用二维NMR变换谱定量地研究氘代DMSO和氘代氯仿中小肽活泼质子的交换动力

用核磁共振二维交换谱方法研究了类肽化合物Ｃｂｚ－Ｔｙｒ－ＯＣ６Ｈ１３中活泼质子的交换动力学,结果表明,在ＤＭＳＯ－ｄ６和ＣＤＣｌ３溶液中,四种活泼质子与溶剂中残留水的交换快慢顺序为：Ｓｅｒ－ＯＨ〉Ｔｙｒ－ＯＨ〉Ｓｅｒ－ＮＨ〉Ｔｙｒ－ＮＨ,在此基础上,对氨基酸中氨基所处的局部环境进行了讨论。     

质子交换膜中的传质分析

质子交换膜燃料电池是最有应用前景的汽车动力替代系统。质子交换膜中的传质是质子交换膜燃料电池性能的控制因素之一。论文从宏观和微观角度分析了质子交换膜中的质子和水分的传递机理,分析了操作参数对质子在质子交换膜中传递的影响。研究发现:外载荷对质子和水分在质子交换膜中的传递有很大影响;（H₅O₂）⁺是水合质子的主要结构形式;通过（H₅O₂）⁺中氢氧键不断形成与断裂,电荷在质子交换膜中得以传递。研究结果对理解质子交换膜中的传质机理及其推广应用具有积极意义。     

小白鼠肌肉组织的NMR质子自旋交换分析

本文在Zimmerman-Brittin两相质子交换核磁共振弛豫模型基础上,分析了NMR弛豫实验中检测信号与各相表现和本征弛豫多数的关系,编写了自动化处理实验数据的计算机程序,这一技术可用于复相系统中不同成分的NMR表现和本征弛豫特性研究中,本文中的样品是选用健康新鲜的小白鼠肌肉,没加任何处理,用h-h,s-h,s-s脉冲序列,反转恢复法(π-τ-π/2)在强场下(0.92T)做T₁、T₂测定实验,分析结果表明本征弛豫参数T₁=1050ms,T₂=4500μs的成分是由肌肉中的"自由水"引起的,其质子相对含量为69%;本征弛豫参数T₁=530ms,T₂=26μs的成分是由肌肉中的"束附水"引起的,其质子相对含量为9%,本征弛豫多数T₁=530ms,T₂=1250μs的成分是由肌肉中的各种大分子和有机物引起的,其质子相对含量为9%,本征弛豫参数T₁=470ms,T₂=1250μs的成分由样品中的脂肪引起的,其质子相对含量为13%,在肌肉组织中的质子与水中质子之间有强烈的交换作用,其交换率k=1000s^-1.在脂肪中的质子与其它成分之间没有交换作用。     

质子交换LiNbO3晶体的光谱特性与抗光折变机理的研究

测量了质子交换LiNbO₃,波导层的红外光谱和光电导.实验结果表明,它们抗光折变能力的提高所造成的是其光电导比纯LiNbO₃,晶体高5—10倍. 关键词：     

MeV氢微团簇离子与固体介质的电荷交换

利用静电加速器提供的0.6—1.8MeV的H⁺，H⁺₂，H⁺₃离子，轰击不同厚度的碳膜，分别测量这些离子通过碳膜后各种产物的产额. 得到了不同能量的H⁺通过碳膜后中性原子H和负离子H^-的产额随入射质子速度的变化关系；分别得到能量为1.2MeV,1.8MeV的H⁺₂，H⁺₃团簇离子通过不同厚度碳膜的透射产额及其与团簇离子在碳膜中驻留时间的关系；对结果进行了理论分析与讨论. 关键词： 团簇离子 电荷交换     

人体胰岛素质子交换反应的核磁共振研究

用线型拟合的方法通过核磁共振谱图测得了人体胰岛素R6六聚体中酰胺质子与重氢的交换速度.因为用这一方法对实验谱图进行计算模拟时考虑了核磁共振谱线所提供的所有信息,所以我们获得了化学位移非常接近的蛋白质酰胺质子与重氢的交换速度,这是用其它方法难以得到的数据.结果表明,用本文所述方法获得的酰胺质子的交换速度与由2DNMR计算所得的蛋白质结构有非常好的吻合.在获得酰胺质子交换速度的基础上,本文详细讨论了交换反应速度与蛋白质结构的关系,结果表明,在该蛋白质中影响酰胺质子交换速度大小的因素以强弱顺序排列为:质子在肽链中的位置 > 是否参与形成氢键 > 蛋白质的二级及三级结构.     

BiFeO3/Ni81Fe19磁性双层膜中的交换偏置及其热稳定性研究

研究了磁场诱导生长的BiFeO₃/Ni₁₈Fe₁₉磁性双层膜中 的交换偏置及其热稳定性. 结果表明: BiFeO₃/Ni₁₈Fe₁₉双层膜中的交换偏置场H_ex未表现出明显的磁练习效应. 在负饱和磁场等待过程中, BiFeO₃/Ni₁₈Fe₁₉双层膜磁滞回线的前支和后支曲 线都随着在负饱和磁场中等待时间t_sat的增加向正场方向偏移. 交换偏置场H_ex的大小随着等待时间t_sat的增加而减小, 矫顽力H_c基本不变. 交换偏置场H_ex的大小随测量温度T_m的升高变化不明显, 表现出良好的热稳定性; 但矫顽力H_c随T_m的升高而显著减小. 良好的热稳定性应该来源于铁电性和反铁磁性间的共同耦合作用. 关键词： 多铁性 磁性薄膜 交换偏置 热稳定性     

磁性物质交换Hamiltonian中两项的竞争

对于一个N电子体系, 正确的交换Hamilton应该由两项组成，为H_ex=-2A1ii·s_j-2A₂ii·sj，而不是以往的铁磁学理论使用的H_ex=-2Aii ·s_j （其中A为A₁与A₂的代数和， A₁>0, A₂<0）, 以往的理论使用了一个不合理的交换Hamiltonian量.-2A₁ii·s_j与-2A₂ii< /sub>·s_j在数学上是同类项，但是在物理上不是 同类项，它们有不同的本征态和本征值.根据量子力学中的态叠加原理，这个电子系统的本 征态矢为X〉=1A²₁+A²₂(A₁ 1〉+A₂‖2〉),其中Dirac符号1〉表示系统所有电子 的自旋平行排列时的态（简称平行自旋态）矢量，2〉表示系统所有电子或最近邻电子的自 旋反平行排列时的态（简称反平行自旋态）矢量，H_ex的本征值（即系统的 交换能） 为E=-Nz（A₁-A₂）-2NzA₂²A₁ +A₂=-Nz（A₂-A₁）-2NzA²₁A< sub>1+A₂,其中z为最近邻电子数.当A₂=0时，X〉=1〉，E =-A₁, 系统具有Wei ss 铁磁性；当A₁ =0 时，X〉=2〉，E =-A₂，系统具有Neel 反铁磁性；当A₁ =A₂（即A=0）时，X〉=12 (1〉+2〉)，E=-A₁，系统处于自旋玻璃（spin glass）态；当A₁>A ₂时，X〉=1A²₁+A²₂［(A₁-A₂)1〉+A₂(1〉+2〉)］,平行自旋态与自旋 玻璃态共存；当A₁2时，X〉=1A²₁+A2₂［(A₂-A₁)2〉+A₁( 1〉+2〉)］，反平行自旋态与自旋玻 璃态共存.与原来理论中的Weiss铁磁态或Neel反铁磁态相比，平行自旋态与自旋玻璃态共存 或反平行自旋态与自旋玻璃态共存使系统的交换能降低.自旋玻璃态中电子自旋之间取向的 随机性或无序性是由交换Hamiltonian中-2A₁iis_j与-2A₂ii·s_j之间的竞争引起的，不是热运 动引起的. 关键词： 交换哈密顿量 铁磁态 反铁磁态 自旋玻璃态     

交换作用对CeF3晶体磁性和磁光效应的影响

研究了顺磁性晶体CeF₃内交换作用有效场随温度的变化关系，给出了其形式为H_in=(-0.68-0.002T)×10^-6M.结合该关系，用量子理论的计算得到了与实验值吻合较好的磁化率倒数、Verdet常数倒数随温度的变化关系，并且用光磁效应的概念和规律对结果作了进一步分析，指出光诱导促进了该晶体内电子间的交换作用. 关键词： 3晶体')" href="#">CeF₃晶体 交换作用 磁光效应 光磁效应     

s-f交换作用和电子交换作用对s电子比热容的影响

根据s-d交换作用模型，考虑了s-f交换效应对稀土金属电子-声子耦合的影响，具体讨论了s电子的比热容．计算结果表明，s电子的比热容可以写为如下的形式：γ＝γ₀＋γ_ep＋γ_ex＋γ_s-f. 关键词：     

Measurement of Chemical Exchange Rate Constants with Solvent Protons Using Radiation Damping

When chemical exchange occurs between a concentrated and a diluted species like the proton exchange between water and proteins in biochemical systems, it is difficult to use the conventional methods for a quantitative dynamical study. In this paper, a new approach which utilizes radiation damping of the strong water magnetization exchanging with the weak resonance of the mobile protons in biomolecules is proposed. It is demonstrated with a dilute guanidine solution, using the simple inversion-recovery pulse sequence, that the exchange rate constants between water and guanidine protons are evaluated by solving the Bloch equations modified with both the radiation damping and the chemical exchange effects.     

含Cr (Ⅲ)溶液中配位水质子的1H NMR研究

本文用¹H NMR对水合Cr(Ⅲ)络离子中配位水和质子交换速率进行研究。在溶液pH为0~3.17范围测得质子的平均寿命约为10^-5S。在pH为0~0.76范围质子交换反应动力学为一、二级混合过程。pH为0.76~1.6范围表现为一级过程。在Cr(Ⅲ)-H₂O-Gly系统中,实验得出配位水质子的活动性减小。     

Z-spectroscopy with Alternating-Phase Irradiation

Magnetization transfer (MT) MRI and Z-spectroscopy are tools to study both water-macromolecule interactions and pH-sensitive exchange dynamics between water and the protons of mobile chemical groups within these macromolecules. Both rely on saturation of frequencies offset from water and observation of the on-resonance water signal. In this work, an RF saturation method called Z-spectroscopy with Alternating-Phase Irradiation (ZAPI) is introduced. Based on the T(2)-selectivity of the irradiation pulse, ZAPI can be used to separate the different contributions to a Z-spectrum, as well as to study the T(2) distribution of the macromolecules contributing to the MT signal. ZAPI can be run at resonance for water and with low power, thus minimizing problems with specific absorption rate (SAR) limits in clinical applications. In this paper, physical and practical aspects of ZAPI are discussed and the sequence is applied in vitro to sample systems and in vivo to rat head to demonstrate the method.     

Spin dynamics of polarization inversion spin exchange at the magic angle in multiple spin systems

Polarization inversion spin exchange at the magic angle (PISEMA) [J. Magn. Reson. A 109, 270 (1994)] is an important experiment in NMR structural characterization of membrane proteins in oriented lipid bilayers. This paper presents a theoretical and experimental study of the spin dynamics in PISEMA to investigate the line-narrowing mechanism. The study focuses on the effect of neighboring protons on the spin exchange of a strongly coupled spin pair. The spin exchange is solved analytically for simple spin systems and is numerically simulated for many-spin systems. The results show that the dipolar couplings from the neighboring protons of a strongly coupled spin pair perturb the spin exchange only in the second order, therefore it has little contribution to the linewidth of PISEMA spectra in comparison to the separated-local-field spectra. The effects from proton resonance offset and the mismatch of the Hartmann-Hahn condition are also discussed along with experimental results using model single-crystal samples.     

Residue-specific NH exchange rates studied by NMR diffusion experiments

We present a novel approach to the investigation of rapid (>2s(-1)) NH exchange rates in proteins, based on residue-specific diffusion measurements. (1)H, (15)N-DOSY-HSQC spectra are recorded in order to observe resolved amide proton signals for most residues of the protein. Human ubiquitin was used to demonstrate the proposed method. Exchange rates are derived directly from the decay data of the diffusion experiment by applying a model deduced from the assumption of a two-site exchange with water and the "pure" diffusion coefficients of water and protein. The "pure" diffusion coefficient of the protein is determined in an experiment with selective excitation of the amide protons in order to suppress the influence of magnetization transfer from water to amide protons on the decay data. For rapidly exchanging residues a comparison of our results with the exchange rates obtained in a MEXICO experiment showed good agreement. Molecular dynamics (MD) and quantum mechanical calculations were performed to find molecular parameters correlating with the exchangeability of the NH protons. The RMS fluctuations of the amide protons, obtained from the MD simulations, together with the NH coupling constants provide a bilinear model which shows a good correlation with the experimental NH exchange rates.     

Chemical exchange of hydroxyl protons in quercetin measured by pulsed field gradient NMR

The diffusion behavior of hydroxyl protons (OH) in quercetin in 100% DMSO-d₆ (deuterium dimethylsulfoxide) and a 90% DMSO-d₆ solution containing 10% H₂O was investigated with 600 MHz ¹H pulsed field gradient (PFG) nuclear magnetic resonance (NMR). Only resonances of the 5-hydroxyl protons (OH5) were well resolved in NMR spectra of quercetin for all solutions under study. This phenomenon is explained by the intramolecular hydrogen bonding between OH5 protons and the 4-carbonyl oxygen (CO4). During diffusion experiments, the OH5 protons showed a biexponential diffusion decay, indicating an exchange process with water. As water content in the solvents increased, the lifetime (τ _q) of the OH5 protons decreased from 96.7±10.0 ms in 100% DMSO-d₆ to 14.3±1.4 ms in the 90% DMSO-d₆ solution containing 10% H₂O, indicating an increase in the exchange rate (k _q = l/τ _q) of the OH5 protons. This study demonstrates that the diffusion approach with PFG-NMR is much faster and easier for estimating the short lifetime or fast exchange rate of hydroxyl protons in quercetin.     

Optimization of the irradiation power in chemical exchange dependent saturation transfer experiments

In chemical exchange dependent saturation transfer imaging experiments, exchangeable solute protons are saturated and the transfer of saturation to water is subsequently detected. When the applied irradiation power is comparable to the resonance frequency difference between the water protons and saturated solute protons, the proton transfer (PT) efficiency is reduced due to concomitant direct saturation effects. In this study, the PT process is modeled using a two-pool system. An empirical general proton transfer ratio (PTR) equation for arbitrary RF irradiation power is derived, and its optimal power to maximize the PTR is analyzed. The results are confirmed experimentally on 4.7 T using a poly-L-lysine solution. The theory provides a useful tool for optimizing the irradiation power of the PT sequences in the presence of direct saturation effects.     

Proton residual dipolar couplings by NMR magnetization exchange in cross-linked elastomers: determination and imaging.

Proton nuclear magnetic resonance (NMR) magnetization exchange is used to investigate residual dipolar couplings in a series of cross-linked poly(styrene-cobutadiene) elastomers. A new model for the dipolar unit is used for the evaluation of the signal decay in magnetization exchange experiments. It takes into account an extended residual dipolar coupling network along the polymer chain. It is shown that in the regime of short mixing times, information about the residual dipolar coupling between methine and methylene protons can be obtained which is not affected by other inter- and intramolecular dipolar couplings. The dynamic order parameter of methine-methylene protons is measured and correlated with cross-link density. This study certifies the quality of a filter for magnetization from residual dipolar couplings which exploit magnetization exchange. The filter can be used to generate contrast in NMR images of heterogeneous elastomers. The first proton NMR parameter image of a dynamic order parameter is presented for a phantom made from poly(styrene-cobutadiene) samples with different cross-link densities.     

An evaluation of the contributions of diffusion and exchange in relaxation enhancement by MRI contrast agents

Magnetic compounds are known to enhance water proton relaxation, either by diffusion or by proton exchange. An experimental procedure to distinguish both mechanisms is proposed and validated by relaxation measurements made in water-methanol solutions of Dy(3+), Ni(2+), Gd(3+), Tempo, and AMI-25. The test discriminates according to the character of the transverse relaxation in water-methanol solutions: a mono-exponential decay corresponds to diffusion, while a bi-exponential decay indicates the contribution of a proton exchange. The study of ferritin and akaganeite particle solutions confirms the occurrence of a proton exchange between protons belonging to hydroxyl groups of the particle surface and free water protons.