取代苯乙酮羰基17O-NMR化学位移的研究

提出计算取代苯乙酮羰基¹⁷O-NMR化学位移的公式：δ_cal=550.0+Δo+Δm+Δp，通过线性回归法确定了12种取代基参数.以44种取代苯乙酮为样本点作回归检验表明该公式的置信度为99.5%，计算值与实验值的偏差Δδ在5.0（相对误差约0.5%）以内的羰基¹⁷O-NMR化学位移的计算值在90%左右.     

Hydroxyl Substituent Chemical Shift (SCS) Effects in Alcohols: The 17O NMR of Diols

The ¹⁷O NMR spectra for a series of saturated diols were investigated. From these studies both hydroxyl induced substituent chemical shift (SCS) effects of hydroxyl oxygen ¹⁷O NMR chemical shifts were determined. In addition, linear correlations between the ¹⁷O chemical shift of the hydroxyl oxygen (ROH) and the ¹³C chemical shift for the methyl group in the corresponding hydrocarbon (RCH₃) were obtained.

     

<Superscript>29</Superscript>Si, <Superscript>27</Superscript>Al, <Superscript>1</Superscript>H and <Superscript>23</Superscript>Na MAS NMR Study of the Bonding Character in Aluminosilicate Inorganic Polymers

²⁹Si, ²⁷Al, ¹H and ²³Na solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) has been used to relate nominal composition, bonding character and compressive strength properties in aluminosilicate inorganic polymers (AIPs). The ²⁹Si chemical shift varies systematically with Si-to-Al ratio, indicating that the immediate structural environment of Si is altering with nominal composition. Fast ¹H MAS and ²⁹Si T _SiH/T _1ρ relaxation measurements demonstrated that occluded pore H₂O mobility within the disordered cavities is slow in comparison with H₂O mobility characteristics observed within the ordered channel structures of zeolites. The ²⁷Al MAS NMR data show that the Al coordination remains predominantly 4-coordinate. In comparison with the ²⁹Si MAS data, the corresponding ²⁷Al MAS line shapes are relatively narrow, suggesting that the AlO₄ tetrahedral geometry is largely unperturbed and the dominant source of structural disorder is propagated by large distributions of Si–O bond angles and bond lengths. Corresponding ²³Na MAS and multiple-quantum MAS NMR data indicate that Na speciation is dominated by distributions of hydration states; however, more highly resolved ²³Na resonances observed in some preparations supported the existence of short-range order. New structural elements are proposed to account for the existence of these Na resonances and an improved model for the structure of AIPs has also been proposed. Authors' address: John V. Hanna, NMR Facility, Institute of Materials and Engineering Science, Lucas Heights Research Laboratories, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234, Australia     

Location of β-emitting12N in V crystal following recoil implantation

Nuclear dipolar broadening in the NMR spectra of β-emitting¹²N implanted in single crystal V was studied as a function of external magnetic field, orientation of the crystal axes relative to the field, and temperature of the sample. The implanted¹²N was located in an interstitial tetrahedral site. The surrounding V atoms nearest to the¹²N were displaced from the regular lattice position; the lattice expansion of large size Δa/a=0.5 was determined.     

Natural Abundance 17O NMR Studies on Methyl N-Arylcarbamates: Torsion Angle and Electronic Effects

Natural abundance ¹⁷O NMR data for 14 substituted methyl N-arylcarbamates obtained in acetonitrile solution at 75°C are reported. The ¹⁷O NMR chemical shifts of hindered ortho N-arylcarbamates are shielded relative to unhindered ones; a quantitative relationship is observed between the carbonyl ¹⁷O NMR chemical shifts and molecular mechanics (MM2) predicted torsion angles. The carbonyl ¹⁷O NMR chemical shifts of meta and para substituted N-arylcarbamates are correlated with Hammett sigma constants.     

Characterization of the essential oil of Agastache rugosa by NMR spectroscopy

The composition of essential oil from Agastache rugosa (Fish. et Mey) O.Kuntze was studied by ¹H and ¹³C NMR spectroscopy. Essential oil was isolated from the aerial part of plants growing in the Central Botanical Garden of the NAS of Belarus during flowering and fruiting. The oil chemical composition was found to depend little on the sampling time. It was shown that NMR spectroscopy could be successfully used to both monitor the content of the hepatotoxic substance (pulegone) and characterize the quality and authenticity of essential oils.     

17O DOR and other solid-state NMR studies concerning the basic properties of zeolites LSX

We demonstrate complementary ¹H, ¹⁷O, ²⁷Al and ²⁹Si measurements for basic low-silica-X zeolites, which were unloaded and pyrrole and formic acid-loaded. It was found that the acid–base-system is not stabile, if the loading exceeds one pyrrole molecule or two formic acid molecules per supercage.¹⁷O DOR NMR spectra exhibit at least four lines, which are broadened by a distribution of chemical shifts in a similar extend as the ²⁹Si MAS NMR spectra are broadened by distribution of Si–O–Al angles. A strong cation influence upon ¹⁷O shifts was observed. But there was no strong influence of the acid molecules on the mean value of the ¹⁷O shift of the spectra.     

Complete and incomplete fusion studies in7Li and16O induced reactions on51V by measurement of excitation functions and recoil ranges

Excitation function and mean projected recoil ranges of nuclei produced in the⁷Li and¹⁶O induced reactions on⁵¹V target were measured by conventional stacked foil and thick-target thick-recoil-catcher technique for bombarding energiesE ≤ 50.0 MeV for⁷Li ions andE ≃ 60.0-96.0 MeV for the¹⁶O ions. The measured recoil ranges are converted to momentum transfer. The momentum transfer information was used to get clues about some aspects of the interaction such as complete and incomplete fusion reaction mechanism which correspond to full and reduced momentum transfer respectively. The measured excitation functions are compared with the calculation based on the statistical model which describes only equilibrium decay of the compound nucleus using the CASCADE code. The comparison of the CASCADE code with the measured excitation functions for the residue radioisotopes⁵¹Cr and⁵⁴Mn for the⁷Li +⁵¹V system indicates the reaction mechanisms is complete fusion of⁷Li with the target nucleus⁵¹V. Similarly the comparison of the CASCADE code with the measured excitation functions of the residue radioisotopes for the system¹⁶O +⁵¹ V indicates that the four reaction mechanisms (i) complete fusion of¹⁶O, (ii) incomplete fusion of¹²C, (iii) incomplete fusion of⁸Be and (iv) incomplete fusion of⁴He respectively with the target might be contributing to reaction cross sections.     

Natural Abundance 17O NMR Study of Substituted α,α,α-Trifluoromethoxybenzenes

Natural abundance ¹⁷O NMR chemical shift data for meta- and para-substitued α,α,α-trifluoromethoxybenzenes recorded in acetonitrile at 75° C are reported. The ¹⁷O NMR signals for the trifluoromethoxy compounds are deshielded by greater than 65 ppm compared to analogous methoxy compounds. A quantitative relationship between ¹⁷O NMR chemical shifts for the trifluoromethoxy and methoxy benzenes is reported.     

Framework and extra-framework aluminium in wet ion exchanged Fe-ZSM5 and the effect of steam during the decomposition of N2O

The role of extra-framework and framework aluminium in wet-ion exchanged Fe-ZSM5 has been studied using ²⁹Si NMR and ²⁷Al triple quantum magic angle spinning (3QMAS) NMR. A series of samples were studied, the parent material, the wet ion exchanged Fe-ZSM5 and Fe-ZSM5 that has been used in the decomposition of N₂O with varying reaction conditions. Various framework and extra-framework aluminium species have been identified. It was found that cationic Fe species prefer to replace the Brønsted acid protons in their charge balancing role at those aluminium sites associated with the largest quadrupolar product. The framework aluminium atoms that pertain to the smaller quadrupolar product, which are either charge balanced by extra-framework aluminium or a proton, are much less prone to exchange. In the catalytic decomposition of N₂O it seemed that water present in small amounts enhances the catalytic activity. However, water also decreases the long term stability and performance by dealuminating the zeolite framework. With a high amount of water present, Fe-ZSM5 was destabilised and catalytically inferior.     

Experimental evidences of clusters with different short range order in amorphous alloys

⁵⁶Fe,⁵⁷Fe,¹⁰B and¹¹B isotopes were used for binary alloys. The signals of B (40,5 MHz) and Fe (43 MHz) from α-Fe in binary Fe−B crystalline and amorphous alloys were found besides the signals of these nuclei in t-and o-phase or clusters like these phases. The NMR on (51)V impurity nuclei in Fe−B alloys was used as well. Only amorphous Fe-(^<15 at.%B) alloys had the clusters with o-, t-Fe₃B and α-Fe short range order.     

NMR proton relaxation and chemical exchange in the system H16 2O/H17 2O-[2H6]dimethylsulphoxide

NMR proton relaxation rates of normal and ¹⁷O enriched water in a mixture of 68 mol% water and 32 mol% [²H₆]dimethylsulphoxide were measured for temperatures between 298 K and 183 K. In the range between 240 K and 204 K the limit of fast proton-proton exchange between H¹⁶ ₂O and H¹⁷ ₂O is not obeyed, and relaxation curves deviate from mono-exponential behaviour. By fitting the relaxation curves to a model of NMR two-phase relaxation the proton-proton exchange rate within the aqueous component could be obtained. With decreasing temperature, proton-proton exchange slows down and a residence time of about 125 ms at 215 K is found, but it becomes faster again for still lower temperatures. From the phase-averaged relaxation rates of water in the ¹⁷O enriched mixtures, the ¹⁷O induced proton relaxation rate was derived as a function of temperature. This yields the rotational correlation times of the water molecule in the mixture and the dipolar spin-lattice coupling parameter. The latter is considerably lower than the one predicted from the geometry of water.     

Temperature Dependence of <Superscript>1</Superscript>H and <Superscript>17</Superscript>O NMR Shifts of Water: Entropy Effect

Density functional theory together with statistical thermodynamics based on the equilibrium constants method and concept of orientational entropy were applied to reproduce the temperature dependences of ¹H and ¹⁷O nuclear magnetic resonance (NMR) chemical shifts in liquid water. Despite a rather simple theoretical model, a satisfactory agreement between calculated NMR quantities and corresponding experimental data was found. By using only a single adjustable parameter of arbitrary directionality, we succeeded to imitate the first-order temperature effect for both (¹H and ¹⁷O) NMR signals in the neat water. ¹H and ¹⁷O magnetic shielding tensors of water molecules in various water clusters have been calculated using the density functional theory. The full geometry optimization was performed using Becke's three-parameter hybrid method and the Lee–Yang–Parr correlation functional (B3LYP) combined with 6-311++G^** basis set. Magnetic shielding tensors have been calculated using the modified hybrid functional of Perdew, Burke and Ernzerhof, and the gauge-including atomic orbital approach was applied to ensure gauge invariance of the results. Solvent effects were taken into account by the polarized continuum model. Authors' address: Vytautas Balevicius, Faculty of Physics, Vilnius University, Sauletekio 9, Vilnius 10222, Lithuania     

Solid-state 27Al MRI and NMR thermometry for catalytic applications with conventional (liquids) MRI instrumentation and techniques

Multidimensional images of Al2O3 pellets, cordierite monolith, glass tube, polycrystalline V2O5 and other materials have been detected by 27Al, 51V, and 23Na NMR imaging using techniques and instrumentation conventionally employed for imaging of liquids. These results demonstrate that, contrary to the widely accepted opinion, imaging of "rigid" solids does not necessarily require utilization of solid state NMR imaging approaches, pulse sequences and hardware even for quadrupolar nuclei which exhibit line widths in excess of 100 kHz, such as 51V in polycrystalline V2O5. It is further demonstrated that both 27Al NMR signal intensity and spin-lattice relaxation time decrease with increasing temperature and thus can potentially serve as temperature sensitive parameters for spatially resolved NMR thermometry.     

Studies of heterogeneous catalysis using high-resolution solid state NMR

Recent results obtained at the institute of Catalysis from studies of heterogeneous catalysis using high-resolution¹H,¹³C,¹⁵N,²⁷Al,²⁹Si,³¹P and⁵¹V solid state NMR have been summarized. Emphasis is made on: (1) structural studies of active in catalysis compounds and sites in supported oxides, hydrides and inorganic acids; (2) studies of structures and properties of surface OH groups active in Bronsted acid catalysis; (3) studies of Lewis acidity of heterogeneous catalysts using¹⁵N NMR of adsorbed N₂O and (4) studies of adsorption mechanisms for molecules of reactants over various catalysts.     

Inhomogeneous state of the electron system in the Sr14 ? x Ca x Cu24O41 superconducting cuprate: 63Cu-17O NMR study

Charge fluctuations in quasi-one-dimensional hole-doped Sr₁₄Cu₂₄O₄₁ (Ca-0) and Sr₂Ca₁₂Cu₂₄O₄₁ (Ca-12) spin-ladder cuprates have been studied with the use of ⁶³Cu-¹⁷O NMR. Spin-echo decay rates ¹⁷(1/T ₂) and ⁶³(1/T ₂) have been measured in the temperature range of T = 10–300 K. The variation of ¹⁷(1/T ₂) and ⁶³(1/T ₂) in the Ca-0 compound is monotonic in the entire temperature range of the NMR study. In the Ca-rich compound, pronounced peaks have been observed in the decay rates ¹⁷(1/T ₂) and ⁶³(1/T ₂) at temperatures of 25 and 50 K, respectively. This result indicates the presence of collective low-frequency (τ_c ∼ T ₂) charge density fluctuations in superconducting Ca-12 with an activation energy of E _A = 100(10) K. The fluctuations gradually slow down as the temperature decreases. The amplitude of the charge density fluctuations is only 0.01–0.02 hole per site. ¹⁷O-⁶³Cu spin-echo double-resonance (SEDOR) experiments in Sr_{14 − x} Ca _x Cu₂₄O₄₁ oxides with x = 0 and 12 have been performed depending on the temperature and orientation of single crystals in a magnetic field. The constants of an indirect heteronuclear ¹⁷O-⁶³Cu interaction of nuclear spins mediated by conduction electrons have been measured. The estimates of the indirect interaction constants for nearest neighbors O1-Cu and O2-Cu, as well as SEDOR experiments with selective excitation of separate sections of ¹⁷O and ⁶³Cu NMR spectra, provide convincing evidence of the microscopically inhomogeneous spatial distribution of spin density developing in a crystal. Original Russian Text ? Yu.V. Piskunov, V.V. Ogloblichev, S.V. Verkhovsky, 2007, published in Pis’ma v Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2007, Vol. 86, No. 11, pp. 850–855.     

Experimental observation of the spin screening effect in superconductor/ferromagnet thin film heterostructures

When studying the nuclear magnetic resonance (NMR) of ⁵¹V nuclei in superconductor/ferromagnet thin film heterostructures, anomalous behavior of the NMR signal was observed. This effect was manifested as a systematic distortion of the high-field wing of the resonance line. We consider this to be the first experimental evidence for penetration of ferromagnetism into a superconductor.     

Hydrostatic pressure effects on oxygen-related irradiation-produced defects in silicon

Abstract

Hydrostatic pressure has been used as a variable to investigate the E_c-0.164 eV acceptor level for the oxygen-vacancy (O—V) defect in γ-ray irradiated Si, and the annealing/formation of oxygen-related defects in neutron-irradiated Si. The acceptor level is found by deep level transient spectroscopy to move closer to the conduction band and away from the valence band at rates of 3.9 meV/kbar and 2.4 meV/kbar, respectively, i.e., the level moves higher in the gap. There is also a relatively large inward (outward) breathing mode lattice relaxation (4.6±1.2 ų/electron) accompanying electron emission (capture) from this level. Both results reflect the antibonding nature of the level and are qualitatively consistent with the Watkins—Corbett model for the O—V defect. The annealing rate was found by infrared absorption to increase with pressure for the O—V defect at 350°C with a derived activation volume of ?4.5 ų/defect, where the negative sign implies inward relaxation (contraction) on annealing. Pressure has relatively little effect on annealing of the C—Si—O C(3) defect which is interstitial in nature, but strongly favors the formation of the dioxygen (2 oxygen atoms per vacancy, i.e., O₂—V) defect. The intensity of the O₂—V band after annealing at 20 kbar is 5 times higher than that following similar annealing at 0 kbar. Additionally, this intensity at 20 kbar is higher than that achievable by any isochronal or isothermal annealing steps at 0 kbar. These annealing/formation results are discussed qualitatively in terms of models for the various defects.     

Muon spin relaxation in spin gap state of BaVS3

Positive muon spin relaxation measurements were performed on a spin-1/2 system BaVS₃, which shows a metal-insulator transition at T_MI= 70 K. We found a marked muon-spin depolarization below T_X= 30 K without appreciable critical divergence. The possibility of muonium formation in the insulating state rather than electron spin freezing is discussed taking into account the quenching of V spins evidenced by ⁵¹V NMR and NQR measurements. This revised version was published online in August 2006 with corrections to the Cover Date.     

In–Ga–Zn–O MESFET with transparent amorphous Ru–Si–O Schottky barrier

Rectifying transparent amorphous Ru–Si–O Schottky contacts to In–Ga–Zn–O have been fabricated by means of reactive sputtering without any annealing processes nor semiconductor surface treatments. The ideality factor, effective Schottky barrier height and rectification ratio are equal to 1.6, 0.9 eV and 10⁵ A/A, respectively. Ru–Si–O/In–Ga–Zn–O Schottky barriers were employed as gate electrodes for In–Ga–Zn–O metal–semiconductor field‐effect transistors (MESFETs). MESFET devices exhibiting on‐to‐off current ratio at the level of 10³ A/A in a voltage range of 2 V, with subthreshold swing equal to 420 mV/dec were demonstrated. A channel mobility of 7.36 cm²/V s was achieved. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)