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71.
Goldbourt A Vinogradov E Goobes G Vega S 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,169(2):306-350
A high resolution two-dimensional solid state NMR experiment is presented that correlates half-integer quadrupolar spins with protons. In this experiment the quadrupolar nuclei evolve during t1 under a split-t1, FAM-enhanced MQMAS pulse scheme. After each t1 period ending at the MQMAS echo position, single quantum magnetization is transferred, via a cross polarization process in the mixing time, from the quadrupolar nuclei to the protons. High-resolution proton signals are then detected in the t2 time domain during wPMLG5* homonuclear decoupling. The experiment has been demonstrated on a powder sample of sodium citrate and 23Na-1H 2D correlation spectra have been obtained. From the HETCOR spectra and the regular MQMAS spectrum, the three crystallographically inequivalent Na+ sites in the asymmetric unit were assigned. This MQMAS-wPMLG HETCOR pulse sequence can be used for spectral editing of half-integer quadrupolar nuclei coupled to protons. 相似文献
72.
We describe a new experiment for measuring homonuclear-decoupled anisotropic chemical shift patterns in doubly 13C-labeled compounds under magic-angle spinning. The experiment combines a pair of selective and non-selective 180 degrees pulses to suppress the 13C-13C scalar and dipolar interactions. This is combined with the recently developed SUPER technique to recouple the chemical shift anisotropy. Demonstrations on 13Calpha and 13CO-labeled amino acids and peptides show that accurate chemical shift powder patterns can be obtained. This permits the use of chemical shift anisotropy for conformational studies of suitably extensively 13C-labeled peptides and proteins. 相似文献
73.
Price WS Stilbs P Söderman O 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2003,160(2):139-143
The influence of finite length gradient pulses on NMR diffusion experiments on liquids confined to diffuse between two parallel planes is investigated. It is experimentally verified that the pore size decreases when determined using finite gradient pulses if the results are analyzed within the short gradient pulse approximation. The results are analyzed using the matrix formulation. The observed minima in the echo decay profiles are considerably less sharp than theoretical analysis would indicate and we suggest that this is due to the presence of a distribution of pore sizes in the sample. In addition, effects due to the presence of background gradients are discussed. It is argued that effects due to the finite length gradient pulses are relatively minor and in realistic applications the effects due to inhomogeneities in pore sizes and effects due to background gradients will constitute more serious problems in pore size determinations by means of NMR diffusometry. 相似文献
74.
Shen J 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2001,149(2):234-238
Unlike prefocused pulses and shaped pulses based on the linear response theory, delayed-focus pulses (X.-L. Wu et al., 1991, Magn. Reson. Med. 20, 165--170) produce a selective spin echo after a predefined short delay without using a pi refocusing pulse. In this paper, a series of delayed-focus pulses of different flip angles are proposed based on optimization using Fourier series representation and simulated annealing. The resistance of these delayed-focus pulses to T(2) relaxation is also demonstrated using numerical simulation of Bloch equations. 相似文献
75.
Steffen M Vandersypen LM Chuang IL 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2000,146(2):369-374
The rotation of a spin subject to an on-resonance soft pulse and simultaneously to a soft pulse at a nearby frequency may strongly deviate from the desired rotation expected for a single on-resonance pulse. The deviation is the result of transient frequency shifts of the spin caused by the off-resonance irradiation. We show that the resulting error can be corrected by shifting the frequency of the on-resonance pulse in such a way that it tracks the shift of the spin frequency. Experimentally, the effectiveness of this simple and intuitive method is demonstrated for simultaneous inversions at nearby frequencies in the case of both coupled and uncoupled spins. Simulations predict that the correction technique is effective for arbitrary pulse shapes and tip angles and is particularly useful when the frequency window of the shaped pulse is two to eight times the frequency separation between the chemical shifts of the two spins. 相似文献
76.
77.
The use of chiral liquid crystals as NMR solvent is a powerful tool to visualize and quantify enantiomers. This technique is much more robust than traditional liquid state techniques. Recent developments have been performed to simplify proton spectra obtained in these solvents which are usually complex to analyze. In the different published sequences the enantiomeric differentiation can be visualized but none of them rely the different (1)H-(1)H couplings to have a coherent set for each enantiomer especially in cases of racemic mixtures. In this work to overcome such limitations, we present a new NMR pulse sequence using semi-selective pulses to assign for each enantiomer the different (1)H-(1)H couplings. The aim is to obtain the signal of only one enantiomer, through a first Selective ReFocussing (SERF) filtering block implemented for the enantio-selection followed by a second SERF block for measuring a chosen coupling. The whole sequence is called (1)H SERF-filtered-SERF. These techniques permit for the first time to assign all dipolar couplings to each enantiomer of racemic mixtures dissolved in chiral oriented media. We demonstrate that using this experiment it is possible to visualize enantio-differentiation even in the case where the multiplets are not resolved in the SERF experiments, pushing back the limits of the enantiomeric visualization. 相似文献
78.
利用数值求解原子在强激光场中的含时薛定谔方程,对一维氦原子处于两色红外组合场中产生的高次谐波进行了研究,研究发现,在组合场驱动下,谐波谱的截止位置可以拓展到 ,从而得到脉宽较短的多个阿秒脉冲,通过改变两束激光的相位延迟,最终得到了33.8as的单个脉冲。进一步利用小波变换分析了阿秒脉冲的发射特征,发现单个阿秒脉冲实现是对电子长路径抑制的结果. 相似文献
79.
皮秒脉冲在色散缓变光纤中的孤子效应压缩 总被引:11,自引:4,他引:11
本文给出了描述皮秒脉冲在色散缓变单模光纤中孤子效应压缩过程的数学模型。通过数值求解,首次对该孤子效应压缩进行了全面的计算和分析。结果表明,与常规光纤相比,采用色散缓变程度合适的光纤压缩皮秒脉冲,不仅能显著地提高压缩后脉冲的峰值功率和脉冲压缩比,而且能有效地消除压缩后脉冲的次峰和脉座。对于确定的脉冲输入,发现,当光纤的色散缓变程度取某一最佳值时,能获得最佳的压缩效果。进一步研究表明,色散的这一最佳变 相似文献
80.
New Types of Planar Chiral [2.2]Paracyclophanes and Construction of One‐Handed Double Helices 下载免费PDF全文
Prof. Yasuhiro Morisaki Risa Sawada Dr. Masayuki Gon Prof. Yoshiki Chujo 《化学:亚洲杂志》2016,11(18):2524-2527
New types of planar chiral (Rp)‐ and (Sp)‐4,7,12,15‐tetrasubstituted [2.2]paracyclophanes were synthesized from racemic 4,12‐dihydroxy[2.2]paracyclophane as the starting compound. Regioselective dibromination and transformation afforded a series of planar chiral (Rp)‐ and (Sp)‐4,7,12,15‐tetrasubstituted [2.2]paracyclophanes, which can be used as chiral building blocks. In this study, left‐ and right‐handed double helical structures were constructed via chemoselective Sonogashira–Hagihara coupling. The double helical compounds were excellent circularly polarized luminescence (CPL) emitters with large molar extinction coefficients, good photoluminescence quantum efficiencies, and large CPL dissymmetry factors. 相似文献