Double-quantum-filtered NMR signals in inhomogeneous magnetic fields

The possibility of exciting and detecting proton NMR double-quantum coherences in inhomogeneous static and radiofrequency magnetic fields was investigated. For this purpose specialized pulse sequences which partially refocus the strongly inhomogeneous evolution of the spin system and generate double-quantum buildup and decay curves were implemented on the NMR MOUSE (mobile universal surface explorer). The theoretical justification of the method was developed for the simple two-spin-1/2 system. The performances of the same pulse sequences were also tested on a solid-state high-field NMR spectrometer. It was shown that DQ decay curves have a better signal-to-noise ratio in the initial time regime than DQ buildup curves. The double-quantum buildup and decay curves were recorded for a series of cross-linked natural rubber samples. These curves give access to quantitative values of the ratio of proton total residual dipolar couplings which are in good agreement with those measured in homogeneous fields. A linear dependence of these ratios on the sulfur-accelerator content was found.     

Imaging the long-range dipolar field in structured liquid state samples

We describe imaging experiments in which the pattern of the dipolar field generated by spatially modulated nuclear magnetization is directly visualized in simply structured phantoms. Two types of experiment have been carried out at 11.7 T using (1)H NMR signals. In the first, the field from a single spin species is imaged via its own NMR signal. In the second, the NMR signal from one spin species is used to image the field generated by a second species. The field patterns measured in these experiments correspond well with those calculated using simple theoretical expressions for the dipolar field. The results also directly demonstrate the spatial sensitivity of the signal generated using dipolar field effects, indicating that the range of the field depends upon the inverse of the spatial frequency with which the magnetization is modulated.     

Apparent diffusion behaviour of intermolecular double-quantum coherence modulated by a distant dipolar field in solution NMR

A modified correlated spectroscopy (COSY) revamped with asymmetric Z-gradient echo detection sequence was designed to investigate the influence of diffusion behaviour on intermolecular double-quantum coherence signal attenuation during the pre-acquisition period. Theoretical formulas were deduced and experimental measurements and simulations were performed. It is found that the diffusion behaviour of intermolecular double-quantum coherence in the pre-acquisition period may be different from that of conventional single-quantum coherence, depending on the relative orientation of diffusion weighting gradients to coherence selection gradients. When the orientation of the diffusion weighting gradients is parallel or anti-parallel to the orientation of the coherence selection gradients, the diffusion is modulated by the distant dipolar field. This study is helpful for understanding the signal properties in intermolecular double-quantum coherence magnetic resonance imaging.     

Natural rubber/clay nanocomposites: Influence of poly(ethylene glycol) on the silicate dispersion and local chain order of rubber network

A novel preparation of natural rubber (NR)/Na⁺-montmorillonite (MMT) nanocomposites in only one step by using poly(ethylene glycol) (PEG) has been investigated. PEG behaves as dispersing agent favouring the intercalation of rubber chains into the silicate galleries and providing substantially improved clay dispersion. Intercalated/exfoliated miscible hybrids were observed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The influence of PEG on the network structure has also been evaluated by static proton double-quantum nuclear magnetic resonance spectroscopy (¹H DQ NMR) at low-field. Silicate nanoparticles with a high aspect ratio (clay tactoids) and a more crosslinked rubber network have been obtained for an optimum PEG/MMT ratio. Both effects were responsible of the enhancement on mechanical properties.     

Intermolecular double quantum coherences (iDQc) and diffusion-weighted imaging (DWI) imaging of the human brain at 1.5 T

To study the sensitivity of intermolecular double quantum coherences (iDQc) imaging contrast to brain microstructure and brain anisotropy, we investigated the iDQC contrast between differently structured areas of the brain according to the strength and the direction of the applied correlation gradient. Thus diffusion-weighted imaging (DWI) and diffusion tensor imaging (DTI) maps have been obtained. This procedure, which consists of analyzing both iDQc and DWI images at different gradient strength and gradient direction, could be a promising tool for clinical brain investigations performed with higher than 1.5 T magnetic fields.     

不均匀场下基于分子间双量子相干核磁共振技术的果肉检测

核磁共振（NMR）谱图可在不破坏生物样品的状态下提供组织成分组成及其含量的信息,已被广泛应用于生物、医学和食品检测等领域.NMR谱图分辨率越高,提供的与组织成分相关的信息越丰富、越准确,也越有利于未知成分的定性和定量分析.传统的高分辨NMR谱图通常要在均匀磁场下采集.但在实际应用中,均匀的磁场较难获得.这就使得我们采集的NMR谱图的分辨率,以及由此获得的生物组织成分组成和含量等信息的准确性受到影响.源于远程偶极相互作用的分子间双量子相干（iDQC）技术对磁场均匀度不敏感,可在不均匀场下获得高分辨率NMR谱图.本文采用基于iDQC技术的IDEAL-Ⅱ序列对甲基丙烯酸丁酯、蕃茄和西瓜三种样品进行了NMR实验,结果证明基于iDQC技术在不均匀场下获得水果的高分辨NMR谱图是可行的,这对食品科学以及食品检测具有积极的意义.     

Separation of isotropic chemical and second-order quadrupolar shifts by multiple-quantum double rotation NMR

Using a two-dimensional multiple-quantum (MQ) double rotation (DOR) experiment the contributions of the chemical shift and quadrupolar interaction to isotropic resonance shifts can be completely separated. Spectra were acquired using a three-pulse triple-quantum z-filtered pulse sequence and subsequently sheared along both the ν₁ and ν₂ dimensions. The application of this method is demonstrated for both crystalline (RbNO₃) and amorphous samples (vitreous B₂O₃). The existence of the two rubidium isotopes (⁸⁵Rb and ⁸⁷Rb) allows comparison of results for two nuclei with different spins (I = 3/2 and 5/2), as well as different dipole and quadrupole moments in a single chemical compound. Being only limited by homogeneous line broadening and sample crystallinity, linewidths of approximately 0.1 and 0.2 ppm can be measured for ⁸⁷Rb in the quadrupolar and chemical shift dimensions, enabling highly accurate determination of the isotropic chemical shift and the quadrupolar product, P_Q. For vitreous B₂O₃, the use of MQDOR allows the chemical shift and electric field gradient distributions to be directly determined—information that is difficult to obtain otherwise due to the presence of second-order quadrupolar broadening.     

Accurate measurements of small J coupling constants under inhomogeneous fields via intermolecular multiple-quantum coherences

Two new NMR pulse sequences, based on intermolecular multiple-quantum coherences (iMQCs), were developed to obtain apparent J coupling constants with a scaling factor from one to infinity relative to the conventional J coupling constants. Here the apparent J coupling constants were defined as apparent peak separations in unit of Hz in a reconstructed spectrum for a coupled spin system. Except for the adjustable scaling factor for apparent J coupling constants, the sequences hold the advantage of high acquisition efficiency, and retain the spectral information such as chemical shifts, multiplet patterns, and relative peak areas under inhomogeneous fields. For spin systems with small scalar coupling constants, well-resolved J-spectra can be achieved by selecting a proper scaling factor. Theoretical predictions are in good agreement with simulation results and experimental observations.     

High-resolution NMR spectra in inhomogeneous fields utilizing the CRAZED sequence without coherence selection gradients

Coherence selection gradients have been considered as indispensable for high-resolution NMR spectroscopy in inhomogeneous fields utilizing the CRAZED-type sequences. However, our experimental results demonstrate that these gradients can be omitted if an appropriate phase cycling is applied. The measured linewidth of reconstructing 1D high-resolution spectral peaks does not depend on the dipolar correlation distance determined by the coherence selection gradients, but is only affected by diffusion and T(2) relaxation. This finding suggests the need to reconsider the mechanism for the iMQC-based high-resolution spectroscopy.     

核磁共振中多量子相干扩散行为的理论表述和计算机模拟

改进了Warren所提出的CRAZED脉冲序列以研究分子间多量子相干的扩散过程 ,讨论了利用核磁共振测量分子内和分子间多量子相干表观自扩散系数的理论表述 ,采用粒子的随机行走模型模拟其扩散行为 .在短脉冲近似和长脉冲梯度场两种实验条件下 ,分别获得了因扩散引起的不同相干阶数的相对信号衰减强度随梯度场脉冲间隔时间的变化曲线 ,由此得到分子内多量子相干和分子间多量子相干的表观扩散率与溶液分子扩散系数的关系 .还将计算机模拟结果与理论预测进行分析和比较 ,发现二者能很好地吻合 .研究结果表明 ,分子间多量子相干的表观扩散率与常规的分子内多量子相干的表观扩散率明显不同 ,因此 ,分子间多量子相干的表观扩散率可能提供一种新的核磁共振成像的对比度机理