胸腺五肽的NMR研究

应用改进的DPFGSE 1D-TOCSY 和1D-NOESY 核磁共振方法测定胸腺五肽的氨基酸残基,从重叠的¹H谱中分离出各自旋系统内氢的亚谱信号;继而由DPFGSE 1D-NOE 技术测定肽链氨基酸残基的连接顺序. 结合二维相关谱对胸腺五肽的碳、氢信号做了全归属. 并进行了计算机分子模拟,结果与NOESY 实验相符.     

1,2-取代乙烯衍生物结构的核磁共振研究

该文对1,2-取代乙烯衍生物的化学结构的NMR测定方法进行了研究. 结果表明,多频率位移激发双梯度自旋回波1D NOE新方法用于阐明这类化合物的化学结构具有独到之处. 强偶合自旋体系信号的选择性粒子数转移 (SPT)影响可得到有效抑制,NOE信号为吸收型,微小(约0.8%)的NOE信号也可明确测定,重叠复杂的谱峰可分离和辨认,测定顺反异构体不需要标准样品对照,结果准确、可靠. 该文以2-甲氧基-4-(2-苯基-2-环己基氨基甲酰基-乙烯基)-乙酸苯酯为例,阐明1D NOE方法在1,2-取代乙烯衍生物的化学结构和立体化学研究中的应用.     

在CP MAS NMR中测量质子自旋扩散速率的方法

自旋扩散在固体核磁共振的许多现象中都起着非常重要的作用。现有几种理论方案以估算扩散系数。然而在实践中这种估算既不实际也不可靠。本文提出了确定自旋扩散速率的新方案,它利用的是CP MAS NMR中的稀核退极化规律。带质子的稀核磁化矢量在退极化中表现出两个阶段,慢衰减的第二阶段是单一指数过程,它提供了自旋扩散速率的直接度量。自旋扩散实质上是极化转移的一种宏观表现形式,这种转移通过一系列成对自旋的flip-flop进行,可以用一维随机走步模型描述。从退磁过程半对数曲线的斜率可以求得平均flip-flop时间。自旋扩散系数可以由此估算。在一些典型的刚性有机固体和结晶高分子聚合物中,求得平均flip-flop的时间是700微秒左右。它比偶极相关时间大一个数量级。这意味着,自旋扩散时间常数与自旋—自旋弛豫时间常数是很不相同的,虽然这两个相应过程虽密切相关的。由质子线宽估计自旋扩散系数是不可靠的。     

无限深阱势的非线性谱生成代数与新型相干态

利用对称一维无限深阱势的哈密顿算符和自然算符构造出该势场的非线性谱生成代数,并在此基础上得到了一种新的非线性相干态.该相干态具有时间稳定性,既可以看成本征值为算符函数的降算符本征态,也可以看成广义极小测不准状态的转动态.     

HMQC-TOCSY技术在植物环肽和配糖体中的应用

核磁共振HMQC-TOCSY二维技术可在氢谱方向和碳谱方向分别得到独立的自旋系统内氢核和碳核的全相关信息.该技术对于分子内具有多个自旋系统的植物环肽和配糖体的结构解析尤为适用.本文以环肽annosquamosin A和三萜皂甙prostratoside A为例说明该技术在这两类化合物中的应用.     

THE APPLICATION OF HMQC-TOCSY TO THE PLANT GLYCOSIDES AND PLANT CYCLOPEPTIDES

核磁共振HMQC-TOCSY二维技术可在氢谱方向和碳谱方向分别得到独立的自旋系统内氢核和碳核的全相关信息.该技术对于分子内具有多个自旋系统的植物环肽和配糖体的结构解析尤为适用.本文以环肽annosquamosin A和三萜皂甙prostratoside A为例说明该技术在这两类化合物中的应用.     

基于金刚石氮-空位色心的精密磁测量

磁是一种重要的物理现象,对其进行精密测量推动了许多科技领域的发展.各类测磁技术,包括霍尔传感器、超导量子干涉仪、自旋磁共振等,都致力于提升空间分辨率和灵敏度.近年来,金刚石中的氮-空位色心广受关注.这一固态单自旋体系具有许多优点,例如易于初始化和读出、可操控、具有较长相干时间等,这使得它不仅在量子信息、量子计算等领域崭露头角,而且在量子精密测量上显现出巨大的应用前景.基于氮-空位色心,利用动力学解耦、关联谱等技术,已实现若干高灵敏度、高分辨率的微观磁共振实验,其中包括纳米尺度乃至单分子、单自旋的核磁共振和电子顺磁共振.氮-空位色心也可以用于微波和射频信号的精密测量.本文对围绕上述主题开展的一系列研究工作进行综述.     

阻挫对准一维非对称子格反铁磁链自旋波激发的影响

子格对称性破缺使得s=1/2准一维海森伯自旋链具有三支自旋波激发谱(其中一支属于声学模，两支属于光学模). 计算表明：阻挫导致两支光学模能隙简并解除；阻挫引起声学模自旋波激发谱软化，但并不导致光学模激发谱软化；阻挫导致两支光学模激发谱中的一支明显下移，这意味着阻挫使光学模激发变得重要且容易实现；阻挫引起的自旋偏离对于属于不同子格的自旋是不同的；阻挫对于系统基态磁性长程序的削弱随着阻挫增强变得越来越明显. 通过与严格对角化方法和DMRG方法的数值结果比较，还分析了自旋波近似的合理性和不足之处. 关键词： 准一维反铁磁自旋系统 自旋波激发 光学模 能隙简并     

旋转坐标系同核NOE差谱

提出一种测定旋转坐标系NOE差谱的NMR技术.与通常的NOE技术相比,其特点是:应用范围较广,可节省测定时间,NOE信号为纯吸收型,可测定NOE的大小,并且可得到某些谱峰高度重叠,采用通常技术难于测定的有机化合物的NOE谱.     

固体中13C CP/MAS谱编辑一些改进

本文将基本的谱编辑脉冲序列与消旋转边带的TOSS脉冲序列联用,可以实现强磁场下¹³C CP/MAS谱编辑.通常,固体中非质子化碳与甲基碳的自旋晶格弛豫时间差别很大,此差别可作为谱编辑过程中区分它们的一条附加判据.对具有复杂分子结构的体系,此判据的作用尤其重要.文中的实例将表明:一个完整的¹³C CP/MAS谱编辑一般可通过SCPTOSS谱(短接触时间交叉极化谱);SCPPITOSS (短接触时间交叉极化极化反转)谱,LCPDTOSS (长接触时间交叉极化及去极化)谱及部分弛豫的LCPDTOSS谱适当组合而得到.     

小波包熵的复杂体系近红外光谱信息提取

有用信息提取是复杂体系近红外检测的重点和难点之一。由于复杂体系光谱中存在各种噪声、基线漂移、谱带重叠及复杂背景的干扰,常规方法不能准确地从光谱中获得有用信息。为此,将小波包变换(DWPT)和信息熵理论相结合--小波包熵(EWPIE)提取复杂体系光谱中的有用信息。思路是采用小波包变换对光谱信号进行多频带分解,根据有用信号与噪声的频带分布特点,基于信息熵理论滤除干扰的频率分量,采用正交校正法(OSC)剔除与被测组分无关的信息,然后对处理后的频率分量进行重构,从而实现复杂体系有用信息的准确提取。通过对复杂体系光谱数据建立多元校正模型来验证该方法的效果。采用牛奶的近红外光谱数据,以牛奶中脂肪和蛋白质浓度为研究对象,建立了偏最小二乘法(PLS)模型。结果显示,牛奶中脂肪和蛋白质的预测均方根误差(RMSEP)分别为0.132%和0.121%,与单纯的DWPT和OSC相比,EWPIE能够有效地提取有用信息,避免了无用信息的干扰,明显提高了模型的预测精度,对复杂体系的准确检测具有一定的理论意义和实际应用价值。     

二维接力-HOHAHA和NOE差谱法测定甙类化合物的结构

该文提出一种新的二维接力-HOHAHA实验方法.研究结果表明,该方法可用于从高度重迭的谱图中分离出各个糖体的¹H NMR信号,并且与NOE差谱实验相结合可以用于测定甙类化合物中糖体间和糖体与甙元间的连接位置.本方法以¹H NMR为基础,故其灵敏度比以¹³C NMR为基础的甙化位移方法高得多.     

Improvement of spectral editing in solids: A sequence for obtaining (13)CH + (13)CH(2)-only (13)C spectra

An improved spectral editing method for solids is described which allows one to obtain a set of subspectra in roughly two-thirds the amount of time as our original CPPI editing method for the same signal to noise. This improvement is afforded by a new pulse sequence that is used to acquire a (13)CH + (13)CH(2) spectrum which has very little (13)CH(3) or nonprotonated carbon contamination. By using this new sequence the (13)CH-only subspectrum is obtained much more efficiently. Criteria for optimizing the signal to noise in the edited subspectra are discussed. Copyright 2000 Academic Press.     

Improvement of Spectral Editing in Solids: A Sequence for Obtaining CH + CH2-Only C Spectra

An improved spectral editing method for solids is described which allows one to obtain a set of subspectra in roughly two-thirds the amount of time as our original CPPI editing method for the same signal to noise. This improvement is afforded by a new pulse sequence that is used to acquire a ¹³CH + ¹³CH₂ spectrum which has very little ¹³CH₃ or nonprotonated carbon contamination. By using this new sequence the ¹³CH-only subspectrum is obtained much more efficiently. Criteria for optimizing the signal to noise in the edited subspectra are discussed.     

More line narrowing in TROSY by decoupling of long-range couplings: shift correlation and 1JNC' coupling constant measurements

Since the introduction of RDCs in high-resolution NMR studies of macromolecules, there is a growing interest in the development of accurate, and sensitive methods for determining coupling constants. Most methods for extracting these couplings are based on the measurement of the splitting between multiplet components in J-coupled spectra. However, these methods are often unreliable since undesired multiple-bond couplings can considerably broaden the multiplet components and consequently make accurate determination of their position difficult. To demonstrate one approach to this problem, G-BIRD((r)) decoupled TROSY sequences are proposed for the measurement of (1)J(NH) and (1)J(NC') coupling constants. Resolved or unresolved splittings due to remote protons are removed by a G-BIRD((r)) module employed during t(1) and as a result, spectra with narrow, well-resolved peaks are obtained from which heteronuclear one-bond couplings can be accurately measured. Moreover, introduction of a spin-state-selective alpha/beta-filter in the TROSY sequence allows the separation of the (1)J(NC') doublet components into two subspectra which contain the same number of peaks as the regular TROSY spectrum. The (1)J(NC') couplings are obtained from the displacement between the corresponding peaks in the subspectra.     

Spectral editing of 13C cp/MAS NMR spectra of complex systems: application to the structural characterisation of cork cell walls

A mathematical method of obtaining 13C CP/MAS subspectra of single components of a complex system is presented and applied to three- and four-component systems. The method is based on previously reported work that exploits different proton relaxation properties for different domains of an heterogeneous system. However, unlike the original method that obtained subspectra through a trial-and-error approach, the method here presented solves the problem mathematically, thus avoiding the time-consuming and non-rigorous trial-and-error step. The method is applied to mixtures of three and four polymers and to a more complex system: cork cell walls. As expected, as the number of components increases, the sharing of relaxation properties between different components is increasingly probable, either due to incidental coincidence of relaxation times or to specific interactions and intimate mixing of compounds. While this hinders the calculation of the subspectra of single chemical components, it may provide useful information about inter-component interactions. This possibility was demonstrated by the application of this method to cork cell walls. Both three-component and four-component approaches showed that three domains exist in cork cell walls: carbohydrate/lignin matrix, mobile suberin close to (probably bonded to) lignin groups (about 42% w/w) and hindered suberin close to (probably bonded to) carbohydrate-OCH2O groups (about 4% w/w).     

异质结构对多通道滤波器禁带的展宽

采用光学传输矩阵法首次研究了掺有缺陷的一维三元异质结构光子晶体的传输特性。研究显示,三元异质结构光子晶体与三元周期结构光子晶体相比光子禁带显著扩大。在异质结构光子晶体中引入缺陷并调整缺陷的数目可以实现多通道滤波现象。本文主要讨论了在该结构产生一、二、三通道滤波现象。     

Quantitative analysis of sugar composition in honey using 532‐nm excitation Raman and Raman optical activity spectra

Raman spectroscopy based on the 1064‐nm laser excitation was suggested as a handy non‐invasive technique allowing to quickly determine sugar content in honey and similar food products. In the present study, the green 532‐nm laser radiation is explored instead as it provides higher‐quality spectra in a shorter time. The sample fluorescence was quenched by purification with activated carbon. For control mixture decomposition of Raman spectra to standard subspectra led to a typical error of the sugar content of 3%. Raman optical activity (ROA) spectra that could be measured at the shorter excitation wavelength as well provided a lower accuracy (~8%) than the Raman spectra because of instrumental sensitivity and noise limitations. The results show that Raman spectroscopy provides elegant and reliable means for fast analyses of sugar‐based food products. Copyright © 2016 John Wiley & Sons, Ltd.     

Non-equilibrum population of the Fe3+ electronic states after the electron capture in57Co: LiTaO3

Mössbauer emission spectra of⁵⁷Co: LiTaO₃ show as a consequence of the nuclear decay anomalous emission line intensities in the subspectra of Fe²⁺ and Fe³⁺. Magnetic field and angle dependence of Fe³⁺ intensities can be explained by taking into account polarization-and crystal-field effects in the excited states. The experimental results for LiTaO₃ are in good agreement with theory and previous measurements on LiNbO₃.     

Mössbauer studies of hemoglobin in high altitude polycythemia

The Mössbauer spectra have been measured in erythrocytes from normal adults and the patients with high altitude polycythemia (HAPC). The results indicated that two subspectra “a” and “b”, corresponding to oxy- and deoxyhemoglobin respectively, were present in all blood samples, and a third subspectrum “c” was found to exist in almost all samples from the patients. The parameters of the third subspectra “cl” in most samples from the patients were similar to those of carbon monoxyhemoglobin. The components were considered to be the denatured hemoglobin in RBCs (red blood cells). Together with clinical analysis, a possible mechanism of HAPC has been discussed.