卡泊三醇的核磁共振谱解析

利用核磁共振氢谱（¹H NMR）、碳谱（¹³C NMR）、同核位移相关谱（¹H-¹H COSY）、异核单量子相干谱（HSQC）和异核多键相关谱（HMBC）等多种核磁研究方法对抗银屑病药物卡泊三醇的¹H、¹³C信号进行完全归属.     

棉子糖乙酰化物的2D—NMR研究

应用氢-氢和碳-氢相关谱(~1H-~1H COSY and~(13)C-~1H COSY),同核和异核J-分解谱(JRES and HETJRES),异核中继相干传递二维谱(RELAY)和异核远程化学位移相关谱(COLOC)研究了棉子糖乙酰化物的化学结构,并对COLOC及RELAY实验的参数取值进行了讨论。结果表明,二维核磁共振技术特别是COLOC对于确定配糖体糖基的连接顺序和连接位置是十分有效的方法。     

硒钨簇合物中有机取代基的1H、13C NMR归属

用二维异核多量子化学位移相关谱¹H-¹³C HMQC,HMBC和二维同核NOESY谱研究了两个新合成的双钨核有机硒化合物的结构,归属了该化合物的¹H,¹³C NMR谱线.     

西洋参皂甙的核磁共振波谱研究Ⅰ.西洋参叶中Ocotillol型皂甙的结构分析

本文用常规一维¹H、¹³C核磁共振波谱和远程异核化学位移相关谱。异核化学位移相关谱和同核化学位移相关谱技术研究了西洋参叶中首次分离出的一种Ocotillol型皂甙,确认了化学结构,并对其¹³C、¹H NMR谱线进行了归属。     

1,2-二氢-4-(4-羟基苯基)(2H)二氮杂萘-1-酮的NMR研究

应用多种二维核磁共振谱,即：2D同核化学位移全相关谱(TOCSY),2D NOESY谱,2D 异核多量子相关谱(HMQC)和2D异核¹³C-¹H多键 相关谱(HMBC),对化合物1,2-二氢-4-(4-羟基苯基)(2H)二氮杂萘-1-酮的¹H和¹³C NMR 谱线进行了完整归属,从而系统地分析和讨论了该化合物的结构特征.     

1,2-二氢-4-苯基(2H)二氮杂萘酮的NMR谱研究

报道了1,2-二氢-2-(4-氨基苯基)-4-[4-(4-氨基苯氧基)苯基](2H)二氮杂萘-1-酮的合成,并用2D同核化学位移相关谱(¹H,¹H-COSY),2DROESY谱,2D异核¹³C-¹H相关谱和2D异核¹³C-¹H多键相关谱(HMBC)对该化合物的¹H和¹³C NMR谱进行了完整归属,证明了此化合物是含二氮杂萘酮结构,而不是二氮杂萘醚结构.     

拉呋替丁的波谱学数据和结构确证

对拉呋替丁的氢谱（¹H NMR）、碳谱（¹³C NMR,DEPT）、异核多键相关谱（HMBC）予以解析并进行了报道,对其所有的¹H NMR和¹³C NMR谱信号进行了归属;讨论了红外特征吸收,热差和热重分析;质谱的裂解途径和离子特征也与拉呋替丁的分子结构相符.      

Nb-甲基四氢海曼和合成中间体的1H NMR及立体化学

本文提供了N_b-甲基四氢海曼和合成中间体,共十个化合物的¹H NMR谱。各谱线的归属依据它们的2D NMR的同核二维相关谱,COSY指定。根据NOE效应,指定了化合物的构型。借助分子模型,讨论了可能的构象。     

苄醚树枝体与丙烯酸杂化嵌段共聚物的NMR表征

在ARX-500型谱仪上记录了新合成苄醚树枝体与丙烯酸杂化嵌段共聚物的一维¹H谱、一维¹³C谱和二维异核多量子化学位移相关谱(HMQC).根据NMR谱模拟和NMR实验,得到了该共聚物¹H和¹³C的全归属。     

最高量子相关谱技术在同核偶合常数测定中的应用(英文)

偶合常数是一个重要的NMR参数,其数值与分子中化学键的二面角有关,可以为分子结构研究提供很重要的信息.多维NMR谱由于具有较大的化学位移分辨率,因此常常被用来测定同核或异核自旋-自旋偶合常数.本文介绍了利用最高量子相关技术(MAXY)测定同核偶合常数的方法.MAXY是最近发展的一种多维NMR谱编辑技术,可以使不同官能团(CH,CH₂,CH₃)的相关峰分布于不同的图谱区域,因此比常规的二维谱具有更高的化学位移分辨率.而且被分离开来的NMR相关峰呈吸收性线型,能清楚地展示各自的偶合分裂特征,可以直接用于测定偶合常数.     

一种抗生育有效成份-芫花酯丁的1H NMR结构鉴定

本文报道了用¹H NMR法测定瑞香科植物芜花的花蕾中提取的一种抗生育有效成份-芜花酯丁的结构。以同核相关谱及自旋去偶实验确定部分谱峰的归属,结果表明其结构为I。     

全相关(TOCSY)序列在多肽分析中的应用

TOCSY可提供自旋网络中全部质子的接力信息,是RELAY的新发展,它特别适用于具有若干独立自旋系统的大分子.本文在同核和异核相关实验中均用MLEV-17序列进行全面相关,并对两种多肽进行了分析.     

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.     

五氧硼酸钾结构的1H NMR研究

给出相对于外磁场不同取向的五氧硼酸钾(KB₅)单晶的¹H NMR室温谱.发现当外磁场在晶体的bc平面里,¹H NMR谱最多有6个峰.而在ah或ac平面里,最多仅有5个峰.用计算机拟合NMR谱表明:在五氧硼酸钾中,氢原子是以羟基和水分子集团的形式存在.在羟基集团中,O-H的距离为0.1005±0.001nm和0.1054±0.001nm;而在水分子中,O-H的距离为0.0983±0.001nm和0.0968±0.001nm,并且H-O-H夹角为108°±1°.这些显示本文的数据与中子衍射结果相近,而X射线衍射所得到的质子位置的数据则与我们的结果相距甚远.     

Phase Sensitive Detection of 2D Homonuclear Correlation Spectra in MAS NMR

A pulse scheme for phase sensitive detection of two-dimensional (2D) homonuclear correlation magic angle spinning (MAS) NMR spectra is proposed. This scheme combines the time proportional phase increment phase cycling scheme and the time reversal 2D MAS experiment. This approach enables the direct detection of purely absorptive 2D MAS spectra, containing cross peaks that connect only diagonal peaks of dipolar correlated spins.     

苯并二氢呋喃类木脂素NMR谱的研究

用２Ｄ ＮＭＲ技术研究了从水飞蓟素中分离的一个苯并二氢呋喃类木脂素的结构，证实该类化合物的取代基位置可用ＣＯＬＯＣ谱确定。同时研究了该类化合物以ＤＭＳＯ－ｄ６为溶剂的ＰＭＲ谱的特征，另外对Ｂａｌａｎｏｐｈｏｎｉｎ的ＰＭＲ谱进行了详细归属。     

High-resolution four-dimensional carbon-correlated 1H-1H ROESY experiments employing isotags and the filter diagonalization method for effective assignment of glycosidic linkages in oligosaccharides

Four-dimensional nuclear magnetic resonance spectroscopy of oligosaccharides that correlates 1H-1H ROESY cross peaks to two additional 13C frequency dimensions is reported. The 13C frequencies were introduced by derivatization of all free hydroxyl groups with doubly 13C-labeled acetyl isotags. Pulse sequences were optimized for processing with the filter diagonalization method. The extensive overlap typically observed in 2D ROESY 1H-1H planes was alleviated by resolution of ROESY cross peaks in the two added dimensions associated with the carbon frequencies of the isotags. This enabled the interresidue 1H-1H ROESY cross peaks to be unambiguously assigned hence spatially proximate sugar spin systems across glycosidic bonds could be effectively ascertained. An experiment that selectively amplifies interresidue ROESY 1H-1H cross peaks is also reported. It moves the magnetization of an intraresidue proton normally correlated to a sugar H-1 signal orthogonally along the z axis prior to a Tr-ROESY mixing sequence. This virtually eliminates the incoherent intraresidue ROESY transfer, suppresses coherent TOCSY transfer, and markedly enhances the intensity of interresidue ROESY cross peaks.     

Improvements for MeasuringH–H Coupling Constants in DNA via New Stripe-COSY and Superstripe-COSY Pulse Sequences Combined with a Novel Strategy of Selective Deuteration

Three bond proton-proton vicinal coupling constants are of potential value for analyzing sugar conformations in DNA. However, self-cancellation in antiphase cross peaks and modulation of peak splittings by transverse cross relaxation can alter the apparent coupling constants such that they do not accurately reflect the sugar conformations. Transverse cross relaxation is most effective between strongly coupled geminal proton pairs. Here we report the use of stereospecific deuteration at the H2″ position in the A5 and A6 residues in the 12 base pair DNA sequence [d(CGCGAATTCGCG)2] as a means of investigating the effect of transverse cross relaxation on P.E.COSY type cross peaks. Deuteration of the H2″ proton is expected to reduce the transverse cross relaxation rate by the square of ratio of the proton to deuteron gyromagnetic ratios, i.e., by a factor of 42. Additionally, a striking eight- to ninefold increase in the signal intensity was observed for cross peaks involving the remaining H2′ proton resulting from diminished dipolar relaxation. Further improvements in signal-to-noise ratio were realized by collecting P.E.COSY spectra in strips, using an experiment referred to as stripe-COSY, employing selective excitation pulses which reduced the number of requiredt₁increments by a factor of four. A final improvement was achieved by employing selective time-shared homonuclear decoupling during the acquisition period, in an experiment referred to as superstripe-COSY, to collapse splittings due to passive couplings. Collectively, these approaches provide P.E.COSY-type spectra with two to three orders of magnitude increased sensitivity per unit time and that are relatively free from artifacts.     

用2D NMR表征芳香维甲酸乙酯的化学结构

用¹H-¹H COSY,¹³C-¹H COSY,HMBC,NOESY,DEPT以及同核去偶技术,表征了芳香维甲酸乙酯的化学结构,对其¹H NMR,¹³C NMR化学位移进行了指认.     

A comprehensive approach for accurate measurement of proton-proton coupling constants in the sugar ring of DNA

Stereo-selectivedeuteration has been explored as an approach for improving the accuracy of NMR-derived, three-bond vicinal proton-proton coupling constants in the 12-base-pair DNA Dickerson sequence [d(CGCGAATTCGCG)(2)]. The coupling constants are useful for DNA structure determination in restrained molecular dynamics calculations. Specifically, the A5 and A6 residues were prepared with the H2" proton stereo-selectively replaced with a deuteron. Deuteration of the H2" leads to a 42-fold reduction in the transverse cross-relaxation rate of the H2' spin, effectively negating the contribution of transverse cross relaxation to the cross peak frequencies and phases. Calculated linewidth and polarization transfer functions indicated that the reduced dipolar interaction is also expected to result in a significant increase in intensity for all cross peaks involving the H1', H2', or H3' spin. The spectral complexity is also reduced by selective deuteration. Time-shared homonuclear decoupling of passive spins during acquisition was implemented, reducing the spin system, in some cases, to an effectively isolated two-spin system. This enables the use of a 90 degrees mixing pulse instead of the 35 degrees pulse commonly used in standard P.E.COSY experiments, leading to an additional 75% increase in signal intensity. Selective excitation pulses were used to reduce the number of increments required in the indirect dimension by as much as a factor of 4. The cumulative improvement in sensitivity is striking, approaching three orders of magnitude per unit time. Separate experiments, referred to as Stripe-COSY and Superstripe-COSY, were optimized for each coupling constant measured. Finally, J-doubling was used to obtain the most accurate peak separations. This comprehensive approach shows promise as an effective method for extracting highly accurate homonuclear vicinal coupling constants in DNA.