Prevention of spinning induced sample deterioration during long time solid state NMR experiments of quadrupolar spin systems

A simple solution is proposed to prevent a solid state polycrystalline sample from deterioration during long time high speed spinning experiments in solid state NMR. It is found that if a certain percentage (40% volume) of polyethylene glycol (PEG, (HO–CH₂–(CH₂–O–CH₂–)_n–CH₂–OH)_n) is mixed with the sample that are subject to deterioration, the quality of the sample can be maintained for a long time under high speed spinning for a few days or longer, sufficient for multi-dimensional and/or low-sensitivity experiments. Both 1D and 2D experimental results are shown to support this idea.     

Generalized biaxial shearing of MQMAS NMR spectra

Two dimensional multiple quantum (MQ) MAS NMR experiments have become popular due to the wide applicability of this technique to structural questions in materials science, the abundance of half-integer spin nuclei in the periodic table, and the ease of implementation on typical solid state NMR instruments. In spite of the high-resolution theoretically possible from such experiments, the homogeneous and inhomogeneous broadening factors inherent in many samples of interest can make spectral analysis challenging. We present several possible spectral shearing schemes that may be useful for spectral analysis, and in particular we introduce shearing in the directly detected dimension. We suggest that for amorphous or disordered samples that give broad spectral features, shearing may be used as a general tool for optimal positioning of these features relative to one another and for the characterization of isotropic chemical and quadrupolar shifts.     

Study on ethyl groups with two different orientations in [N(C2H5)4]2CuBr4

The crystal structure and phase transition temperature of [N(C₂H₅)₄]₂CuBr₄ are studied using X-ray diffraction and differential scanning calorimetry (DSC); measurements revealed a tetragonal structure and the two phase transition temperatures T_C of 204 K and 255.5 K. The structural geometry near T_C is discussed in terms of the chemical shifts for ¹H magic angle spinning (MAS) nuclear magnetic resonance (NMR) and ¹³C cross-polarization (CP)/MAS NMR. The two inequivalent ethyl groups are distinguishable by the ¹³C NMR spectrum. The molecular motions are discussed in terms of the spin–lattice relaxation times T_1ρ in the rotating frame for ¹H MAS NMR and ¹³C CP/MAS NMR. The T_1ρ results reveal that the ethyl groups undergo tumbling motion, and furthermore that the ethyl groups are highly mobile.     

Triple, quintuple and higher order multiple quantum MAS NMR of quadrupolar nuclei

The optimization of the coherence transfers involved in five, seven and nine-quantum versions of the recently discovered MQMAS technique, is analysed numerically. Data reported in this paper may serve as starting parameters for the experiment set up. An analysis of the intensity and resolution given by each type of experiment is performed, which confirms the need to use very high rf fields for MQ transfers. It follows that five-quantum is achievable rather easily but the use of seven and nine-quantum MAS experiments becomes increasingly difficult due to the demand for high rf power and decreasing sensitivity. The advantages of using the z-filter MQMAS method with respect to a two-pulse sequence are analysed. The method for qualitatively and quantitatively interpret the MQMAS spectra is described. The nature of the spinning side bands along the multiple quantum dimension is explained. It is shown that the rotor synchronization can be conveniently used to eliminate these side bands, but only for 3QMAS experiments. The use of the multiple-quantum method in combination with static samples and VAS, DAS and DOR techniques is finally discussed.     

Algebraic description of spin 3/2 dynamics in NMR experiments

The dynamics of spin 3/2 systems is analyzed using the density matrix theory of relaxation. By using the superoperator formalism, an algebraic formulation of the density matrix's evolution is obtained, in which the contributions from free relaxation and RF application are easily factored out. As an intermediate step, an exact form for the propagator of the density matrix for a spin 3/2 system, in the presence of static quadrupolar coupling, inhomogeneous static magnetic field, and relaxation is demonstrated. Using this algebraic formulation, exact expressions for the behavior of the density matrix in the classical one-, two-, and three-pulse experiments are derived. These theoretical formulas are then used to illustrate the bias introduced on the measured relaxation parameters by the presence of large spatial variations in the B0 and B1 fields. The theoretical predictions are easily evaluated through simple matrix algebra and the results agree very well with the experimental observations. This approach could prove useful for the characterization of the spatial variations of the signal intensity in multiple quantum-filtered sodium MRI experiments.     

Nuclear magnetic resonance of Nb in LiNbO3: effect of structural distortions on lineshapes

The expression for the angular dependence of the first moment of the nuclear magnetic resonance central transition (± 1/2 ↔ 1/2) lineshapes of a quadrupolar nuclei with half integer spins in a disordered solid is derived and used for investigation of the structural distortions in LiNbO₃.     

直肠癌及直肠正常组织的IR和1H及31P NMR谱研究

对12例直肠组织的红外光谱图进行了测定,并对6例直肠癌变及正常组织的固体1H和31P NMR谱与另外6例直肠癌变及正常组织的液体1H和31P-NMR谱进行研究.结果表明,(1)直肠癌变和正常组织的红外光谱中存在明显差异.(2)在固体1H和31P NMR谱中,1H NMR谱上癌组织的脂肪酸与水相关的特征峰面积的比值I(5+6+7)/I(1+2+3+4)明显变低,依据I(5+6+7)/I(1+2+3+4)比值可区分癌变与正常组织.31P NMR谱上,癌变组织的最强峰的化学位移明显向高场偏移.(3)在液体1H和31P NMR谱中,1H NMR谱上癌组织中3.20处峰强较正常组织高,表明与癌变密切相关的胆碱类化合物包括游离的胆碱、磷酸胆碱及甘油磷酸胆碱等的量增大.31P NMR谱上,癌变组织的强度最大峰的化学位移分别为1.18,1.26,1.29,1.37,正常组织的化学位移为1.70和2.18,癌变组织的强度最大峰的化学位移明显向高场偏移.通过癌变与正常组织代谢物1H NMR谱峰强度和1P NMR谱峰化学位移的差异,可以区分直肠癌变和正常组织,核磁共振1H和31P NMR谱技术可能发展成为一种诊断直肠癌的新方法.     

过渡金属核磁共振谱

以数种过渡金属的核磁共振研究介绍了有关技术在近年的发展;内容集中于如何从图谱取得化学信息。讨论分为固体谱与液体谱两部分,固体谱会着重谱线的分析,液体谱则集中对有关化学位移的理论解释。     

H, V and N nuclear magnetic resonance studies of structure and properties of vanadia supported on TiOx/SiO2

¹H magic-angle spinning nuclear magnetic resonance (MAS NMR) spectra of TiO_x/SiO₂ catalysts suggest the interaction of surface TiO_x. species with Si-OH groups of the silica. Simultaneously, Ti-OH groups from surface titania species appear. The distribution of TiO_x species over SiO₂ is non-uniform, since a considerable part of surface OH groups remains unreacted with supported titania. Supported vanadia species interact both with Si-OH and Ti-OH groups. ⁵¹V NMR spectra suggest the interaction of vanadia with supported titania species and show the non-uniform distribution of titania over the SiO₂ surface. Deposition of titania as well as vanadia produces strong electron-accepting (Lewis) sites which interact with the terminal N atom of adsorbed N₂O molecules, resulting in a downfield shift of the resonance in ¹⁵N NMR spectra. The acid strength of electron-accepting sites is similar in both cases. Only about 10% of the total amount of supported titania and vanadia create Lewis sites.     

Application of Si and Al magic angle spinning nuclear magnetic resonance to studies of the building materials of historical monuments

We report the application of ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) studies on building stones from historical monuments to obtain direct information about the degree of degradation and to observe the changes in the consolidated material after treatment with tetraethoxysilane (TEOS). Using the data obtained from deteriorated materials, a diagnostic laboratory, a suitable treatment and recommendations for building conservation may infer. A case study is presented using stones from Guanajuato City Main Church (Central Mexico). X-ray diffraction patterns to characterize the species present in the stones agree with the solid state NMR results.     

Homonuclear correlation experiments for quadrupolar nuclei, spinning away from the magic angle

We present a set of homonuclear correlation experiments for half-integer quadrupolar spins in solids. In all these exchange-type experiments, the dipolar interaction is retained during the mixing time by spinning the sample at angles other than the “regular magic angle” (54.7°). The second-order quadrupolar interaction is averaged by different strategies for the different experiments. The multiple-quantum off magic angle spinning (MQOMAS) exchange experiment is essentially a regular MQMAS experiment where the quadrupolar interaction is averaged by combining magic angle spinning with a multiple- to single-quantum correlation scheme. The sample is spun at the magic angle at all times except during the mixing time which is added to establish homonuclear correlation. In the multiple-quantum P₄ magic angle spinning (MQP₄MAS) exchange experiment, the sample is spun at one of the angles at which the fourth-order Legendre polynomial vanishes (P₄ magic angle), the remaining second-order quadrupolar interaction now governed by a second-rank tensor is refocussed by the multiple to single-quantum correlation scheme. In the dynamic angle spinning (DAS) exchange experiment, the second-order quadrupolar interaction is averaged by correlating the evolution from two complementary angles. These experiments are demonstrated and compared, in view of their specific advantages and disadvantages, for ²³Na in the model compound Na₂SO₃.     

Potassium tetracyanoplatinate (II) trihydrate (K2Pt(CN)4·3H2O) studied by high resolution solid state C MAS NMR

Prudent analysis of the solid state ¹³C MAS NMR spectra of polycrystalline K₂Pt(CN)₄ · 3H₂O (KTCP)⁻ reveals that in crystals of this compound there are two types of carbon nuclei with slightly different ¹³C chemical shift tensors, contrary to what is found for the solution NMR spectrum and previous static powder NMR studies on this compound and the high resolution solid state NMR studies on other similar compounds. The ¹³C MAS spectra measured at different rotor spinning speeds are satisfactorily simulated though the use of a newly developed computer program based on a novel density matrix formulation. The present method is eminently successful even though the spectra are rather complicated because of (1) the relatively large anisotropies of the chemical shift tensors; (2) the high-order dipolar interactions between ¹³C and ¹⁴N nuclei because of the strong quadrupolar coupling constants of ¹⁴N nuclei; and (3) the indirect J-coupling between the ¹³C and ¹⁹⁵Pt. The principal elements as well as their orientations of the two ¹³C chemical shift tensors are evaluated from the spectral simulations.     

Quantum logical operations for spin 3/2 quadrupolar nuclei monitored by quantum state tomography

This article presents the realization of many self-reversible quantum logic gates using two-qubit quadrupolar spin 3/2 systems. Such operations are theoretically described using propagation matrices for the RF pulses that include the effect of the quadrupolar evolution during the pulses. Experimental demonstrations are performed using a generalized form of the recently developed method for quantum state tomography in spin 3/2 systems. By doing so, the possibility of controlling relative phases of superimposed pseudo-pure states is demonstrated. In addition, many aspects of the effect of the quadrupolar evolution, occurring during the RF pulses, on the quantum operations performance are discussed. Most of the procedures presented can be easily adapted to describe selective pulses of higher spin systems (>3/2) and for spin 1/2 under J couplings.     

Sodium-23 MAS NMR study on nuclear quadrupole interaction in NA(1-x)Ag(x)NO2.

Ag-impurity effects on the first- and second-order quadrupole interaction (QI) at ²³Na site in an isomorphic mixed system, Na_1−xAg_xNO₂ (x=0, 0.0084, 0.026, 0.079, 0.094, 0.16), have been investigated by employing ²³Na (I=3/2) magic angle spinning nuclear magnetic resonance (MAS NMR) technique. The central transition (CT) and satellite transition (ST) are simultaneously observed with this system. From the spectral analysis, the quadrupole parameter and its distribution width are obtained as a function of Ag concentration. From the intensity loss of CT MAS centerband and of the envelope function of ST MAS sidebands due to impurities, the range of their influence on the second- and first-order QI is estimated. The estimated ranges contain the second and first neighbouring Na sites from the resonating ²³Na nucleus for the first- and second-order QI, respectively.     

魔角旋转固体核磁共振探头中转子的研制

转子作为魔角旋转（MAS）探头一个至关重要的部件,是固体样品高速旋转的载体,被广泛应用于各种固体核磁共振（NMR）实验.但国内关于MAS转子的研究极少,以至其长期被国外市场垄断.本文通过对MAS转子的深入研究,设计了常规的4 mm MAS转子;并对MAS转子进行了流固耦合仿真,分析其应力应变大小;同时进行了模态仿真,确定了MAS转子的各阶振型及临界转速;最后制作了转子,进行了转速测试和固体NMR实验.结果表明,本文设计和制作的转子能在14 kHz转速下正常运行,并在4 kHz及12.5 kHz转速下采集了金刚烷标样的¹H NMR信号,结果表明该转子能满足常规固体NMR实验的需求.     

Sodium-23 MAS NMR study on nuclear quadrupole interaction in Na1−xAgxNO2

Ag-impurity effects on the first- and second-order quadrupole interaction (QI) at ²³Na site in an isomorphic mixed system, Na_1−xAg_xNO₂ (x=0, 0.0084, 0.026, 0.079, 0.094, 0.16), have been investigated by employing ²³Na (I=3/2) magic angle spinning nuclear magnetic resonance (MAS NMR) technique. The central transition (CT) and satellite transition (ST) are simultaneously observed with this system. From the spectral analysis, the quadrupole parameter and its distribution width are obtained as a function of Ag concentration. From the intensity loss of CT MAS centerband and of the envelope function of ST MAS sidebands due to impurities, the range of their influence on the second- and first-order QI is estimated. The estimated ranges contain the second and first neighbouring Na sites from the resonating ²³Na nucleus for the first- and second-order QI, respectively.     

Two-dimensional chemical shift/heteronuclear dipolar coupling spectra obtained with polarization inversion spin exchange at the magic angle and magic-angle sample spinning (PISEMAMAS)

High-resolution two-dimensional ¹⁵N chemical shift/¹H-¹⁵N dipolar coupling polarization inversion spin exchange at the magic angle (PISEMA) spectra of a polycrystalline sample of ¹⁵N-acetylvaline were obtained with and without magic-angle sample spinning. These spectra demonstrate the advantages of the PISEMA experiment over conventional approaches to separated local-field spectroscopy, especially the high resolution in the dipolar dimension where the spinning sidebands have uniformly narrow linewidths.     

多量子比特核磁共振体系的实验操控技术

随着量子信息与量子计算科学的发展,量子信息处理器被广泛地用于量子计算、量子模拟、量子度量等方面的研究.为了能在实验上实现这些日益复杂的方案,将量子计算机的潜能转化成现实,需要不断提高可操控的量子体系比特位数,实现更复杂的量子操控.核磁共振自旋体系作为一个优秀的量子实验测试平台,提供了丰富而又精密的量子操控手段.近几年来在此平台上进行了不少的多量子比特实验,发展并积累了一系列的多量子比特实验技术.本文首先阐述了核磁共振体系多量子比特实验中的实验困难,然后结合7量子比特标记赝纯态制备以及其他有关实验,对多比特实验过程中应用到的实验技术进行介绍.最后对核磁共振体系多量子比特实验技术方向的进一步研究进行了总结和展望.     

Triple quantum nutation in the two-level NMR system in the rotating frame

The authors present the detailed theory and the new results associated with the triple quantum (TQ) nutation and the line narrowing effect of the TQ resonance in the two-level NMR system which we reported previously. The TQ resonance is induced in the spin-locked system by the oscillating field produced by the sinusoidal phase modulation (PM) of the RF field. The theory predicts that the TQ nutation is accompanied by several higher frequency oscillations and we detected them experimentally by improving the detection system. These higher frequency oscillations are due to the fluctuation of the angle between the transverse or effective field causing the TQ nutation and the RF field. We obtain the result that the modulation index 2phim of the PM is the key parameter that essentially controls the conditions of the TQ resonance and the narrowing effect. Under the exact TQ resonance, the ratio of the TQ resonance frequency to the Larmor frequency of the RF field depends only on phim, and the secular part of the magnetic dipole Hamiltonian of a like spin system in the triply rotating frame disappears at a particular value of phim. The condition is different from that of the well-known magic angle condition.