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     

具有表面弛豫的液体自扩散的Monte Carlo模拟

研究多孔介质中液体的自扩散行为能获得介质的微观结构信息,有助于了解介质中液体的传输性质.以具有不同孔隙大小的无限长圆柱体模型中的液体为对象,采用Monte Carlo随机行走方法,模拟存在表面弛豫时液体的自扩散系数和核自旋磁化强度随时间的变化,导出将NMR弛豫参数和随机行走参数联系在一起的表达式.结果表明:在快扩散区,液体的核自旋磁化强度随弛豫时间呈单指数衰减,且自扩散系数在短时情况下独立于表面弛豫率;在慢扩散区,液体的核自旋磁化强度衰减和自扩散系数在短时情况下均与表面弛豫率无关.模拟结果与理论分析相吻合,可用于求解介质的表面积与体积之比及孔径大小等结构信息.     

具有表面弛豫的液体自扩散的M0nte Carlo模拟

研究多孔介质中液体的自扩散行为能获得介质的微观结构信息,有助于了解介质中液体的传输性质.以具有不同孔隙大小的无限长圆柱体模型中的液体为对象,采用Monte Cado随机行走方法,模拟存在表面弛豫时液体的自扩散系数和核自旋磁化强度随时间的变化,导出将NMR弛豫参数和随机行走参数联系在一起的表达式.结果表明:在快扩散区,液体的核自旋磁化强度随弛豫时间呈单指数衰减,且自扩散系数在短时情况下独立于表面弛豫率;在慢扩散区,液体的核自旋磁化强度衰减和自扩散系数在短时情况下均与表面弛豫率无关.模拟结果与理论分析相吻合,可用于求解介质的表面积与体积之比及孔径大小等结构信息.     

热辐射输运问题的高效蒙特卡罗模拟方法

惯性约束聚变研究中,热辐射光子在介质中的输运以及热辐射光子与介质的相互作用是重要研究课题,蒙特卡罗方法是该类问题的重要研究手段之一.隐式蒙特卡罗方法虽然能正确地模拟热辐射在介质中的输运过程,但当模拟重介质(材料的吸收系数大)问题时,该方法花费的计算时间将变得很长,导致模拟效率很低.本文以离散扩散蒙特卡罗方法为基础,开发了"离散扩散蒙特卡罗方法辐射输运模拟程序",可以较好地解决重介质区的计算效率问题,但是离散扩散蒙卡罗方法在模拟轻介质区时精度不够高.辐射输运问题中通常既有轻介质也有重介质,为了能同时解决蒙特卡罗方法模拟的效率和精度问题,本文研究了离散扩散蒙特卡罗方法与隐式蒙特卡罗方法相结合的模拟方法,并提出了新的扩散区与输运区界面处理方法,研制了混合蒙特卡罗方法的辐射输运模拟程序.典型辐射输运问题模拟显示:在模拟重介质问题时,该程序能大幅缩短模拟时间,且能取得与隐式蒙特卡罗方法一致的结果;在模拟轻重介质均存在的问题时,与隐式蒙特卡罗方法相比,混合蒙特卡罗方法的模拟精度与其相当且计算效率同样能够得到显著提升.     

基于过抽样Gabor变换的核磁共振FID信号增强算法

基于作者先前提出的过抽样实值离散Gabor变换,本文提出了一有效的算法用于核磁共振自由感应衰减（NMR FID）信号的减噪. 由于NMR FID信号在时域中是一短暂的振荡衰减信号,使得变换后的NMR FID信号能量在时频域中集中在少数变换系数上,而噪声则遍布在整个变换系数上,因此通过对变换系数幅度进行阈值限制方法可达到明显地增强NMR FID信号的目的. 文中在理论和模拟实验上分析表明,过抽样Gabor变换比临界抽样Gabor变换更适宜于NMR FID信号的减噪,因为在过抽样条件下比在临界抽样条件下的综合窗及其对应的分析窗,无论是在时域中还是在频域中都可具有更好的局域分布集中性,同时,Gabor变换在过抽样条件下也比在临界抽样条件下具有更高的时频精度.     

固体核磁共振技术在甲醇制烯烃反应中的应用

甲醇制烯烃过程是由非石油路线生成低碳烯烃的重要途径之一.分子筛因具备独特的孔结构和可调变的酸性质,而成为甲醇制烯烃过程的核心催化剂.固体核磁共振(NMR)是鉴定物质结构、阐释催化反应机理的强有力的工具,在甲醇制烯烃的研究中被广泛应用.本文主要总结了近年来利用原位固体NMR、多维多核NMR、脉冲梯度场NMR等固体NMR技术研究甲醇制烯烃反应机理取得的重要进展.原位固体NMR可以在真实反应条件下监测催化反应中反应物、中间体和产物的动态演变过程;多维多核NMR可以在不破坏催化剂结构情况下确定反应中间体结构信息,特别是¹²⁹Xe NMR可以很灵敏探测反应中催化剂的孔道结构变化;脉冲梯度场NMR可用于测定孔道内分子的扩散系数,阐明分子筛的扩散机制.     

液体NMR中平板间多量子相干受限扩散行为的有限差分模拟

将平板间单量子相干受限扩散理论表述推广到多量子相干,并结合积算符矩阵、Bloch方程和有限差分方法进行模拟. 通过模拟找出平板间受限扩散信号衰减随平板间距变化的规律,并与实际体系比较. 结果表明：平板间n量子相干的自旋回波信号衰减曲线与单量子类似,且其产生同样衍射图样所需的脉冲梯度场强度仅为单量子的1/|n|,可用于测量微小的平板间距. 本文的模拟方法可进一步推广到复杂体系的研究.     

超快速COSY类2D NMR实验弛豫假峰的抑制

在脉冲梯度场基础上研究了进一步缩短COSY类2D NMR实验数据采集时间的新方法.利用主动屏蔽梯度场线圈的梯度场恢复时间仅为100μs数量级这一特点,提出一类基于脉冲梯度场消除弛豫假峰的脉冲序列.并以DQF-COSY脉冲序列为例加以验证.实验结果表明:采用文中的方法,取序列重复时间远小于T₁和T₂是切实可行的;梯度场技术能很好地抑制弛豫假蜂以达到2D NMK数据的快速采集.     

磁流变液构成的类梯度结构振动传递特性

提出了一种磁流变液构成的类梯度结构,并通过理论建模、数值计算和实验研究了该结构的振动传递特性.磁流变液在磁场作用下具有液固转换的特殊理化性质,而液固转换过程就是磁流变液的振动传递阻抗变化过程.因此,基于磁流变液的这一特性,通过控制磁场,构建了类梯度结构.基于弹性波传递的一维波动方程,建立了垂直入射的弹性波在类梯度结构中传递的波动方程.然后,使用连续介质的离散化方法和传递矩阵法进行求解,得到振级落差的表达式,对其进行数值计算,分析类梯度结构的振级落差随弹性波频率和磁场强度的变化趋势.最后,对类梯度结构的振动传递特性进行了实验研究,分析了磁场强度对类梯度结构振动传递特性的影响.研究结果表明,与均匀场作用的磁流变液相比,类梯度结构对弹性波的衰减效果更好,且该结构具备良好的可调控特性.     

激光梯度场中荧光关联谱学的实验研究

研究了荧光关联谱(fluorescence correlation spectroscopy,简称FCS)在FCS测量中外加激光梯度场的影响.实验显示,微区内粒子的扩散时间随梯度场强度增加而增加,近似呈线性关系.同时,微区内平均粒子数目随梯度场相应地增加.粒子的极化率越大,相同条件下受到激光梯度场的影响就越大. 关键词： 荧光关联谱(FCS) 激光梯度场 扩散时间     

Gas diffusion in a pulmonary acinus model: experiments with hyperpolarized helium-3

Diffusion of hyperpolarized helium-3 in epoxy phantoms was experimentally studied by pulsed-gradient nuclear magnetic resonance (NMR). One phantom with a dichotomic branching structure densely filling a cubic volume was built using the Kitaoka algorithm to model a healthy human acinus. Two other phantoms, one with a different size and the other one with a partial destruction of the branched structure, were built to simulate changes occurring at the early stages of emphysema. Gas pressure and composition (mixture with nitrogen) were varied, thus exploring different diffusion regimes. Preliminary measurements in a cylindrical glass cell allowed us to calibrate the gradient intensity with 1% accuracy. Measurements of NMR signal attenuation due to gas diffusion were compared to a classical Gaussian model and to Monte Carlo simulations. In the slow diffusion regime, the Gaussian model was in reasonable agreement with experiments for low gradient intensity, but there was a significant systematic deviation at larger gradient intensity. An apparent diffusion coefficient Dapp was deduced, and in agreement with previous findings, a linear decrease of Dapp/D0 with D0(1/2) was observed, where D0 is the free diffusion coefficient. In the regime of intermediate diffusion, experimental data could be described by the Gaussian model for very small gradient intensities only. The corresponding Dapp/D0 values seemed to reach a constant value. Monte Carlo simulations were generally in fair agreement with the measurements in both regimes. Our results suggest that, for diffusion times typical of medical magnetic resonance imaging, an increase in alveolar size has more impact on signal attenuation than a partial destruction of the branched structure at equivalent surface-to-volume ratio.     

A simulation algorithm based on Bloch equations and product operator matrix: application to dipolar and scalar couplings

A product operator matrix is proposed to describe scalar couplings in liquid NMR. Combination of the product operator matrix and non-linear Bloch equations is employed to describe effects of chemical shift, translational diffusion, dipolar field, radiation damping, and relaxation in multiple spin systems with both scalar and dipolar couplings. A new simulation algorithm based on this approach is used to simulate NMR signals from dipolar field effects in the presence of scalar couplings. Several typical coupled spin systems with both intra-molecular scalar couplings and inter-molecular dipolar couplings are simulated. Monte Carlo methods are incorporated into simulations as well to analyze diffusion process in these complicated spin systems. The simulated results of diffusion and relaxation parameters and 2D NMR spectra are coincident with the experimental measurements, and agree with theoretical predictions as well. The simulation algorithm presented herein therefore provides a convenient means for designing pulse sequences and quantifying experimental results in complex coupled spin systems.     

Atomistic study on the activation enthalpies for interface mobility and boundary diffusion in an interface-controlled phase transformation

A multi-lattice kinetic Monte Carlo atomistic simulation method has been used to simulate the austenite to ferrite interface-controlled transformation in pure iron. By performing simulations with different amounts of “free volume” at the interface, quantitative relations between the activation energies for interface mobility, boundary self diffusion and bulk self diffusion were investigated. The effect of different interface orientations on the distribution of free volume over the interface, as determined by interface crystallography, and its consequences for interface mobility activation energy was also evaluated. The essential role of thermal fluctuations in free volume distribution at the interface has been shown. The activation enthalpy for boundary diffusion is shown to be larger than the interface mobility activation enthalpy.     

Apparent diffusion behaviors of spins in the presence of distant dipolar field in two-component solution NMR

The diffusion behaviors of spins in the presence of distant dipolar field in two-component spin systems during the second evolution period of a modified CRAZED sequence before acquisition were investigated. Theoretical formulas were deduced based on the distant dipolar field model. The simulation results and experimental observations are consistent with the theoretical predictions. This study shows that the relative intensities of signals from intermolecular zero-quantum coherences (iZQCs) and intermolecular double-quantum coherences (iDQCs) have the same diffusion attenuation characteristic under the combined effect of diffusion weighting gradients and distant dipolar field during the second evolution period. This diffusion attenuation may be different from that of conventional single-quantum coherence signal, depending on the relative orientation of the diffusion weighting gradients to the coherence selection gradients. The results presented herein are helpful for understanding the effect of distant dipolar field from a spin system on the diffusion behavior of other spin system and the signal properties in the iZQC or iDQC magnetic resonance imaging.     

漫射近似理论的有效使用范围分析

利用蒙特卡罗方法模拟了半无限大生物组织内部深度分辨的光能流率的分布情况。分析了漫射近似理论的有效使用范围。当组织厚度大于 3/ 2个光子的平均自由程时 ,应用漫射近似理论能得到很好的结果 ,反之 ,漫射理论不能使用。也就是说 ,当组织厚度z >0 1875cm时 ,应用漫射理论能得到很好的结果 ;当组织厚度z <0 1875cm时 ,漫射理论不能使用     

低场低能区金刚石内载流子飞行时间的蒙特卡洛模拟

金刚石是一种重要的宽禁带半导体材料,对金刚石内载流子输运过程的研究将有助于了解金刚石用作各种电子器件的潜能。利用Monte Carlo模拟方法,研究了在低场低能区金刚石内载流子的飞行时间。在模拟中考虑了抛物线型能带模型和声学声子散射机制,以及样品对光的吸收和载流子在Brillouin区边界的Bragg反射。通过模拟,得到了低场低能区金刚石材料内载流子的飞行时间分布,并与相关的实验结果进行了比较分析,验证了该模拟模型的正确性。研究结果表明,在低场低能区,金刚石材料内主要的散射机制是声学声子散射。在研究金刚石材料内载流子的迁移输运问题时,可以采用较为简单的抛物线型能带模型,但在研究薄样品中的载流子输运时应当考虑材料的光吸收对初始载流子分布的影响,而且在场强较高以及样品厚度较大时,应当考虑载流子在Brillouin区边界的Bragg反射。     

不同射线能量及线衰减系数条件下体源探测效率的函数模型

基于放射性废物桶内所含介质材料和放射性核素分段均匀分布的假设, 采用蒙特卡罗程序模拟计算多种射线能量、多种样品密度条件下的线衰减系数和体源探测效率, 通过多元非线性拟合得到以线衰减系数和能量为自变量的体源探测效率函数。基于壳源法, 通过多个点源组合测试近似替代均匀体源的实验测量, 对3种能量射线和3种密度的样品进行验证实验, 利用蒙卡模拟与数值拟合结合方法和实验测量两种方式获得各自的体源探测效率, 完成活度估算。两种方式活度估算结果相对误差均小于23%。通过蒙卡模拟与数值拟合结合方法所得结果与实验结果基本吻合, 证明了该方法的有效性。     

Measurements of restricted diffusion using an oscillating gradient spin-echo sequence

An oscillating gradient spin-echo (OGSE) pulse sequence was used to measure the apparent diffusion coefficient (D(app)) of water in the short diffusion time regime in the presence of restrictions. The diffusion coefficients of water in a simple water sample and a water and oil mixture were measured to be the same for different periods of the gradient oscillation, as expected when there are no restriction effects. The D(app) of water in the spaces between closely packed beads was also measured as a function of the gradient oscillation periods in the range 11 to 80 ms. The D(app) of water in restricted systems varies with the period of the gradient oscillation and the dispersion depends on the scale of the restriction. For a sample of packed beads of diameter 9.1 +/- 0.7 microm, the pore surface-to-volume ratio was estimated experimentally by this method to be 1.3 +/- 0.1 microm(-1), corresponding to a mean pore diameter of 6.4 +/- 0.7 microm. A Monte Carlo computer simulation of the NMR OGSE signal from the spins diffusing in a system of compartments was also implemented and the D(app) demonstrated similar behavior with gradient oscillation periods.