Efficient heteronuclear dipolar decoupling in solid-state NMR using frequency-swept SPINAL sequences

Aiming to improve heteronuclear spin decoupling efficiency in NMR spectroscopy of solids and liquid crystals, we have modified the original Small Phase Incremental ALteration (SPINAL) sequence by incorporating a frequency sweep into it. For the resulting sequence, termed SW_f-SPINAL, the decoupling performance of a large number of sweep variants was explored by both numerical simulations and NMR experiments. It is found that introducing a frequency sweep generally increases both the ‘on-resonance’ decoupling performance and the robustness towards parameter offsets compared to the original SPINAL sequence. This validates the concept of extending the range of efficient decoupling by introducing frequency sweeps, which was recently suggested in the context of the frequency-swept SW_f-TPPM method. The sequence found to be best performing among the SW_f-SPINAL variants consists of fully swept 16 pulse pairs and is designated (32)-SPINAL-32. Its good decoupling performance for rigid spin systems is confirmed by numerical simulations and also experimentally, by evaluating the CH₂ resonance of a powder sample of l-tyrosine under MAS. For moderate MAS frequencies, the new sequence matches the decoupling achieved with SW_f-TPPM, and outperforms all other tested sequences, including TPPM and SPINAL-64. (32)-SPINAL-32 also shows excellent decoupling characteristics for liquid crystalline systems, as exemplified by experiments on the 5CB liquid crystal.     

19F-decoupling of half-integer spin quadrupolar nuclei in solid-state NMR: application of frequency-swept decoupling methods

In solid-state NMR studies of minerals and ion conductors, quadrupolar nuclei like ⁷Li, ²³Na or ¹³³Cs are frequently situated in close proximity to fluorine, so that application of ¹⁹F decoupling is beneficial for spectral resolution. Here, we compare the decoupling efficiency of various multi-pulse decoupling sequences by acquiring ¹⁹F-decoupled ²³Na-NMR spectra of cryolite (Na₃AlF₆). Whereas the MAS spectrum is only marginally affected by application of ¹⁹F decoupling, the 3Q-filtered ²³Na signal is very sensitive to it, as the de-phasing caused by the dipolar interaction between sodium and fluorine is three-fold magnified. Experimentally, we find that at moderate MAS speeds, the decoupling efficiencies of the frequency-swept decoupling schemes SW_f-TPPM and SW_f-SPINAL are significantly better than the conventional TPPM and SPINAL sequences. The frequency-swept sequences are therefore the methods of choice for efficient decoupling of quadrupolar nuclei with half-integer spin from fluorine.     

熔融织构(Nd-Eu-Gd)-Ba-Cu-O超导体的各向异性磁通跳跃及其不稳定性研究

对c轴择优取向的熔融织构样品(Nd_0.33Eu_0.33Gd_0.33) Ba₂Cu₃O_7-δ（含Gd(211)相）的磁通跳跃现象进行 了系统研究.结果表明，在外加磁 场平行于样品c轴条件下，在2到3K的温度范围内明显观测到了部分磁通跳跃现象，而 在5K及以上温区并未出现.在磁场垂直于样品的c轴情况，在2K到T_c的整个温 区都没有观察到磁通跳跃现象.这种各向异性磁通跳跃现象可归因于各向异性钉扎力和几何 退磁因子的结果.随着温度的增加，磁通跳跃数目减少，且M(H)曲线的第三象限是磁通 跳跃的最不稳定过程.最后，研究了磁通跳跃对磁场扫描速率的依赖关系，并讨论了磁通蠕 动对磁通跳跃的影响. 关键词： 0.33Eu_0.33Gd_0.33)Ba₂Cu₃O_7-δ超导体')" href="#">(Nd_0.33Eu_0.33Gd_0.33)Ba₂Cu₃O_7-δ超导体 OCMG方法 磁通跳跃     

Supercycled SW(f)-TPPM sequence for heteronuclear dipolar decoupling in solid-state nuclear magnetic resonance

The performance of a supercycled SW(f)-TPPM sequence for heteronuclear dipolar decoupling in solid-state NMR is analyzed here. The decoupling performance of this sequence with respect to experimental parameters, such as, the phase angle, proton offset and MAS frequency is studied. A comparison is made with two other commonly used decoupling schemes in solid-state NMR namely, SPINAL-64 and SW(f)-TPPM, on a sample of U-13C-labeled tyrosine. Our results show that supercycled SW(f)-TPPM performs better than the former sequences. Also, numerical spin dynamics studies are presented which support the experimentally observed efficiency in the decoupling.     

Effect of Sweep Direction on Sidebands in Adiabatic Decoupling

The appearance of sidebands in adiabatic decoupling can be substantially reduced simply by matching the sweep rate and direction of adiabatic pulses with the evolution of differentJcouplings. Alternatively, a matched adiabatic defocusing pulse is applied just before the decoupling is turned on, providing an efficient means for complete suppression of sidebands.     

Some comments on the Coriolis attenuation problem

To explore the Coriolis attenuation problem we have carried out a schematici _13/2 rotor plus single quasi-particle band-mixing calculation. The results reveal that the calculations are largely insensitive towards the location of the Fermi energy near the low-K single particle states only, and therefore are incapable of taking into account the transition from ‘full’ decoupling to ‘partial’ decoupling as the Fermi level is increased. We trace the possible reasons for this insensitivity and find that this may be primarily due to thebcs approximation for calculating the quasiparticle energies.     

Magnetic resonance imaging on CO(2) miscible and immiscible displacement in oil-saturated glass beads pack

In this study, the displacement processes were observed as gaseous or supercritical CO₂ was injected into n-decane-saturated glass beads packs using a 400-MHz magnetic resonance imaging (MRI) system. Two-dimensional images of oil distribution in the vertical median section were obtained using a spin-echo pulse sequence. Gas channeling and viscous fingering appeared obviously in immiscible gaseous CO₂ displacement. A piston-like displacement front was detected in miscible supercritical CO₂ displacement that provided high sweep efficiency. MRI images were processed with image intensity analysis methods to obtain the saturation profiles. Final oil residual saturations and displacement coefficients were also estimated using this imaging intensity analysis. It was proved that miscible displacement can enhance the efficiency of CO₂ displacement notably. Finally, a special coreflood analysis method was applied to estimate the effects of capillary, viscosity and buoyancy based on the obtained saturation data.     

Adiabatic decoupling sidebands

An analytical solution is given for amplitudes and phases of adiabatic decoupling sidebands as a function of spin inversion time tau. Since all the adiabatic decoupling phases theta(t, tau) refocus at two periods (2T) of the decoupling pulse, the sidebands are located at n/2T rather than at n/T as observed in other decoupling schemes. The real (R(n)(tau)) and imaginary (I(n)(tau)) amplitudes of the sidebands have symmetry R(n)(tau) = R(-n)(tau) and I(n)(tau) = -I(-n)(tau), forming a mirror image between the counterparts of the sidebands. When frequency sweep changes direction all I(n)(tau) are inverted while all R(n)(tau) remain unchanged, leading to pure absorption sidebands with two accumulations as demonstrated by Kupce and Freeman, and to an exchange of sidebands between counterparts. The sum of the real parts for sidebands n = 1 and 2 is almost a constant near on-resonance decoupling, and it increases substantially for large decoupling offsets. The phase defocusing can be minimized for all decoupling offsets by inserting an initial decoupling period with T(ini) = T/2, eliminating all sidebands located at n/2T (n = +/-1, +/-3, +/-5, ...).     

Multiple resonance heteronuclear decoupling under MAS: dramatic increase of spectral resolution at moderate magnetic field and MAS frequencies

The effects of multiple-resonance heteronuclear decoupling under magic angle spinning (MAS) on the resolution of one-dimensional ¹⁹F and ³¹P and various two-dimensional MAS NMR spectra and on the residual non-refocusable coherence lifetimes in fluorinated aluminophosphate AlPO₄-CJ2, i.e. a compound that contains numerous highly abundant nuclei but no homonuclear spin bath, has been investigated. The design of the four-channel (¹H, ¹⁹F, ²⁷Al, ³¹P) MAS probe used for this study is first described. ¹H and ¹H–²⁷Al double-resonance decouplings allows lengthening the optimized transverse relaxation and increasing the resolution in the ¹⁹F and ³¹P dimensions. Under the application of multi-nuclear decoupling, a two-dimensional ¹⁹F–³¹P CP-HETCOR correlation spectrum for AlPO₄-CJ2 is recorded with unprecedented high-resolution in the two dimensions. Moreover, because ¹H-decoupling increases the ¹⁹F , it has been applied during the entire duration of the 2D NMR experiments, allowing the direct use of residual small interactions to generate ¹⁹F–¹⁹F and ¹⁹F–²⁷Al 2D NMR correlation spectra in AlPO₄-CJ2.     

Franz–Keldysh oscillations at the miniband edge in a GaAs/AlxGa1 −xAs superlattice

We have systematically measured the electroreflectance spectra of a GaAs (7.0 nm)/Al_0.1Ga_0.9As (3.5 nm) superlattice at various electric fields to investigate Franz–Keldysh (FK) oscillations. In the low-field regime, we clearly observe the FK oscillations toward the low-energy side of theM₁critical point (mini-Brillouin-zone edge). As the electric field is increased, the direction of the FK oscillations is reversed, then the oscillations disappear. The change of the oscillation direction correlates with the transformation of the electronic structures from the miniband to the Stark-ladder states in the Wannier-Stark localization. We discuss these experimental results on the basis of a theory of the FK oscillations and envelope-function forms calculated by a transfer matrix method with Airy functions.     

182Os核yrast带结构SU(3)→U(5)→SU(3)形状相变的有序性研究

对于发生在同一个原子核中的转动诱导发生基准态结构的量子相变,可以理解为一种从高有序激发模式向着低有序激发模式的演化：被布居到高角动量态的高有序激发核,以E2跃迁的方式先行退耦到yrast带,再退耦到共存区(或临界点)时释放了有序的结构能,诱发价核子对耦合强度改变,重新组合出低有序的激发模式基准态,实现了基准态结构的过渡.对核量子相变的这种描述,与朗道经典热相变理论之间有了某些相似的术语和物理内涵.本文把这种理解推广到了相继的二次相变中.以¹⁸²Os 核为例作了说明,并展 关键词： 量子相变 基态结构演化 F_max方案')" href="#">微观sdIBM-F_max方案 182Os核')" href="#">¹⁸²Os核     

应变Si1－xGex/(111)Si空穴有效质量模型

利用应变Si_1-xGe_x/(111)Si材料价带E(k)-k关系,研究获得了沿不同晶向的空穴有效质量,并在此基础上,建立了空穴各向同性有效质量模型.结果表明,与弛豫材料相比,应变Si_1-xGe_x/(111)Si材料价带带边空穴有效质量各向异性更加显著,带边空穴各向同性有效质量随Ge组分明显减小.该研究成果可为Si基应变PM 关键词： 1-xGe_x')" href="#">应变Si_1-xGe_x 空穴有效质量 价带     

Sr2RuO4正常态的c方向的磁阻的研究

研究了典型的层状钙钛矿结构超导单晶Sr₂RuO₄在c方向的磁阻(Δρ/ρ₀)(H∥ab,J∥c)的变化.实验发现,磁阻表现出强烈的各向异性,并且随着温度T的降低,磁阻效应越明显;当在平面ab内旋转磁场H的方向时,磁阻成周期性变化;实验表明,磁场沿(110)方向时,出现磁阻的极大值.分别从Sr₂RuO₄的费米面的各向异性、载流子散射率、c方向能带色散的各向异性等方面来解释这些输运性质. 关键词： 2RuO₄')" href="#">Sr₂RuO₄ 磁阻     

Influence of the sample orientation in Sn<Subscript>2</Subscript>P<Subscript>2</Subscript>S<Subscript>6</Subscript> crystals on the hydrostatic piezoelectric coefficients

The influence of the sample orientation on the effective value of the hydrostatic piezoelectric coefficients d _h ⁽ⁱ⁾ of Sn₂P₂S₆ crystals has been studied. The hydrostatic piezoelectric coefficients d _h ⁽¹⁾ and d′ _h ⁽³⁾ , were measured, d _h ⁽¹⁾ =(244±3) pC/N and d′ _h ⁽³⁾ =(92±1) pC/N. The hydrostatic piezoelectric coefficient d _h ⁽³⁾ for orthogonal axis system was calculated to be d _h ⁽³⁾ =(87±2) pC/N. The, optimal orientation of the sample has been found as (Xy l)−20°-cut. Maximal value of the effective hydrostatic piezoelectric coefficient d _h ⁽¹⁾ equals 260 pC/N. Double rotated samples were also studied. The orientation of the samples insensitive to the pressure has been found. The theoretical mean value of hydrostatic piezoelectric coefficient (d _h ) _mean corresponding to randomly oriented Sn₂P₂S₆ grains in a poled composite has been calculated to be (d _h ) _mean =136 pC/N.     

Novel photoluminescence properties of InAlO3（ZnO）m superlattice nanowires

One-dimension InAlO 3 (ZnO) m superlattice nanowires were successfully synthesized via chemical vapor deposition.Transmission electron microscopy measurements reveal that the nanowires have a periodic layered structure along the 0001 direction.The photoluminescence properties of InAlO 3 (ZnO) m superlattice nanowires are studied for the first time.The near-band-edge emissions exhibit an obvious red shift due to the formation of the localized tail states.The two peaks centered at 3.348 eV and 3.299 eV indicate a lever phenomenon at the low-temperature region.A new luminescence mechanism is proposed,combined with the special energy band structure of InAlO 3 (ZnO) m.     

Field history dependence of nonlinear dielectric properties of Ba0.6Sr0.4TiO3 ceramics under bias electric field: Polarization behavior of polar nano-regions

Nonlinear dielectric properties of Ba_0.6Sr_0.4TiO₃ ceramics prepared by citrate method were investigated under bias electric field with respect to field history. X-ray diffraction analysis and temperature dependence of the dielectric constant (ε_r) confirmed a macroscopically paraelectric state for the specimen at room temperature. A slim polarization versus electric field (P-E) hysteresis loop of the specimen at room temperature indicated the existence of polar nano-regions (PNRs) superimposed on the paraelectric background. The nonlinear dielectric properties in continuous cycles of bias field sweep displayed a strong sensitivity to the field history. This phenomenon was qualitatively explained in terms of an irreversible polarization evolution of the PNRs under the bias fields. A considerable decline of the tunability with the cycle number suggests an appreciable contribution of the PNRs to the dielectric nonlinearity. The polarization and size of the PNRs were determined by fitting the dielectric constants to a multipolarization mechanism model.     

A nanogravimmetric investigation of the charging processes on ruthenium oxide thin films and their effect on methanol oxidation

The charging processes and methanol oxidation that occur during the oxidation-reduction cycles in a ruthenium oxide thin film electrode (deposited by the sol-gel method on Pt covered quartz crystals) were investigated by using cyclic voltammetry, chronoamperometry and electrochemical quartz crystal nanobalance techniques. The ruthenium oxide rutile phase structure was determined by X-ray diffraction analysis. The results obtained during the charging of rutile ruthenium oxide films indicate that in the anodic sweep the transition from Ru(II) to Ru(VI) occurs followed by proton de-intercalation. In the cathodic sweep, electron injection occurs followed by proton intercalation, leading to Ru(II). The proton intercalation/de-intercalation processes can be inferred from the mass/charge relationship which gives a slope close to 1 g mol⁻¹ (multiplied by the Faraday constant) corresponding to the molar mass of hydrogen. From the chronoamperometric measurements, charge and mass saturation of the RuO₂ thin films was observed (440 ng cm⁻²) during the charging processes, which is related to the total number of active sites in these films. Using the electrochemical quartz crystal nanobalance technique to study the methanol oxidation reaction at these films was possible to demonstrate that bulk oxidation occurs without the formation of strongly adsorbed intermediates such as CO_ads, demonstrating that Pt electrodes modified by ruthenium oxide particles can be promising catalysts for the methanol oxidation as already shown in the literature.     

A two-dimensional artifact from asynchronous decoupling

Many heteronuclear NMR experiments employ decoupling to collapse the heteronuclear multiplet, using decoupling schemes with a periodic phase modulation like WALTZ, MLEV, or GARP. Because of the periodic nature of these schemes, cycling sidebands are generated, whose intensity can be strongly reduced by decoupling asynchronously. We show that the most common implementation of asynchronous decoupling on modern spectrometers is such that the cycling sidebands are subjected to a periodic modulation. For multidimensional experiments, this results in ridges that can seriously compromise the quality of the spectrum. Based on our model, the artifact in a 2D [(1)H]-(15)N NOE equilibrium experiment is simulated and it is shown that the artifact can be prevented by using synchronous decoupling.     

Unambiguous Assignment of the 13C NMR Resonances of the Side-Chain Carbon Atoms of Dipropylglyoxal Bis(Amidinohydrazone) by DEPT and Selective Heteronuclear Proton Decoupling Techniques

The previously unassigned carbon-13 NMR resonances of the side-chain carbon atoms of the enzyme inhibitor dipropylglyoxal bis(amidinohydrazone) (DPGBG) have been unambiguously assigned with the aid of DEPT measurements and experiments involving the selective decoupling of the protons of one of the methylene groups. The chemical shifts of the side-chain carbon atoms of DPGBG decrease in a nearly linear fashion as a function of the position of the atom in the side chain, the terminal methyl groups having the lowest shift value. The carbon-13 shifts are positively correlated with the chemical shifts of the corresponding hydrogen atoms.     

A method for C(alpha) direct-detection in protonless NMR

Attempts are made to efficiently decouple (13)C nuclei without significant loss of coherence during the application of the decoupling package. Such attempts are based on the S(3)E spin-state selection method. A newly developed double S(3)E (DS(3)E) is particularly efficient for C(alpha) detection for proteins as large as 480 kDa.