Determination of the (Na+) Sternheimer antishielding factor by 23Na NMR spectroscopy on sodium oxide chloride, Na3OCl

The (Na⁺) Sternheimer antishielding factor γ_∞ (Na⁺) was determined by ²³Na NMR spectroscopy on sodium oxide chloride, Na₃OCl. The quadrupolar coupling constant of the sodium ion in Na₃OCl was determined to QCC=11.34 MHz, which presents the largest coupling constant of a sodium nucleus observed so far. Applying a simple point charge model, the largest principal value of the electric field gradient at the sodium site was calculated to V_zz=−6.76762·10²⁰ V/m². From these values we calculated the (Na⁺) Sternheimer antishielding factor to γ_∞ (Na⁺)=−5.36. In sodium oxide, Na₂O, we observed an isotropic chemical shift of δ_CS=55.1 ppm, referenced to 1 M aqueous NaCl (δ=0 ppm).     

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.     

Far-infrared laser stark spectroscopy of CH3OH and13CH3OH

The high resolution laser Stark spectra of methanol and¹³C-substituted methanol have been studied up to Stark fields of about 60 000V/cm with the HCN and DCN lasers. Numerous families of absorption lines have been observed in both parallel and perpendicular polarizations. For methanol, the transitions J _k =7₅ 6₄ A, _t=0; J _k =11₄ 10₃ E _l , _t=0; and J _k =17₃ 16₂ E₂, _t=0 have been identified while the assignments for¹³C-substituted methanol are J _k =14₈ 15₇ A, _t=0; J _k =15₃ 14₂ A⁺, _t=0; J _k =10₇ 9₆ A, _t=0; and J _k =27₉ 27₈ E₁, _t=0. Zero-field frequencies for the assigned transitions are given with improved accuracy over those calculated from available molecular constants, especially for¹³CH₃OH.     

Synthesis and luminescence properties of Eu, Ce and Tb-activated Sr3La2(BO3)4 under UV excitation

The spectroscopic properties in UV-excitable range for the phosphors of Sr₃La₂(BO₃)₄:RE³⁺ (RE³⁺=Eu³⁺, Ce³⁺, Tb³⁺) were investigated. The phosphors were synthesized by conventional solid-state reactions. The photoluminescence (PL) spectra and commission international de I'Eclairage (CIE) coordinates of Sr₃La₂(BO₃)₄:RE³⁺ were investigated. The f-d transitions of Eu³⁺, Ce³⁺ and Tb³⁺ in the host lattices are assumed and corroborated. The PL and PL excitation (PLE) spectra indicate that the main emission wavelength of Sr₃La₂(BO₃)₄:Eu³⁺ is 611 nm, and Sr₃La₂(BO₃)₄:Ce³⁺ shows dominating emission peak at 425 nm, while Sr₃La₂(BO₃)₄:Tb³⁺ displays green emission at 487, 542, 582 and 620 nm. These phosphors were prepared by simple solid-state reaction at 1000 °C. There are lower reactive temperature and more convenient than commercial phosphors. The Sr₃La₂(BO₃)₄:Tb³⁺ applied to cold cathode fluorescent lamp was found to emit green light and have a major peak wavelength at around 542 nm. These phosphors may provide a new kind of luminescent materials under ultraviolet excitation.     

Fluorescence features of Sm ions in Na2SO4-MO-P2O5 glass system—Influence of modifier oxide

Na₂SO₄-P₂O₅:Sm³⁺ glasses mixed with three different alkaline earth modifier oxides viz., MgO, CaO and BaO were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature; the Judd-Ofelt theory was successfully applied to characterize these spectra. From this theory, various radiative properties like transition probability A, branching ratio β_r, the radiative lifetime τ_r, for various emission levels in the spectra of these glasses have been determined and reported. An attempt has also been made to throw some light on the relationship between the structural modifications and luminescence efficiencies in the change of scenario for modifying oxides in the glass network.     

Solid-State Rb NMR Study in Powdered RbMnCl3

Structural phase transition at 290 K and the implication on the intermediate phase above 290 K in powdered RbMnCl₃ are observed by using a solid-state ⁸⁷Rb NMR spectroscopy. Quadrupole coupling constants (e²qQ/h), the asymmetry parameters (η), and the relative peak intensities for two physically nonequivalent Rb sites, Rb(I) and Rb(II), are determined from nonlinear least-squares fits to the ⁸⁷Rb NMR powder patterns in the temperature range from 260 to 330 K. Quadrupole coupling constants and the asymmetry parameters are examined for the detection of the phase transition resulting in a significant structural change in the Rb(II) site. In addition, changes in the relative peak intensity between the Rb(I) and Rb(II) sites seem to suggest the existence of an anomalous intermediate phase, which is complemented by the differential scanning calorimetry and X-ray diffraction studies.     

Laser stark spectroscopy of13CH3F

The far-infrared laser Stark spectrum of¹³CH₃F has been observed using the 190 m line of the DCN laser. The spectrum was taken at room temperature for both parallel and perpendicular polarizations up to 60,000V/cm. We identify the transition as J_k=32₁₄31₁₄ in the ground vibrational state. The measured zero-field frequency for this transition is in agreement with that calculated from the available molecular constants.     

Na0.25K0.25Bi0.5TiO3无铅压电陶瓷的介电特性研究

用固相反应法制备了Na_0.25K_0.25Bi_0.5TiO₃ (NKBT50)陶瓷，研究了该陶瓷在室温至400℃温度范围内的介电性能.发现该陶瓷的介电温谱与烧结气氛、极化状态有关.在空气中烧结的未极化样品在70℃附近存在介电和损耗峰，而极化后及在氧气氛中烧结的样品并不存在该介电、损耗峰.分析认为70℃的介电和损耗峰与氧空位形成的缺陷偶极子的极化弛豫有关.热激电流显示，陶瓷的去极化温度为225℃，与此相对应的介电、损耗峰也 关键词： 介电性能 氧空位 极化弛豫 钛酸铋钠钾     

Microwave dielectric properties of (1 − x)(Mg0.95Co0.05)TiO3–x(Na0.5La0.5)TiO3 ceramic system

The microstructures and the microwave dielectric properties of the (1 − x)(Mg_0.95Co_0.05)TiO₃–x(Na_0.5La_0.5)TiO₃ ceramic system were investigated. Two-phase system was confirmed by the XRD patterns and the EDX analysis. A co-existed second phase (Mg_0.95Co_0.05)Ti₂O₅ was also detected. The microwave dielectric properties are strongly related to the density and the matrix of the specimen. A new microwave dielectric material 0.88(Mg_0.95Co_0.05)TiO₃–0.12(Na_0.5La_0.5)TiO₃, possessing an excellent combination of dielectric properties: ε_r  22.36, Q × f  110,000 GHz (at 9 GHz), τ_f  2.9 ppm/°C), is proposed as a candidate dielectric for GPS patch antennas.     

Structural and electrical properties of (Na0.85K0.15)0.5Bi0.5TiO3 thin films deposited on LaNiO3 and Pt bottom electrodes

(Na_0.85K_0.15)_0.5Bi_0.5TiO₃ thin films were deposited on LaNiO₃(LNO)/SiO₂/Si(1 0 0) and Pt/Ti/SiO₂/Si(1 0 0) substrates by metal-organic decomposition, and the effects of bottom electrodes LNO and Pt on the ferroelectric, dielectric and piezoelectric properties were investigated by ferroelectric tester, impedance analyzer and scanning probe microscopy, respectively. For the thin films deposited on LNO and Pt electrodes, the remnant polarization 2P_r are about 22.6 and 8.8 μC/cm² under 375 kV/cm, the dielectric constants 238 and 579 at 10 kHz, the dielectric losses 0.06 and 0.30 at 10 kHz, the statistic d_33eff values 95 and 81 pm/V. The improved piezoelectric properties could make (Na_1−xK_x)_0.5Bi_0.5TiO₃ thin film as a promising candidate for piezoelectric thin film devices.     

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.     

Adsorption of Na onto γ-alumina studied by solid-state Na and Al nuclear magnetic resonance spectroscopy

The adsorption of Na⁺ on γ-alumina surfaces at four coverages of Na₂CO₃ [5, 10, 15 and 20% (w/w)] was characterized by solid-state ²³Na and ²⁷Al nuclear magnetic resonance (NMR) spectroscopy. The experimental results suggest that two distinct adsorbed species are present on the alumina surface: surface species and surface salts. At the lower coverages of Na₂CO₃ (5 and 10%), the surface species is predominant, in which the Na⁺ cations are associated with the oxygen atoms of γ-alumina. Increasing the loading level to 15% results in the appearance of a second adsorbed species that is attributed to the surface salt, Na₂CO₃, deposited on the solid surface. Further adsorption of Na₂CO₃ leads to an increase in the amount of surface salt while the amount of surface species remains unchanged. ¹H---²⁷Al Cross-polarization magic angle spinning (CP-MAS) experiments give the evidence that some Na⁺ cations in the form of surface species are coordinated with the Brönsted acid sites of γ-alumina. This may be the main driving force that improves appreciably the catalytic efficiency of an Na₂CO₃---Al₂O₃ catalyst.     

Site occupation of doping La3+ cations and phase transition in Na0.5Bi0.5TiO3–BaTiO3 solid solution

The effects of La doping on the ferroelectric properties of 0.92Na0.5Bi0.5TiO3-0.08BaTiO3(NBT-BT) solid solution have been studied both experimentally and theoretically.The experimental results show that an abnormal ferro-toantiferroelectric phase transition is induced by La doping in NBT-BT.The first-principles calculations indicate that La3+ cations selectively substitute for the A site in NBT-BT as donors.Furthermore,the computed binding energy reveals that La cations is most likely to substitute Ba 2+or Na+,not Bi3+,at A site as donors in NBT-BT,as supported by our Raman spectra.The ferro-to-antiferroelectric phase transition of La-doped NBT-BT is believed to originate from the lattice aberrance and redistribution of valence electrons,thus strengthening the bonding of A-O,enhancing the hybridization between the A cation d orbital and O 2p orbital,and resulting in the deflection of the polar direction of NBT-BT lattice.     

A new method for suppressing the central transition in I=3/2 NMR spectra with a demonstration for 23Na in bovine articular cartilage

The splitting and the lineshape of the satellite transitions of 23Na are measures of the residual quadrupolar interaction and its distribution, which are related to the degrees of order and binding of sodium in biological tissues. However, these transitions are often masked by the stronger signals of the central transition and the isotropic sodium ions. A way to suppress the central signals, while preserving the lineshape and the intensity of the satellites, is suggested and tested on a liquid crystal and on bovine articular cartilage.     

Na solid state MAS NMR of sodium halides occluded in zeolites

Occlusion of sodium chloride and sodium bromide in zeolitic pores was performed by heating mixtures of the salts with zeolites NaY and NaA under high vacuum conditions. The obtained samples were subjected to various further pretreatments like washing with water and zinc-exchange, and were investigated spectroscopically with the ²³Na MAS NMR technique at various Zeeman field strengths. In the case of NaY, the halides are occluded in both types of cages of the faujasite structure. About 90% of the sodalite cages are shown to have incorporated salt which is concluded to be part of [Na₄Hal]³⁺ clusters as in the case of sodalite type materials.     

Rotational spectra of gauche perfluoro-n-butane, C4F10; perfluoro-iso-butane, (CF3)3CF; and tris(trifluoromethyl)methane, (CF3)3CH

The microwave spectra of the gauche conformer of perfluoro-n-butane, n-C₄F₁₀, of perfluoro-iso-butane, (CF₃)₃CF, and of tris(trifluoromethyl)methane, (CF₃)₃CH, have been observed and assigned. The rotational and centrifugal distortion constants for gauche n-C₄F₁₀ are: A = 1058.11750(7) MHz, B = 617.6832(1) MHz, C = 552.18794(1) MHz, Δ_J = 0.0257(5) kHz, δ_J = 0.0052(3) kHz. A C-C-C-C dihedral angle, ω, of ∼55° has been determined. These values agree well with those obtained from a coupled cluster (CCSD/cc-PVTZ) calculation. The rotational and centrifugal distortion constants for iso-C₄F₁₀ and iso-C₄HF₉ are: B_o = 816.4519(4) MHz, D_J = 0.023(2) kHz, and B_o = 903.6985(25) MHz, D_J = 0.043(4) kHz, respectively. The dipole moment of iso-C₄F₁₀ and iso-C₄HF₉ have been measured and found to be 0.0338(8) and 1.69(9) D, respectively.     

Radially dependent antishielding factor γ(r) of the Sc3+ ion in the solid state

We report the results of our calculation of γ(r), the radially dependent antishielding factor of Sc³⁺ ion in the crytalline environment. Watson sphere model is used to approximately represent the crystal potential. Differential equations resulting from non-orthogonal Hartree-Fock perturbation theory are solved to obtain perturbations to core electron states. Contribution to γ(r) from electron self-consistency effect has been evaluated by using the latter wave-functions in the many-body expression of Schmidtet al.     

13CH3OH and13CD3OH optically pumped fir laser: New large offset emission and optoacoustic spectroscopy

27 new, large offset, FIR laser lines from¹³CH₃OH and one from¹³CD₃OH have been discovered by pumping with a high tunability waveguide CW CO₂ laser. Optoacoustic measurements of isotopic methyl alcohol have also been performed and the pump offsets of the new and of previously known lines have been measured and checked. Frequency tunability by Stark effect has been observed for 6 strong lines. Some assignments are discussed.     

Photoluminescence properties of Eu in Y(PO3)3 under VUV excitation

The photoluminescence properties of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) are investigated. The excitation spectrum of Y_0.85(PO₃)₃:0.15Eu₃⁺ shows that both the (PO₃)₃³⁻ groups and the CT bands of O²⁻-Y³⁺ can efficiently absorb the excitation energy in the region of 120-250 nm. Under 147 nm excitation, the optimal emissive intensity of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) is about 36% of the commercial phosphor (Y,Gd)BO₃:Eu³⁺, which hints that the absorbed energy by the host matrix could be efficiently transferred to Eu³⁺. We try to study the concentration quenching mechanism of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) under 147 and 172 nm excitation.