水峰调制下的3,4-Seco-olean-11,13-dien-4,15α,22β,24-tetraol-3-oic Acid的NMR结构解析

对海南半红树植物黄槿(Hibiscus tiliaceus)内生菌中提取的一个新化合物进行核磁共振结构解析的研究. 在核磁共振测试时发现水峰信号与部分样品信号发生了重叠, 直接影响了该化合物谱图数据的分析. 本工作通过实验确证了在氘代二甲亚砜(DMSO-d₆)溶剂中水峰化学位移与含水量之间的变化规律. 依据该规律, 利用定量加入纯水的方法对实际样品中的水峰信号进行了调制, 解决了水峰信号与样品信号的重叠问题, 得到了较理想的¹H NMR, ¹³C NMR一维谱和COSY, HMQC, HMBC等二维谱. 利用核磁共振提供的信息完成了对新化合物结构的解析, 确定该化合物为齐墩果烷三萜类化合物3,4-seco-olean-11,13-dien-4,15α,22β,24-tetraol-3-oic acid.     

新药盐酸美利曲辛的有机波谱分析

采用核磁共振波谱(NMR)、电喷雾质谱(ESI MS)、紫外(UV)、红外(IR)吸收光谱等技术确证新药盐酸美利曲辛的分子结构;应用NOE谱技术确定盐酸美利曲辛分子中芳香氢的各自化学位移信号;解释该结构在NMR、ESI MS、UV、IR等谱图中的特征吸收峰、共振峰及特征离子的一一对应归属.     

以去氢弯孢霉素NMR结构解析讲授本科生波谱分析课程

以去氢弯孢霉素核磁共振波谱(NMR)解析为例,讲授本科化学和药学相关专业波谱分析课程NMR解析。去氢弯孢霉素结构包含苯环、双键、酚羟基、羰基和酯基等常见基团,NMR信号几乎无重叠、辨识度高,非常适合作为核磁共振波谱结构解析中化学位移、耦合常数和二维核磁共振波谱的授课内容。     

一种面向多组分定量的通用谱图解析方法

在一个多组分系统中各组分的定量分析是非常重要的。现代光谱如拉曼光谱(RS)、傅里叶变换红外(FT-IR)光谱、紫外-可见(UV-Vis)光谱、核磁共振(NMR)、质谱(MS)等,可通过获取丰富峰信号的谱图对样品进行各角度的详尽描述。然而,由于谱图的复杂性及其解析工作的繁重,使得仅通过样品谱图来同时量化混合物中的每个组分成为很具挑战性的工作。在这项研究中,我们首次介绍了一个名为定量主成分分析(q PCA)的可靠策略,快速计算混合物中每个成分的比例,而不需要任何手动解谱。通过使用纯组分的谱图作为参考,多组分系统的谱图可以通过PCA自动分辨并解析,然后就可以使用我们的计算方法来计算每个组分的比例。计算机建模实验和RS、FT-IR、UV-Vis、NMR、MS实验都证明了这一策略胜任多组分系统的快速定量工作。     

核磁共振电信号内标法在人体尿液定量分析中的应用

研究了Varian谱仪核磁共振电信号内标法在人体尿液代谢物浓度测定上的应用,通过实验证明了该方法进行定量分析的可靠性.NMR电信号内标法原理上是通过Varian谱仪去耦通道在常规一维谱图上产生一个参考信号,并利用谱仪软件程序来调整该信号在频谱上的强度、频率、衰减速率等参数.避免了代谢组学中NMR定量实验需要添加已知浓度物质(例如TSP)作为内标而引起的内标物与样品相互作用、谱峰重叠、内标物不溶及弛豫时间太长等问题.研究结果表明,Varian谱仪去耦通道产生的电信号稳定可靠(标准偏差0.36%),能够用于定量分析;当样品浓度大于20 mmol/L或小于2 mmol/L时,该方法测定的相对误差分别为1%和5%.通过配制低浓度的尿液模型样品,验证了电信号内标法测量人体尿液代谢物的浓度的可行性,最后使用该方法测量真实的人体尿液中常见代谢物的浓度,测定结果与医院常用生化分析仪器的测定结果相符.     

酞侧基聚芳醚酮的核磁共振研究(Ⅰ)──链结构及NMR谱的归属

用1D NMR方法研究酞侧基聚芳醚酮(PEK-C)链结构,用二维同核化学位移相关与二维异核化学位移相关实验方法对1D NMR谱峰进行归属,探讨了二维异核远程相关实验在缩聚高分子研究中的应用,为PEK-C修饰机理以及共混相容机理的研究提供重要信息。溶液NMR谱图数据表明,PEK-C具有较规整的链结构。     

聚甲基丙烯酸正丁酯的核磁共振异核相关二维谱

<正> 核磁共振二维谱是研究高聚物分子结构的有力工具.有时一张谱图,就能得到高聚物序列结构或共聚物构型的直接证据.对高聚物结构分析有重要意义.自1983年Brown首次报道聚氯乙烯的二维J谱以来.美国Macromolecules等杂志竟相报道各种聚合物的二维谱图.目前已经报道过的聚合物核磁共振二维谱有二维J谱、~(19)F-~1H异核相关谱、~(13)C-~1H异核相关谱、~1H COSY谱、~(19)F COSY谱、NOESY     

可充电池的磁共振研究

快速增长的对安全能源的需求,促使科研工作者不断探索高能量密度的可充锂离子电池(LIBs)。发展原位表征技术能更好地研究电池工作中的锂离子镶嵌机制和电池失效因素。固体核磁共振(NMR)能有效的测试短程化学环境:通过对~1H、~(6,7)Li、~(11)B、~(13)C、~(17)O、~(19)F、~(23)Na和~(31)P等同位素来探测电池材料的微观结构。除了魔角旋转(MAS)高分辨NMR谱图研究电池材料的精细结构之外,核磁共振还能无损地捕获、研究电池材料在充放电循环中的演化。因此,原位核磁共振NMR及成像(MRI)可拓展到电池充放电循环中的锂离子的动态演化以及锂离子浓度的时空分布信息。互为补充地,电子顺磁共振(EPR)及成像(EPRI)能有效地跟踪和捕获电极过渡金属、阴氧离子(O_2~(n-))的氧化还原过程。这些实时捕获的动态信息能更好地指导电极材料的构效、微观设计和电池组装的改进,最终获得优异的电化学性能。     

多虑平类化合物的核磁共振图谱特征分析

多虑平类化合物在溶液体系中可能存在着构象交换过程,在其核磁共振图谱中出现的谱线展宽(包峰)或缺失现象增加了化合物结构解析的难度,甚至产生误导。该文以多虑平类化合物11-[(3-二甲基氨基)亚丙基]-6,11-二氢二苯并[b,e]氧杂-2-甲醛为样本,通过改变实验条件证明该化合物在几种溶液体系中均存在着构象交换。实验表明升温可以改善这类化合物的核磁共振测试效果,在80℃下获取的谱图信号清晰完整,信号展宽和缺失现象得到有效抑制。利用升温条件下获取的谱图,顺利实现了对11-[(3-二甲基氨基)亚丙基]-6,11-二氢二苯并[b,e]氧杂-2-甲醛的结构解析。     

基于多重氢键组装的双杯冠合成及对铯离子的络合

合成了一种基于多重氧键组装形成的新型双杯冠化合物,利用核磁共振氢谱(1H NMR)和碳谱(13C NMR)以及高分辨质谱(ESI-HRMS)对组装前体分子结构进行了表征.通过一维和二维核磁共振氢谱(2D NOESY)研究了该双杯冠的的自组装结构,并采用核磁共振和紫外-可见光谱的方法测定了其对铯离子的络合.实验表明,通过氢键组装形成的双杯冠化合物,由于阻止了单杯冠分子内组装而限制了冠醚环构象改变,其萃取率由单杯冠的82％提高到96％.     

Fast multidimensional localized parallel NMR spectroscopy for the analysis of samples

A parallel localized spectroscopy (PALSY) method is presented to speed up the acquisition of multidimensional NMR (nD) spectra. The sample is virtually divided into a discrete number of nonoverlapping slices that relax independently during consecutive scans of the experiment, affording a substantial reduction in the interscan relaxation delay and the total experiment time. PALSY was tested for the acquisition of three experiments 2D COSY, 2D DQF‐COSY and 2D TQF‐COSY in parallel, affording a time‐saving factor of 3–4. Some unique advantages are that the achievable resolution in any dimension is not compromised in any way: it uses conventional NMR data processing, it is not prone to generate spectral artifacts, and once calibrated, it can be used routinely with these and other combinations of NMR spectra. Copyright © 2010 John Wiley & Sons, Ltd.     

Covariance nuclear magnetic resonance spectroscopy

Covariance nuclear magnetic resonance (NMR) spectroscopy is introduced, which is a new scheme for establishing nuclear spin correlations from NMR experiments. In this method correlated spin dynamics is directly displayed in terms of a covariance matrix of a series of one-dimensional (1D) spectra. In contrast to two-dimensional (2D) Fourier transform NMR, in a covariance spectrum the spectral resolution along the indirect dimension is determined by the favorable spectral resolution obtainable along the detection dimension, thereby reducing the time-consuming sampling requirement along the indirect dimension. The covariance method neither involves a second Fourier transformation nor does it require separate phase correction or apodization along the indirect dimension. The new scheme is demonstrated for cross-relaxation (NOESY) and J-coupling based magnetization transfer (TOCSY) experiments.     

Analysis and optimization of saturation transfer difference NMR experiments designed to map early self-association events in amyloidogenic peptides

Saturation transfer difference (STD) methods recently have been proposed to be a promising tool for self-recognition mapping at residue and atomic resolution in amyloidogenic peptides. Despite the significant potential of the STD approach for systems undergoing oligomer/monomer (O/M) equilibria, a systematic analysis of the possible artifacts arising in this novel application of STD experiments is still lacking. Here, we have analyzed the STD method as applied to O/M peptides, and we have identified three major sources of possible biases: offset effects, intramonomer cross-relaxation, and partial spin-diffusion within the oligomers. For the purpose of quantitatively assessing these artifacts, we employed a comparative approach that relies on 1-D and 2-D STD data acquired at different saturation frequencies on samples with different peptide concentrations and filtration states. This artifact evaluation protocol was applied to the Abeta(12-28) model system, and all three types of artifacts appear to affect the measured STD spectra. In addition, we propose a method to minimize the biases introduced by these artifacts in the Halpha STD distributions used to obtain peptide self-recognition maps at residue resolution. This method relies on the averaging of STD data sets acquired at different saturation frequencies and provides results comparable to those independently obtained through other NMR pulse sequences that probe oligomerization, such as nonselective off-resonance relaxation experiments. The artifact evaluation protocol and the multiple frequencies averaging strategy proposed here are of general utility for the growing family of amyloidogenic peptides, as they provide a reliable analysis of STD spectra in terms of polypeptide self-recognition epitopes.     

Principles and features of single-scan two-dimensional NMR spectroscopy

Two-dimensional nuclear magnetic resonance (2D NMR) provides one of the foremost contemporary tools available for the elucidation of molecular structure, function, and dynamics. Execution of a 2D NMR experiment generally involves scanning a series of time-domain signals S(t(2)), as a function of a t(1) time variable which undergoes parametric incrementation throughout independent experiments. Very recently, we proposed and demonstrated a general approach whereby this serial mode of data acquisition is parallelized, enabling the acquisition of complete bidimensional NMR data sets via the recording of a single transient. The present paper discusses in more detail various conceptual and experimental aspects of this novel 2D NMR methodology. The basic principles of the approach are reviewed, various homo- and heteronuclear NMR applications are illustrated, and the main features and artifacts affecting the method are derived. Extensions to higher-dimensional experiments are also briefly noted.     

Communication: Phase incremented echo train acquisition in NMR spectroscopy

We present an improved and general approach for implementing echo train acquisition (ETA) in magnetic resonance spectroscopy, particularly where the conventional approach of Carr-Purcell-Meiboom-Gill (CPMG) acquisition would produce numerous artifacts. Generally, adding ETA to any N-dimensional experiment creates an N + 1 dimensional experiment, with an additional dimension associated with the echo count, n, or an evolution time that is an integer multiple of the spacing between echo maxima. Here we present a modified approach, called phase incremented echo train acquisition (PIETA), where the phase of the mixing pulse and every other refocusing pulse, φ(P), is incremented as a single variable, creating an additional phase dimension in what becomes an N + 2 dimensional experiment. A Fourier transform with respect to the PIETA phase, φ(P), converts the φ(P) dimension into a Δp dimension where desired signals can be easily separated from undesired coherence transfer pathway signals, thereby avoiding cumbersome or intractable phase cycling schemes where the receiver phase must follow a master equation. This simple modification eliminates numerous artifacts present in NMR experiments employing CPMG acquisition and allows "single-scan" measurements of transverse relaxation and J-couplings. Additionally, unlike CPMG, we show how PIETA can be appended to experiments with phase modulated signals after the mixing pulse.     

SAN plot: A graphical representation of the signal,noise, and artifacts content of spectra

The signal-to-noise ratio is an important property of NMR spectra. It allows to compare the sensitivity of experiments, the performance of hardware, etc. Its measurement is usually done in a rudimentary manner involving manual operation of selecting separately a region of the spectrum with signal and noise, respectively, applying some operation and returning the signal-to-noise ratio. We introduce here a simple method based on the analysis of the distribution of point intensities in one- and two-dimensional spectra. The signal/artifact/noise plots, (SAN plots) allows one to present in a graphical manner qualitative and quantitative information about spectra. It will be shown that besides measuring signal and noise levels, SAN plots are also quite useful to visualize and compare artifacts within a series of spectra. Some basic properties of the SAN plots are illustrated with simple application.     

Modern spectrum analysis in multidimensional NMR spectroscopy: comparison of linear-prediction extrapolation and maximum-entropy reconstruction

NMR spectroscopy is an inherently insensitive technique, and many challenging applications such as biomolecular studies operate at the very limits of sensitivity and resolution. Advances in superconducting magnet, cryogenic probe, and pulse sequence technologies have resulted in dramatic improvements in both sensitivity and resolution in the past decade. Conversely, the signal-processing method used most widely in NMR spectroscopy, extrapolation of the time domain signal by linear prediction (LP) followed by discrete Fourier transformation (DFT), was developed in the early 1980s and has not been subjected to detailed scrutiny for its impact on sensitivity and resolution. Here we report the first systematic investigation of the accuracy and precision of spectra obtained by LP extrapolation followed by DFT. We compare the results to spectra obtained by maximum-entropy (MaxEnt) reconstruction, which was developed contemporaneously to LP extrapolation but is not widely employed in NMR spectroscopy. Although it reduces truncation artifacts and increases the amplitudes of strong peaks, we find that LP extrapolation generates false-positive peaks and introduces frequency errors. These defects of LP extrapolation become less pronounced for longer data records and higher signal-to-noise ratio. MaxEnt generally yields more detectable peaks for a given number of data samples, more accurate peak frequencies, and fewer false-positive peaks than LP extrapolation. MaxEnt also permits the use of nonlinear sampling, which can give dramatic improvements in resolution. These results show that the use of MaxEnt together with nonlinear sampling, rather than LP extrapolation, could reduce the amount of instrument time required for adequate sensitivity and resolution by a factor of 2 or more.     

Combined Wavelet Transform with Curve‐fitting for Objective Optimization of the Parameters in Fourier Self‐deconvolution

Fourier self‐deconvolution was the most effective technique in resolving overlapping bands, in which deconvolution function results in deconvolution and apodization smoothes the magnified noise. Yet, the choice of the original half‐width of each component and breaking point for truncation is often very subjective. In this paper, the method of combined wavelet transform with curve fitting was described with the advantages of an enhancement of signal to noise ratio as well as the improved fitting condition, and was applied to objective optimization of the original half‐widths of components in unresolved bands for Fourier self‐deconvolution. Again, a noise was separated from a noisy signal by wavelet transform, therefore, the breaking point of apodization function can be determined directly in frequency domain. Accordingly, some artifacts in Fourier self‐deconvolution were minimized significantly.     

Solid-state NMR covariance of homonuclear correlation spectra

Direct covariance NMR spectroscopy, which does not involve a Fourier transformation along the indirect dimension, is demonstrated to obtain homonuclear correlation two-dimensional (2D) spectra in the solid state. In contrast to the usual 2D Fourier transform (2D-FT) NMR, in a 2D covariance (2D-Cov) spectrum the spectral resolution in the indirect dimension is determined by the resolution along the detection dimension, thereby largely reducing the time-consuming indirect sampling requirement. The covariance method does not need any separate phase correction or apodization along the indirect dimension because it uses those applied in the detection dimension. We compare in detail the specifications obtained with 2D-FT and 2D-Cov, for narrow and broad resonances. The efficiency of the covariance data treatment is demonstrated in organic and inorganic samples that are both well crystallized and amorphous, for spin -1/2 nuclei with 13C, 29Si, and 31P through-space or through-bond homonuclear 2D correlation spectra. In all cases, the experimental time has been reduced by at least a factor of 10, without any loss of resolution and signal to noise ratio, with respect to what is necessary with the 2D-FT NMR. According to this method, we have been able to study the silicate network of glasses by 2D NMR within reasonable experimental time despite the very long relaxation time of the 29Si nucleus. The main limitation of the 2D-Cov data treatment is related to the introduction of autocorrelated peaks onto the diagonal, which does not represent any actual connectivity.     

Theory of covariance nuclear magnetic resonance spectroscopy

Covariance nuclear magnetic resonance (NMR) spectroscopy provides an effective way for establishing nuclear spin connectivities in molecular systems. The method, which identifies correlated spin dynamics in terms of covariances between 1D spectra, benefits from a high spectral resolution along the indirect dimension without requiring apodization and Fourier transformation along this dimension. The theoretical treatment of covariance NMR spectroscopy is given for NOESY and TOCSY experiments. It is shown that for a large class of 2D NMR experiments the covariance spectrum and the 2D Fourier transform spectrum can be related to each other by means of Parseval's theorem. A general procedure is presented for the construction of a symmetric spectrum with improved resolution along the indirect frequency domain as compared to the 2D FT spectrum.