三种脉冲序列制备核自旋单重态效率的比较

核自旋单重态的制备和检测在化合物分子的相关分析中具有重要的应用价值和广阔的应用前景.本文以三肽分子AGG（Ala-Gly-Gly）中两个质子构成的一组孤立的自旋耦合体系为研究对象,利用三组基于不同原理的脉冲序列,分别对该体系制备了核自旋单重态;并分别测定和比较了三种方法制备核自旋单重态的效率及其寿命.研究结果表明,对于同一分子的同一自旋耦合体系中的质子,使用不同的脉冲序列制备得到的核自旋单重态的寿命并不会有明显差异,但基于不同脉冲制备核自旋单重态的效率差异相对较大.     

14N核四极共振中自旋锁定的偏共振效应

用虚拟自旋-1/2算符理论计算了核四极共振自旋系统在自旋锁定脉冲序列作用下的时间演化,获得了自旋锁定信号随锁定脉冲长度和射频频率偏置的变化关系。如果不考虑准备脉冲期间射频频率偏置的影响,那么可简单地用核磁共振中的矢量模型来解释自旋锁定这一现象。 关键词：     

液体多脉冲及二维FT-NMR实验的乘积算符描述的计算机模拟

本文报道了利用乘积算符方法分析多脉冲及二维FT-NMR实验的模拟程序PROPER-MT.该程序对分析弱耦合I_mS_n(I=1/2;S=(1)/2;1 ≤ m十n<4)自旋体系实验脉冲序列是普遍适用的;它可给出实验过程中体系任何时刻算符的解析表达式.用PROPER-MT程序对一些典型的多脉冲及二维FT-NMR实验进行了模拟,特别对多量子滤波及多自旋滤波脉冲序列进行了分析计算,得到了预期的结果.     

基于PC机的脉冲序列发生器

为了降低谱仪的复杂性和成本，文中提出了基于PC机的脉冲序列发生器设计方案. 详细讨论了在Windows 98和Windows XP下通过关中断的方法来保证脉冲序列时序的精度和稳定性，通过实验给出了基于PC机的脉冲序列发生器的短期稳定度和长期稳定度，最后通过自旋回波实验直接验证了该方案的可行性.     

含铁磁颗粒的颗粒膜自旋激发弛豫研究

应用s-d交换作用模型，在对自旋格林函数s-d交换相互作用单环近似下，求出了含铁磁纳米颗粒的颗粒膜中自旋激发弛豫.并以(a-C：H)_1-xCo_x颗粒膜 为例，探讨了自旋激发弛豫随温度的变化规律.结果表明：经自旋极化激发实现的自旋激化弛豫过程与温度无关，而经热激活的自旋激发弛豫过程与温度有关. 关键词： 自旋激发弛豫 颗粒膜 铁磁颗粒     

基于小型化原子磁力计的零场NMR波谱仪搭建与测试

常规高场NMR波谱仪依托超导技术,其体积大、维护成本高,且存在样本磁化率不均匀导致的谱线展宽现象,零场或近零场NMR技术则可实现有效互补．本文自主搭建了一套基于小型原子磁力计的可移动零场NMR波谱仪,采用以多功能采集卡(National Instruments PCIe-6353)为核心的集成控制系统,仪器主磁场强度小于1 nT,可实现高分辨率的J-耦合谱采集．为实现对自旋体系的有效操控,利用样品绝热初态的单脉冲激发实现对三轴脉冲线圈的精确标定．在此基础上,使用改进的组合脉冲序列实现了在¹³C-¹H异核体系下的单自旋选择性操控,验证了零场NMR波谱仪的有效性．     

金刚石集群氮空位(NV)色心自旋态调控设计与实现

金刚石氮空位(nitrogen vacancy,NV)中心的天然能级系统可以在激光泵浦和微波辐射下进行初始化、量子操控和光学读取。实验中需外加特定激光泵浦和微波辐射来实现对NV色心自旋态的操控,并通过荧光数布居变化来表征自旋态。本文基于LabVIEW软件,设计开发了集群NV色心自旋态调控与读出软件系统。结果显示,本系统可以实现对激光和微波脉冲序列的精确编码,编码精度可达3ns,并初步得到了室温下集群NV色心的电子自旋共振谱线,为下一步集群NV色心自旋态调控研究的自动化、集成化奠定了基础。     

^1H自旋扩散方法研究离子化聚氨酯的相态结构

本文用改进的Goldman-Shen脉冲序列研究了聚丁二烯加MDI离子化聚氨酯体系中磁化矢量的自旋扩散过程,通过一些合理的简化,求解了扩散方程,得到了一种可定量的求出多相高聚物微区尺寸的简便方法.     

利用信息流方法优化多激发自旋链中的量子态传输

研究了量子态在一条均匀耦合的反铁磁自旋链中传输时, 信道中自旋激发数变化对其传输性质的影响. 利用信息流方法分析输出端粒子的算符演化动力学, 获得了量子态传输的平均保真度与信道自旋初态之间的关系. 结果表明, 平均保真度的大小只依赖于信道中自旋激发数的奇偶性. 通过比较在奇偶激发信道中获得的最大平均保真度, 构建了优化信道来提升量子态在自旋链中的传输质量. 进一步分析了纠缠在激发信道中的传输情况, 发现纠缠的传输质量不仅和信道中自旋激发的具体个数有关, 还取决于激发自旋的初始排列. 特别地, 当信道中自旋无激发或全部激发时, 纠缠传输的大小和持续时间都优于其他的激发信道. 上述研究结果有助于在实际系统中搭建适合量子态和纠缠传输的量子信道.     

自旋1/2-自旋1耦合系统的HSQC和HDQC实验的研究

对自旋1/2-自旋1耦合系统的单量子HSQC和双量子HDQC脉冲序列进行了理论和实验的探讨. 研究结果表明,文献提出的HDQC实验中实际上还发生了零量子跃迁,因此该实验应该是多量子HMQC实验. 研究结果还表明,HSQC有比HDQC更高的灵敏度.     

Spin-state-selective excitation in selective 1D inverse NMR experiments

A general and very simple strategy for achieving clean spin-state-selective excitation with full sensitivity in carbon-selective gradient-enhanced 1D HMQC and HSQC pulse schemes is presented. The incorporation of an additional hard 90 degrees (13)C pulse applied along a specific orthogonal axis just prior to acquisition into the conventional sequences allows us to select a simultaneous coherence transfer pathway which usually is not detected. The superimposition of this resulting antiphase magnetization to the conventional in-phase magnetization gives the exclusive excitation of the directly attached proton showing only the alpha or beta spin state of the passive (13)C nucleus. The propagation of this particular spin state to other protons can be accomplished by adding any homonuclear mixing process just after this supplementary pulse. Such an approach affords a suite of powerful selective 1D (13)C-edited NMR experiments which are helpful for resonance assignment purposes in overcrowded proton spin systems and also for the accurate determination of the magnitude and sign of long-range proton-carbon coupling constants in CH spin sytems for samples at natural abundance. Such measurements are performed by measuring the relative displacement of relayed signals in the corresponding alpha and beta 1D subspectra.     

New methods for calibration of the RF field strength for indirectly observed nuclei

Two novel pulse sequences, CALIS-1 and CALIS-2, for accurate calibration of the RF field strength for an indirectly observed spin are introduced. CALIS-2 is intended for calibration of e.g., (13)C or (15)N pulses on natural abundance samples whilst CALIS-1 is recommended primarily for enriched samples. Both experiments can be performed without prior knowledge or guess of the RF field strength and no delays in the pulse sequences are critically dependent on coupling constants.     

Optimal control based NCO and NCA experiments for spectral assignment in biological solid-state NMR spectroscopy

We present novel pulse sequences for magic-angle-spinning solid-state NMR structural studies of (13)C,(15)N-isotope labeled proteins. The pulse sequences have been designed numerically using optimal control procedures and demonstrate superior performance relative to previous methods with respect to sensitivity, robustness to instrumental errors, and band-selective excitation profiles for typical biological solid-state NMR applications. Our study addresses specifically (15)N to (13)C coherence transfers being important elements in spectral assignment protocols for solid-state NMR structural characterization of uniformly (13)C,(15)N-labeled proteins. The pulse sequences are analyzed in detail and their robustness towards spin system and external experimental parameters are illustrated numerically for typical (15)N-(13)C spin systems under high-field solid-state NMR conditions. Experimentally the methods are demonstrated by 1D (15)N-->(13)C coherence transfer experiments, as well as 2D and 3D (15)N,(13)C and (15)N,(13)C,(13)C chemical shift correlation experiments on uniformly (13)C,(15)N-labeled ubiquitin.     

Density Matrix Simulations of the Effects of J Coupling in Spin Echo and Fast Spin Echo Imaging

A computer simulation has been used to calculate the effects of J coupling on the amplitudes of echoes produced by CPMG sequences. The program computes the evolution of the density matrix for different pulse intervals and can predict the signals obtainable from spin systems of any size and complexity. Results from the simulation confirm the prediction that a decrease in the effects of J coupling is largely responsible for the bright fat signal seen in fast spin echo imaging at high pulse rates. The effects of J coupling on CPMG echotrains are examined for A3B2 and A3B2C2 spin systems over a wide range of J coupling and chemical shift values and pulse spacings. The effects of J coupling on the point spread function obtained with fast spin echo imaging are also discussed.     

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.     

Simplified multiplet pattern HSQC-TOCSY experiment for accurate determination of long-range heteronuclear coupling constants

A new two-dimensional pulse sequence for accurately determining heteronuclear coupling constants is presented. It is derived from HSQC and HECADE techniques with B0 gradient coherence selection. The main feature of the proposed method is spectra with only one component of the IS doublet; i.e., the final result is equivalent to a selective broadband excitation of either Salpha or Sbeta spin states and a preservation of these states during the entire experiment. The effect is obtained by an appropriate combination of in- and antiphase coherences. It is demonstrated that heteronuclear single-bond as well as long-range coupling constants and their relative signs are readily evaluated. The proposed sequence is equally or less sensitive to a variation of heteronuclear one-bond couplings than previously published, closely related sequences. The new method is applied to a peptide sample for determination of 3JN, Hbeta.     

Three-dimensional 13C shift/1H-15N coupling/15N shift solid-state NMR correlation spectroscopy.

Triple-resonance experiments capable of correlating directly bonded and proximate carbon and nitrogen backbone sites of uniformly 13C- and 15N-labeled peptides in stationary oriented samples are described. The pulse sequences integrate cross-polarization from 1H to 13C and from 13C to 15N with flip-flop (phase and frequency switched) Lee-Goldburg irradiation for both 13C homonuclear decoupling and 1H-15N spin exchange at the magic angle. Because heteronuclear decoupling is applied throughout, the three-dimensional pulse sequence yields 13C shift/1H-15N coupling/15N shift correlation spectra with single-line resonances in all three frequency dimensions. Not only do the three-dimensional spectra correlate 13C and 15N resonances, they are well resolved due to the three independent frequency dimensions, and they can provide up to four orientationally dependent frequencies as input for structure determination. These experiments have the potential to make sequential backbone resonance assignments in uniformly 13C- and 15N-labeled proteins.     

Accurate Measurement of Small Spin–Spin Couplings in Partially Aligned Molecules Using a Novel J-Mismatch Compensated Spin-State-Selection Filter

The accurate measurement of small spin–spin coupling constants in macromolecules dissolved in a liquid crystalline phase is important in the context of molecular structure investigation by modern liquid state NMR. A new spin-state-selection filter, DIPSAP, is presented with significantly reduced sensitivity to J-mismatch of the filter delays compared to previously proposed pulse sequences. DIPSAP presents an attractive new approach for the accurate measurement of small spin–spin coupling constants in molecules dissolved in anisotropic solution. Application to the measurement of ¹⁵N–¹³C′ and ¹H^N–¹³C′ coupling constants in the peptide planes of ¹³C, ¹⁵N labeled proteins demonstrates the high accuracy obtained by a DIPSAP-based experiment.     

New high spin level scheme of ~(87)Sr

High spin states of the odd-A87Sr were populated by the fusion-evaporation reaction82Se(9Be,4n)87Sr at a beam energy of 46 MeV. Excited levels of87 Sr have been extended up to an excitation energy of 7.4 MeV at spin31/2. The coupling of a g9/2neutron hole to the yrast states of the88 Sr core can account for the low-lying states in87 Sr. The structure of the higher spin states is discussed by analogy with those of the neighboring odd-A N =49isotones and possible configurations are proposed.