盐酸马尼地平的核磁共振数据解析

盐酸马尼地平是第三代合成降压新药．本文利用一维、二维核磁共振（NMR）技术,包括¹H NMR、¹³C NMR DEPT-135、¹H-¹H NOESY、¹H-¹H COSY、¹H-¹³C HSQC和¹H-¹³C HMBC,对其¹H和¹³C NMR信号进行了全归属,进一步确证了其分子结构．同时,对其¹H NMR和¹³C NMR谱中一些异常信号进行了讨论．     

靶向新药吉非替尼的核磁共振波谱研究

应用1D、2D NMR实验技术（¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹³C HMQC、¹H-¹³C HMBC等）研究了靶向新药吉非替尼的结构,对其1H NMR和¹³C NMR谱峰作了全归属,并讨论了F原子对吉非替尼的¹H、¹³C NMR的影响.     

海博麦布结构确证

本文采用紫外吸收光谱、红外吸收光谱、质谱、核磁共振波谱(包含¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹H NOESY、¹H-¹³C HSQC和¹H-¹³C HMBC)以及单晶衍射等方法对海博麦布进行结构分析,对其所有的¹H NMR和¹³C NMR谱信号进行了归属,还通过差示扫描量热法、热重分析及粉末X-射线衍射分析对海博麦布晶型进行研究．     

基于咔唑-靛红双-硫代碳酰腙衍生物的NMR研究

采用多种核磁共振（NMR）技术（包括¹H NMR、¹³C NMR、¹H-¹H COSY、¹H-¹³C HSQC、¹H-¹³C HMBC），对基于咔唑-靛红双-硫代碳酰腙新型衍生物2，即1-[（3Z）-2-氧代吲哚-3-亚基]-5-[（9-己基-3-咔唑基）亚基]硫代碳酰腙的¹H和¹³C NMR信号进行了全归属，确定了其结构．     

新型连翘脂素-布洛芬酯合物的波谱学数据解析

以连翘脂素和布洛芬为原料,通过Schotten-Baumann酯化合成了酯合物——连翘脂素-布洛芬酯.对其紫外吸收光谱（UV）、红外吸收光谱（IR）、基质辅助激光解吸/电离飞行时间质谱（MALDI-TOF-MS）、1D和2D核磁共振（NMR）波谱（包括¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹H NOESY、¹H-¹³C HSQC和¹H-¹³C HMBC）进行了解析,对其¹H和¹³C NMR谱峰进行了全归属.     

依卡倍特钠的波谱学数据解析

对胃粘膜保护剂依卡倍特钠的紫外吸收光谱（UV）、红外吸收光谱（IR）、高分辨-质谱（HR-MS）、核磁共振（NMR）波谱（包括¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹³C HSQC和¹H-¹³C HMBC）数据进行了解析,对其所有的¹H和¹³C NMR谱信号进行了归属,通过多种谱学技术确证了依卡倍特钠的结构.     

硼替佐米的波谱学数据解析

对抗肿瘤药硼替佐米的紫外吸收光谱（UV）、红外吸收光谱（IR）、电喷雾离子源-质谱（ESI-MS）、核磁共振（NMR）波谱（包括¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹³C HSQC和¹H-¹³C HMBC）数据进行了解析,对其¹H和¹³C NMR谱峰进行了全归属,通过多种谱学技术确证了硼替佐米的结构.     

卢立康唑的波谱学特征和结构确证

用红外吸收光谱、紫外吸收光谱、核磁共振（NMR）波谱（包含¹H NMR、¹³C NMR、DEPT135、¹H-¹H COSY、¹H-¹³C HMQC和¹H-¹³C HMBC）、质谱、差示扫描量热分析、X-射线粉末衍射和元素分析等方法对卢立康唑进行了结构分析.对卢立康唑所有的¹H和¹³C NMR信号进行了归属,并通过多种谱学技术确证了卢立康唑的结构.     

南蛇藤中倍半萜生物碱的二维NMR研究

用DEPT和二维NMR技术包括:¹H-¹H COSY,¹H-¹³C COSY,NOESY,特别是¹H-¹³C COLOC对两个多酯基取代的倍半萜生物碱的化学及立体结构进行了研究,并对其¹H和¹³C NMR谱峰进行了归属。     

雷酚内酯的波谱学数据与结构确证

对雷酚内酯对照品的紫外吸收光谱（UV）、红外吸收光谱（IR）、质谱（MS）、核磁共振（NMR）谱（包括¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、NOE、¹H-¹³C HSQC和¹H-¹³C HMBC谱图）进行了分析,对其¹H和¹³C NMR谱峰进行了全归属,纠正了文献[5]的归属错误,确证了雷酚内酯对照品的化学结构.     

昆明小鼠常见体液与组织代谢组NMR分析

昆明小鼠是我国特有且广泛使用的模式动物. 利用核磁共振(NMR)技术对昆明小鼠血液、尿液和肝脏等组织中的代谢物进行了较为系统的研究. 通过对昆明小鼠体液和组织中代表性的¹H NMR谱图,并结合COSY(Correlation Spectroscopy),TOCSY(Total Correlation Spectroscopy),J-Res(J-Resolved Spectroscopy),HSQC(Heteronuclear Single Quantum Coherence),HMBC(Heteronuclear Multiple Bond Coherence)等2D NMR谱图进行分析,共解析出82种小分子代谢物,其中尿液中约有46种,血样中约有32种,肝脏提取物中约有43种,肾脏皮质提取物中约有39种,部分代谢物在不同样品均存在. 这为进一步利用昆明小鼠为动物模型的研究提供了基础信息.     

Experimental NMR and MS study of benzoylguanidines. Investigation of E/Z isomerism

Molecules containing the guanidinic nuclei possess several pharmacological applications, and knowing the preferred isomers of a potential drug is important to understand the way it operates pharmacologically. Benzoylguanidines were synthesized in satisfactory to good yields and characterized by NMR, Electrospray Ionization Mass Spectrometry (ESI‐MS) and Fourrier Transform InfraRed Spectroscopy techniques (FTIR). E/Z isomerism of the guanidines was studied and confirmed by NMR analysis in solution (¹H‐¹³C Heteronuclear Single Quantum Coherence (HSQC) and Heteronuclear Multiple‐Bond Correlation (HMBC), ¹H‐¹⁵N HMBC, ¹H‐¹H Correlation Spectroscopy (COSY) and Nuclear Overhauser Effect Spectroscopy (NOESY) experiments) at low temperatures. Compounds with p‐Cl and p‐Br aniline moiety exist mainly as Z isomer with a small proportion of E isomer, whereas compounds with p‐NO2 moiety showed a decrease in proportion of isomer Z. The results are important for the application of these molecules as enzymatic inhibitors. Copyright © 2013 John Wiley & Sons, Ltd.     

葡糖衍生手性N-杂环卡宾前体波谱学数据分析

以溴代正丁烷与1-（2,3,4,6-四-O-乙酰基-β-D-吡喃葡萄糖基）咪唑（化合物1）为原料合成了溴化1-（2,3,4,6-四-O-乙酰基-β-D-吡喃葡萄糖基）-3-正丁基咪唑盐（化合物2）,它是葡萄糖衍生的手性N-杂环卡宾前体.化合物2的结构中存在多个手性碳原子,导致它的核磁共振（NMR）谱较为复杂.在此,用元素分析、红外吸收光谱（IR）以及液相色谱-高分辨质谱（LC-HRMS）对它的组成进行了分析,然后利用1D和2D NMR谱（包括¹H NMR、¹³C NMR、DEPT135、DEPT90、DEPT45、COSY、¹H-¹³C HSQC、¹H-¹³C HMBC）对化合物2的¹H和¹³C NMR信号进行了归属.     

魔角旋转核磁共振波谱学

样品绕与外加恒定磁场方向成魔角β_M=cos^-1(1)/√3的轴向快速旋转(MAS)可以消除固体NMR的多种谱增宽。本文首先介绍了固体中的几种主要的各向异性相互作用,即偶极-偶极,核四极,自旋-自旋或称间接偶极-偶极以及化学位移相互作用。然后用平均哈密顿理论阐述了MAS对这些相互作用的影响。现今的固体高分辨方法有四种,即多脉冲(MP),多量子(MQ),交叉极化和大功率异核去耦合(CP)以及MAS,在这些方法中MAS方法是唯一可以获得各向同性化学位移的。因而要得到类似于液体谱的固体高分辨,MAS往往是最后的手段。以上这些方法的联合运用以及极为广泛的应用研究使得固体高分辨NMR兴旺发达起来了。本文引述了大量原始和最新的文献,力图概述当前该领域中的大部分成就。评论这一领域的理论和实验技术的发展。     

棉酚及其衍生物在溶剂中的氢转移

本文利用~1HNMR法研究棉酚及其胺类衍生物(双苯胺棉酚,双丁基棉酚和双嘧啶棉酚)在不同溶剂(CDCl_3,DMSO-d_6,C_6D_6,CD_3COCD_3,DMF-d_7 等)中和不同的酸碱环境下的氢转移(即结构互交).实验表明,棉酚、双苯胺棉酚、双丁基棉酚和双嘧啶存在着三种不同的异构体.这些异构体在同一溶剂不同环境下可以并存或者相互转变.     

1H and 13C NMR studies of glycine in anisotropic media: double-quantum transitions and the effects of chiral interactions

The (1)H NMR spectrum of glycine in stretched gelatin gel and in cromolyn liquid crystal displays a well-resolved doublet due to (1)H-(1)H dipolar interaction. Multiple spectra were obtained within a wide range of offset frequencies of partially saturating radio-frequency (RF) radiation to generate steady-state irradiation envelopes or z-spectra of glycine. Maximal suppression of the doublet occurred when the irradiation was applied exactly at the centre frequency, between the two glycine peaks. This phenomenon is due to double-quantum transitions and is similar to our previous work on quadrupolar nuclei (2)H (HDO) and (23)Na(+). When the (13)C isotopomer glycine-2-(13)C was used, the same effect was found in twice, split by (1)J(CH)+2D(CH). Additional signals in (1)H and (13)C NMR due to prochiral-chiral interactions were found when glycine-2-(13)C was dissolved in chiral anisotropic gelatin and κ-carrageenan gels. The NMR spectra were successfully simulated assuming a (2)J(HH) coupling constant of -16.5Hz and two distinct dipolar coupling constants for the -(13)CH(2)- group (D(C,HA), and D(C,HB)).     

Observing in-phase single-quantum 15N multiplets for NH2/NH3+ groups with two-dimensional heteronuclear correlation spectroscopy

Two-dimensional (2D) F1-(1)H-coupled HSQC experiments provide 3:1:1:3 and 1:0:1 multiplets for AX(3) and AX(2) spin systems, respectively. These multiplets occur because, in addition to the 2S(y)H(z)(a)-->2S(y)H(z)(a) process, the coherence transfers such as 2S(y)H(z)(a)-->2S(y)H(z)(b) occurring in t(1) period provide detectable magnetization during the t(2) period. Here, we present a 2D F1-(1)H-coupled (1)H-(15)N heteronuclear correlation experiment that provides a 1:3:3:1 quartet for AX(3) spin system and a 1:2:1 triplet for AX(2). The experiment is a derivative of 2D HISQC experiment [J. Iwahara, Y.S. Jung, G.M. Clore, Heteronuclear NMR spectroscopy for lysine NH(3) groups in proteins: unique effect of water exchange on (15)N transverse relaxation. J. Am. Chem. Soc. 129 (2007) 2971-2980] and contains a scheme that kills anti-phase single-quantum terms generated in the t(1) period. The purge scheme is essential to observe in-phase single-quantum multiplets. Applications to the NH(2) and NH(3)(+) groups in proteins are demonstrated.     

A 13C field-cycling NMR relaxometry investigation of proton tunnelling in the hydrogen bond: dynamic isotope effects, the influence of heteronuclear interactions and coupled relaxation

Concerted double proton transfer in the hydrogen bonds of a carboxylic acid dimer has been studied using 13C field-cycling NMR relaxometry. Heteronuclear 13C-1H dipolar interactions dominate the 13C spin-lattice relaxation which is significantly influenced by the polarisation state of the 1H Zeeman reservoir. The methodology of field-cycling experiments for such heteronuclear spin-coupled systems is studied experimentally and theoretically, including an investigation of various saturation-recovery and polarisation-recovery pulse sequence schemes. A theoretical model of the spin-lattice relaxation of this coupled system is presented which is corroborated by experiment. Spectral density components with frequencies omega(C), omega(C) + omega(H), and omega(C) - omega(H) are mapped out experimentally from the magnetic field dependence of the 13C and 1H spin-lattice relaxation and the proton transfer rate at low temperature is determined from their widths. Any dynamic isotope effect on the proton tunnelling in the hydrogen bond arising from 13C enrichment in the skeletal framework of the dimer is found to be smaller than experimental uncertainties (approximately 5%).     

High-resolution heteronuclear correlation spectroscopy based on spatial encoding and coherence transfer in inhomogeneous fields

Two-dimensional (2D) nuclear magnetic resonance (NMR) spectroscopy has been proven to be a powerful technique for chemical, biological, and medical studies. Heteronuclear single quantum correlation (HSQC) and heteronuclear multiple bond correlation (HMBC) are two frequently used 2D NMR methods. In combination with spatially encoded techniques, a heteronuclear 2D NMR spectrum can be acquired in several seconds and may be applied to monitoring chemical reactions. However, it is difficult to obtain high-resolution NMR spectra in inhomogeneous fields. Inspired by the idea of tracing the difference of precession frequencies between two different spins to yield high-resolution spectra, we propose a method with correlation acquisition option and J-resolved-like acquisition option to ultrafast obtain high-resolution HSQC/HMBC spectra and heteronuclear J-resolved-like spectra in inhomogeneous fields.     

Al coordination and water speciation in hydrous aluminosilicate glasses: direct evidence from high-resolution heteronuclear 1H-27Al correlation NMR

In order to shed light on the dissolution mechanisms of water in depolymerized aluminosilicate melts/glasses, a comprehensive one- (1D) and two-dimensional (2D) NMR study has been carried out on hydrous Ca- and Mg-aluminosilicate glasses of a haplobasaltic composition. The applied techniques include 1D 1H MAS NMR and 27Al-->1H cross-polarization (CP) MAS NMR, and 2D 1H NOESY and double-quantum (DQ) MAS NMR, 27Al triple-quantum (3Q) MAS NMR and 27Al-->1H heteronuclear correlation (HETCOR) and 3QMAS/HETCOR NMR. Ab initio calculations were also performed to place additional constraints on the 1H NMR characteristics of AlOH and Si(OH)Al groups. This study has revealed, for the first time, the presence of free OH (i.e. (Ca, Mg)OH), SiOH and AlOH species, in addition to molecular H2O, in hydrous glasses of a depolymerized aluminosilicate composition. The AlOH groups are mostly associated with four-coordinate Al, but some are associated with five- and six-coordinate Al.