue sodium (23Na) signal following acute ischemia may help to identify necrotic tissue and estimate the duration of ischemia. Sodium signal was monitored in a rabbit model of acute (0-4 h) focal cerebral ischemia, using gradient echo 23Na MR images (echo time = 3.2 ms) acquired continuously in 20-min intervals on a 4-Tesla MRI. 2,3,5-Triphenyl-tetrazolium chloride staining was used to identify regions of necrosis. In necrotic tissue, average 23Na image signal intensity decreased by 11% +/- 8% during the first 40 min of ischemia followed by a linear increase (0.19%/min) to 25% +/- 14% greater than baseline after 4 h of ischemia. The time course of 23Na signal change observed in necrotic tissue following focal ischemia in this rabbit model is consistent with an initial decrease in 23Na T2* relaxation time followed by an increase in tissue sodium concentration and provides further evidence that tissue 23Na signal may offer unique information regarding tissue viability that is complementary to other MR imaging techniques.     

NMR studies of Na+-anion association effects in polymer electrolytes

²³Na nuclear magnetic resonance (NMR) measurements on poly(propylene oxide) (PPO) and siloxane based polymer electrolytes containing various sodium salts at a single nominal concentration are reported. In addition, differential scanning calorimetry (DSC) and electrical conductivity studies were carried out on the PPO materials. The NMR-determined mobile Na⁺ concentrations and DSC results provide evidence for ionic aggregation effects which, for some samples, result in salt precipitation at elevated temperatures. ²³Na chemical shifts observed in solid state NMR due to mobile Na⁺ ions are obtainable without the use of high resolution techniques, and exhibit strong dependences on anion and temperature. These results indicate that Na⁺-anion interactions influence ionic transport as well as the number of available carriers.     

~(23)Na NMR方法观察硒缺乏对大白鼠红细胞钠离子浓度的影响

用无损伤~(23)Na NMR检测技术测定了正常和低硒饲料喂养的大白鼠的红细胞内钠离子浓度.结果表明:(1)缺硒可引起胞内钠离子浓度升高,(2)高钠细胞比正常细胞易溶血,(3)在饲料中补充Na_2ScO_3后可使胞内钠离子浓度恢复至正常水平,溶血情况也有所改善。     

23Na TQF NMR imaging for the study of spinal disc tissue

A method for acquiring triple quantum filtered (TQF) (23)Na NMR images is proposed that takes advantage of the differences in transverse relaxation rates of sodium to achieve positive intensity, PI, NMR signal. This PITQF imaging sequence has been used to obtain spatially resolved one-dimensional images as a function of the TQF creation time, tau, for two human spinal disc samples. From the images the different parts of the tissue, nucleus pulposus and annulus fibrosus, can be clearly distinguished based on their signal intensity and creation time profiles. These results establish the feasibility of (23)Na TQF imaging and demonstrate that this method should be applicable for studying human disc tissues as well as spinal disc degeneration.     

Triple-quantum-filtered (23)Na NMR spectroscopy of subcutaneously implanted 9l gliosarcoma in the rat in the presence of TmDOTP(5-1)

The utility of triple-quantum (TQ)-filtered (23)Na NMR spectroscopy for discriminating between intra- and extracellular Na(+)(Na(i)(+) and Na(e)(+), respectively) in a solid tumor in vivo was evaluated using TmDOTP(5-) as a (23)Na shift reagent. Infusion of 80 mM TmDOTP(5-) without added Ca(2+) produced baseline-resolved Na(i)(+) and Na(e)(+) peaks in both single-quantum (SQ) and TQ-filtered (23)Na spectra. The Na(i)(+) signal represented 22+/-4% of the SQ spectrum, but 59+/-10% of the TQ-filtered spectrum. Therefore, the Na(i)(+) contribution in TQ-filtered spectra is much higher than in SQ spectra. Both SQ and TQ-filtered Na(i)(+) signals increased by about 75% 1 h after sacrificing the animal. The TQ-filtered relaxation times did not change during this time, indicating that changes observed in TQ-filtered spectra collected with a preparation time of 3 ms represent changes in the concentration of sodium ions contributing to the TQ-filtered signal. Similar experiments were conducted without TmDOTP(5-) to determine changes in the Na(e)(+) signal in the absence of the shift reagent. The changes in total SQ and TQ-filtered signals 1 h after sacrificing the animal showed that the SQ Na(e)(+) signal decreased by approximately 35%, while the TQ-filtered Na(e)(+) signal did not change significantly. This demonstrates that the TQ-filtered (23)Na signal is relatively insensitive to changes in Na(e)(+) content. To our knowledge, this work represents the first evaluation of multiple-quantum-filtered (23)Na spectroscopy to discriminate between intra- and extracellular Na(+) in a solid tumor in vivo.     

Sensitivity enhancement in (13)C solid-state NMR of protein microcrystals by use of paramagnetic metal ions for optimizing (1)H T(1) relaxation

We discuss a simple approach to enhance sensitivity for (13)C high-resolution solid-state NMR for proteins in microcrystals by reducing (1)H T(1) relaxation times with paramagnetic relaxation reagents. It was shown that (1)H T(1) values can be reduced from 0.4-0.8s to 60-70 ms for ubiquitin and lysozyme in D(2)O in the presence of 10 mM Cu(II)Na(2)EDTA without substantial degradation of the resolution in (13)C CPMAS spectra. Faster signal accumulation using the shorter (1)H T(1) attained by paramagnetic doping provided sensitivity enhancements of 1.4-2.9 for these proteins, reducing the experimental time for a given signal-to-noise ratio by a factor of 2.0-8.4. This approach presented here is likely to be applicable to various other proteins in order to enhance sensitivity in (13)C high-resolution solid-state NMR spectroscopy.     

Solid state water motions revealed by deuterium relaxation in 2H2O-synthesized kanemite and 2H2O-hydrated Na+-zeolite A

Deuterium NMR relaxation experiments, low temperature deuterium NMR lineshape analysis, and FTIR spectra are consistent with a new model for solid state jump dynamics of water in (2)H(2)O-synthesized kanemite and (2)H(2)O-hydrated Na(+)-Zeolite A. Exchange occurs between two populations of water: one in which water molecules are directly coordinated to sodium ions and experience C(2) symmetry jumps of their OH bonds, and a population of interstitial water molecules outside the sodium ion coordination sphere that experience tetrahedral jumps of their OH bonds. For both samples the C(2) jump rate is much faster than the tetrahedral jump rate. (2)H NMR relaxation experiments match well with the fast exchange regime of the model over a wide range of temperatures, including room temperature and above. For hydrated Zeolite A, the kinetic activation parameters for the tetrahedral and C(2) symmetry jumps are Delta H tet++=+17 kJ/mol, Delta S tet++=-109 J/(mol K), Delta H C2++=+19 kJ/mol, and Delta S C2++=-20 J/(mol K). For kanemite, Delta H tet++ =+23 kJ/mol, Delta S tet++=-69 J/(mol K), Delta H C2++ =+23 kJ/mol, and Delta S C2++ =-11 J/(mol K).     

NMR Studies of Heat-Induced Transitions in Structure and Cation Binding Environments of a Strontium-Saturated Swelling Mica

In this work, we combine ²⁷Al, ²⁹Si, ¹⁹F, and ²³Na magic-angle spinning (MAS) nuclear magnetic resonance (NMR) to characterize the structure and interlayer cation environments in a strontium-saturated member of the swelling mica family before and after a heat-induced collapse of the interlayer space. The ²⁷Al and ²⁹Si MAS NMR demonstrate that the sample consists mainly of swelling mica, though the composition does not match the ideal structural formula. Aluminum NMR also shows that a portion of the aluminum shifts from a tetrahedral to an octahedral coordination environment upon heating. Changes in the ²⁹Si and ¹⁹F NMR after heating are consistent with a structural rearrangement of the tetrahedral sheet to permit the binding of larger cations in the ditrigonal cavity. The ²³Na MAS NMR results indicate the presence of three unique sodium environments before and after heating. The heat-invariant resonance is consistent with the presence of sodium carbonate. The other two resonances are associated with interlayer sodium and reflect a migration of sodium to a dominantly anhydrous ditrigonal binding structure with heating. Quantitative elemental analysis and NMR data presented here suggest strontium is bound deep within the ditrigonal cavity of the collapsed micas. Authors' address: Karl T. Mueller, 104 Chemistry Building, Penn State University, University Park, PA 16802, USA