利用17O固体核磁共振波谱分析Ni/CeO2表面镍离子含量

本文以具有重要催化应用前景的Ni/CeO₂体系为例,借助¹⁷O固体核磁共振波谱技术,根据表面氧物种¹⁷O NMR信号的变化,尝试分析了Ni/CeO₂表面层中镍离子的含量.分析结果显示,10% NiCe-500和20% NiCe-300两种Ni/CeO2样品表面第一和第二金属离子层中Ni离子的含量分别位于9%~17%和8%~15%范围内.这一方法或可推广至研究其它一系列顺磁掺杂氧化物的表面掺杂含量.     

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.     

氧化物纳米材料表面结构与性质的固体核磁共振波谱研究

氧化物纳米材料的多种应用与其表面结构和性质密切相关.近年来,固体核磁共振波谱在相关研究中提供了关键信息.本综述总结了近期发展的、以固体核磁共振波谱为主的两种表征氧化物纳米材料表面结构和性质的方法,包括表面选择的同位素标记¹⁷O核磁共振波谱与动态核极化表面增强核磁共振波谱,并对氧化物纳米材料的固体核磁共振波谱研究的发展趋势进行了展望.     

Hydrogen burning of O in the CNO cycle

The direct capture process in the ¹⁷O(p, γ)¹⁸F reaction has been used to determine the reduced proton widths of the states in ¹⁸F near the proton threshold. The observed upper limits on these widths are up to factors of 60 smaller than the previously assumed values implying a corresponding reduction of the stellar reaction rate for the ¹⁷O(p, )¹⁴N reaction. These results together with results from previous work lead to the conclusion that the CNO cycle is tricycling with the reactions ¹⁷O(p,γ)¹⁸F(β⁺ν)¹⁸O(p, )¹⁵N as the third cycle. The implications of these results on the equilibrium abundances of the elements synthesized in this cycle are discussed.     

The two-neutron transfer reactions (O, O) with O, C and Mg targets

Excitation functions, angular distributions and differential ranges were measured for the ²⁶Mg(¹⁸O, ¹⁶O)²⁸Mg reaction at ¹⁸O beam energies of 20–45 MeV. Excitation functions only were measured for the reactions ¹⁴C(¹⁸O, ¹⁹O)¹³C, ¹⁴C(¹⁸O, ¹⁶O)¹⁶C, ¹⁴C(¹⁸O, ²⁰O)¹²C, ¹⁴C(¹⁸O, ¹⁵N)¹⁷N and ¹⁸O(¹⁸O, ¹⁹O)¹⁷O, ¹⁸O(¹⁸O, ¹⁶O)²⁰O, ¹⁸O(¹⁸O, ¹⁵N)²¹F at ¹⁸O beam energies of 13–41 MeV. We have identified these as direct reactions in which a single neutron, a two-neutron cluster, a deuteron and a triton are transferred between projectile and target.

The cross sections for two-neutron transfer reactions were found to be relatively high and those for the ¹⁸O+¹⁸O and the ¹⁴C+¹⁸O reactions were higher than the ones of single-neutron transfers over most of the energy range.

Attempts were made to apply the theory of Buttle and Goldfarb for single-neutron transfer to the case of two-neutron transfer in the ²⁶Mg(¹⁸O, ¹⁶O)²⁸Mg reaction below the Coulomb barrier. It is shown that for those reactions for which the assumptions, implicit in the model, are valid, good agreement is obtained with experiment. We also tried to apply the diffraction model of Dar and Kozlovsky to the calculation of the angular distribution of these reactions. A good fit to the experimental results could be obtained if quite different sets of parameters were used in the calculations for the two bombarding energies.     

Solid state NMR characterisation of crystalline Na2OZrO2SiO2 phases

The NMR interactions of crystalline phases in the system Na₂O-ZrO₂-SiO₂ have been studied by a combination of static and magic angle spinning NMR methods for the first time. A full multinuclear (¹⁷O, ²³Na, ²⁹Si and ⁹¹Zr) approach has been employed that allows the phases to be clearly identified. NMR interactions such as ²⁹Si isotropic chemical shift correlate with the known structural units present. For ²³Na the different sites can often be distinguished on the basis of differing quadrupolar interactions.     

The relativistic stripping model of (p, π) reactions in the Δ resonance region

The relativistic stripping model is presented for the (p, π⁺) reaction in the Δ-resonance region. The Dirac impulse approximation and a Dirac-Hartree calculation are used for the proton nucleus interaction and neutron bound state wave function respectively. The Δ-hole model is employed for the pion-nucleus interaction. This model is applied to the reaction ¹⁶O(p, π⁺)¹⁷O(g.s.).     

An ab initio calculation of 17O and 29Si NMR parameters for SiO2 polymorphs

Ab initio molecular orbital calculations (Hartree–Fock, HF and density functional theories, DFTs) have been carried out for SiO₂ polymorphs coesite, low cristobalite, and -quartz, in order to investigate the reliability of this method for predicting ²⁹Si and ¹⁷O nuclear magnetic resonance (NMR) properties of silicates. Oxygen- and silicon-centered clusters consisting of one (1T) to three tetrahedral (3T) shells (one to four atomic shells), taken from real crystal structure, have been investigated. It is found that for reasonable predication of both the ²⁹Si and ¹⁷O chemical shifts (δ_i^Si and δ_i^O), the minimum cluster is one that gives the correct second neighbors to the nucleus of interest. Both the δ_i^Si and δ_i^O have reached convergence with respect to cluster size at the OH-terminated two tetrahedral (2T) shell (three atomic shells around Si and four atomic shells around O) model. At convergence, the calculated δ_i^Si values agree well (within ±1 ppm) with experimental data. The calculated ¹⁷O electric field gradient (EFG)-related parameters also agree with experimental data within experimental uncertainties. The calculation also reproduces small differences in δ_i^O for O sites with similar tetrahedral connectivities, but shows deviations up to about 10 ppm in relative difference for O sites with different tetrahedral connectivities. The poor performance for the latter is mainly due to the approximations of the HF method. Our study thus suggests that the ab initio calculation method is a reliable mean for predicting ²⁹Si and ¹⁷O NMR parameters for silicates. Such an approach should find application not only to well-ordered crystalline phases, but also to disordered materials, by combining with other techniques, such as the molecular dynamics simulation method.     

Magnetic moments of light nuclei

Magnetic moments of the nuclei ¹⁵N, ¹⁵O, ¹⁷O, ¹⁷F and ¹⁹F are investigated. The importance ; of configuration mixing as well as meson-exchange currents is discussed in detail. Meson-exchange currents are treated in the one-boson exchange limit. Short-range N-N correlations are obtained from solutions of the Bethe-Goldstone equation for doubly closed shell nuclei by the use of realistic N-N potentials which ensure a correct treatment of tensor correlations.     

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.     

Energy spectra of neutrons emitted following muon capture in O and C

The energy spectra of neutrons emitted following muon capture in ¹⁶O and ¹²C are investigated using the continuum shell model. Nuclear wave functions, which have been shown by Ohtsubo and the author to describe the radiative pion capture reaction in the above nuclei well, are adopted. The calculated neutron energy spectra explain well the observed main peaks, at 5 MeV for ¹⁶O and 4 MeV for ¹²C, which are considered to be the giant resonances excited in the muon capture reaction. These peaks are interpreted as the 2⁻ state at 20.3 MeV for ¹⁶O and the 1⁻ state at 22.5 MeV for ¹²C. Comparisons with photon spectra in radiative pion capture reactions are also made. The calculated total capture rates exceed the experimental values by a factor of 2.5 for ¹⁶O and by 30–40% for ¹²C.     

The low-lying levels of O

The low-lying levels of ¹⁸O with even parity form a rotational band. Longitudinal and transverse cross sections are calculated for all levels up to 7 MeV excitation energy. The deformed state is a system of two protons and two neutrons in the deformed s, d orbitals above the core ¹⁴C. Also matrix elements between spherical states are calculated using an effective charge _n = 0.4 for neutrons and 1.4 for protons. The effective charge is determined by fitting theoretical and experimental quadrupole moments of ¹⁷O in the ground state. The effective charge in the calculation of the matrix elements between deformed states takes into account the ¹⁴C core deformation. As in ref. 11), too low transitions probabilities are found in comparison with experimental data.     

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.     

通过宽线固体核磁共振氢谱研究半晶高分子的相结构

宽线固体核磁共振氢谱（¹H NMR）是一种研究半晶高分子相结构的经典方法.本文以半晶聚乙烯的宽线固体¹H NMR谱为例，探讨了通过Gaussian/Sinc、Gaussian和Lorentzian函数组合对宽线固体¹H NMR谱图进行拟合的方案，并根据半晶聚乙烯的相结构成分对拟合得到的各信号成分进行归属.并在此基础上探讨了各个相结构中分子链运动与信号线型的相关性，以及利用宽线固体¹H NMR谱测量半晶高分子结晶度存在的困难.     

19F固体核磁共振技术研究膜蛋白相互作用的进展

固体核磁共振技术因其可实现细胞膜环境中的蛋白质结构研究而广受关注.¹⁹F元素由于灵敏度高、天然丰度高,无生物背景等优点,被广泛应用于生物核磁共振技术中.氟标固体核磁共振技术常被用于细胞膜中蛋白质的相互作用研究,如：抗菌肽与细胞膜的相互作用、聚合膜蛋白结构分析等.此篇综述介绍了常用的蛋白质氟标修饰的实验方法,总结了常用的¹⁹F生物固体核磁共振实验技术,以及介绍了应用¹⁹F固体核磁共振研究膜蛋白的成功案例.此外,此篇综述讨论了¹⁹F固体核磁共振技术在蛋白质研究中的局限性.     

Characterisation of (17)O-enriched alumina from a new hydrothermal preparation

A novel method for the hydrothermal synthesis of ¹⁷O-enriched -Al₂O₃ is presented. Its advantage compared to commonly used methods is that Al₂O₃ is directly produced from metallic Al and ¹⁷O-enriched H₂O without formation of intermediate Al-hydroxide phases that require subsequent dehydration. This is a much more efficient use of the ¹⁷O label as the Al₂O₃ has similar ¹⁷O enrichment level as the H₂O initially used.     

Nuclear reactions between oxygen isotopes

Elastic and inelastic cross sections have been measured for the system ¹⁶O + ¹⁷O at c.m. energies from 12.5 to 15.5 MeV, and for ¹⁶O + ¹⁸O at c.m. energies from 12 to 20 MeV, at angles between 60° and 125°. Position-sensitive detectors were employed, using the kinematic coincidence technique. The data have been analyzed with particular attention to the contributions of multiple-exchange processes.     

COHERENT π0 PHOTOPRODUCTION IN THE QUASI-Δ33 DOORWAY STATE MODEL

The quasi-Δ, doorway state model, previously developed to describe pion-nucleus scattering, ^[1] is applied to the study of cohe-rent π photoproduction on nuclei.The unifying features of this approach for pion elastic scattering and photoproduction are briefly discussed. The relationship to W. Weise's isobar-hole model calculation and plane wave impulse approximation calculations are examined. The results are presented for ¹⁶O(γ, π⁰)¹⁶O and ¹²C(γ, π⁰)¹²C, and compared with the available experimental data. It has a large suppression of cross section from the impulse approximation prediction.     

Polarization of neutrons from the O(d, n)F reaction

The polarizations of neutrons from the ¹⁶O(d, n₀)¹⁷F and ¹⁶O(d, n₁ ¹⁷F reactions have been measured at 30° (lab) in steps of approximately 0.15 MeV from E_d = 3.96 to 5.35 MeV. Polarization angular distributions have been obtained at 3.96 and 5.35 MeV. It is determined that the random phase approximation for the scattering amplitudes is not appropriate for the compound nucleus contributions. The analysis indicates probable interference between the compound nucleus and direct interaction reaction mechanisms.