2D—NMR对皂皮酸—3—氧—葡萄糖醛酸^13C,^1H的完全指定—介绍HMBC和HOHAHA

HMBC是一种测定远程偶合~1H—~(13)C相关的十分灵敏的方法,特别适用于检测和甲基质子远程偶合(~2J,~3J)的碳.HOHAHA谱显示出多次Relay信息,选择适当参数可通过一次实验得到独立自旋体系中所有质子相关信息.本文用HMBC和HOHAHA实验结合同核(~1H)COSY和导核(~(13)C-~1H)COSY确认了Qwhaic acid—3—O—glucuronic acid分子中所有~(13)C和~1H的归属.     

吡啶酮系偶氮染料腙式—偶氮式互变异构的研究——Ⅰ核磁共振波谱在构型测定中的应用

测定了七个吡啶酮系偶氮染料的~(13)C NMR波谱.借助于选择性非灵敏核极化转移增强法(SELINEPT)完成了谱带归属。从pH值对~(13)C化学位移的影响,~1H NMR谱和紫外-可见吸收光谱,指出这类染料的酸-碱变色现象是由腙式和偶氮式构型互变平衡的移动引起的.介质酸性或碱性的增强分别有利于染料以腙式或偶氮式的构型存在.不同结构的吡啶酮染料,其变色pH值是相当不同的.     

双氢埃托啡的二维核磁共振研究

双氢埃托啡(1)为合成的新型高效镇痛药.其~1H和~(13)C NMR谱较为复杂,本文采用二维~1H—~1H COSY—NO ESY和~(13)C—~1H COSY等技术作了研究,确定了其全部~1H和~(13)C谱峰的归属,推断出C—7的构型,并且发现前人对其类似物的一些谱峰指定有误.本结果有助于此类化合物的结构测定和立体化学的研究.     

SHA+脉冲序列用于g-C_3N_4样品~(15)N-~(15)N相关性的固体核磁共振研究（英文）

利用固体核磁共振实验研究了~(15)N标记的g-C_3N_4样品中的~(15)N-~(15)N空间相关性,在高场和魔角旋转条件下对比两种不同的脉冲序列PDSD和SHA+的实验效果.发现当某个氮上连有质子的时候,脉冲序列SHA+比PDSD可以更好地检测~(15)N原子间的极化转移.该研究可以为材料科学领域,特别是含氮掺杂的碳材料,提供一种有价值的研究方法.     

一对阻转异构体NMR谱的解析

本文报道一个孕甾生物碱—富贵草碱A的阻转异构现象,并报道利用无畸变极化转移增强(DEPT)技术、异核化学位移相关谱(HETCOR)、质子NOE谱(NOESY)这些核磁共振技术,对表富贵草碱A的一对阻转异构体的~(13)C NMR化学位移数据,作了完整指定,表富贵草碱A为一对阻旋异构体的混合物,这是孕甾生物碱中的一个阻旋异构现象。     

在极化转移NMR实验中的质子同核耦合调制效应

本文以INEPT脉冲序列为例,从理论和实验上研究了在极化转移NMR实验中的质子同核耦合调制效应,并对与具有1/2自旋的被观测核之间有不同耦合常数的两组质子同时进行极化转移的情况作了探讨.     

2D—NMR研究5—氟脲嘧啶衍生物的结构

2D—NMR是近十年来出现的新技术,在有机分子结构的研究中起着重要作用.本文是用同核、异核化学位移相关二维谱、异核中继根干传递二维谱和异核远程偶合相关二维谱,对四个新的5—氟脲嘧啶衍生物进行了全面的研究,确定了它们的结构及~1H、~(13)C谱线归属.     

关附庚素的选择性远程DEPT、一维COSY和一维接力COSY谱的研究

由于谱峰拥挤和重迭、关附庚素的一部分~1H和~(13)C谱峰用一般核磁共振方法难于确定归属。本工作采用选择性远程DEPT、一维COSY和-维接力COSY等新技术作了研究,其~1H和~(13)C谱峰归属全部得到确定。结果有助于此类化合物的化学结构测定。     

由槐米中提取槲皮素的光谱学表征

从槐树(Sophara Japonica L.)的花蕾(槐米)中提取芦丁,再在酸性条件下由芦丁直接水解得到槲皮素,采用UV,IR,ESI-MSn[质谱(电喷雾电离源)],1H,13C,DEPT(无畸变极化转移增益法)和1H-1HCOSY(氢-氢化学位移相关谱),HSQC(异核单量子相关谱),HMBC(异核多键相关谱)二维核磁技术对槲皮素进行了结构鉴定.     

烷基苯基五元杂环基锡化合物的^13C—NMR研究

本文测定了18个含有各种烷基、苯基、烯丙基、五元杂环及其它极性基团的有机锡化合物的~(13)C—NMR谱。对全部谱线进行了归属。讨论了烷基锡、苯基锡中Sn—C键的性质和极性取代基对C—1δ值的影响。考察了各类C-Sn偶合常数大小顺序,以及~1J_(C-)~(119)Sn与~1J_(C-)~(117)Sn的关系。     

LR-CAHSQC: an application of a Carr-Purcell-Meiboom-Gill-type sequence to heteronuclear multiple bond correlation spectroscopy

A new pulse sequence, long-range CPMG-adjusted heteronuclear single quantum coherence (LR-CAHSQC), is proposed for the determination of long-range JCH coupling constants from a long-range 1H-13C correlation experiment. The long-range heteronuclear coupling constants can be directly extracted from COSY-type antiphase peak patterns. The current approach utilizes CPMG-sequences for polarization transfer, and thus avoids the evolution of homonuclear JHH couplings, which normally may introduce abnormalities into the cross peak pattern. The differences between LR-CAHSQC and normal LR-HSQC are discussed.     

Separated local field spectroscopy of columnar and nematic liquid crystals

We are in this work comparing the efficiencies of various 1H-13C separated local field (SLF) experiments when applied to columnar and nematic liquid crystals. In particular, the performances of the conventional SLF, proton-detected local field (PDLF), and polarization inversion spin exchange at the magic angle (PISEMA) methods in terms of spectral resolution, robustness, and ability to measure long-range couplings are investigated. The PDLF sequence provides in most cases the best dipolar resolution. This is especially obvious for weakly coupled 1H-13C spin pairs.     

13C-1H HSQC experiment of probe molecules aligned in thermotropic liquid crystals: sensitivity and resolution enhancement in the indirect dimension

The spectra of molecules oriented in liquid crystalline media are dominated by partially averaged dipolar couplings. In the 13C-1H HSQC, due to the inefficient hetero-nuclear dipolar decoupling in the indirect dimension, normally carried out by using a pi pulse, there is a considerable loss of resolution. Furthermore, in such strongly orienting media the 1H-1H and 13C-1H dipolar couplings leads to fast dephasing of transverse magnetization causing inefficient polarization transfer and hence the loss of sensitivity in the indirect dimension. In this study we have carried out 13C-1H HSQC experiment with efficient polarization transfer from 1H to 13C for molecules aligned in liquid crystalline media. The homonuclear dipolar decoupling using FFLG during the INEPT transfer delays and also during evolution period combined with the pi pulse heteronuclear decoupling in the t1 period has been applied. The studies showed a significant reduction in partially averaged dipolar couplings and thereby enhancement in the resolution and sensitivity in the indirect dimension. This has been demonstrated on pyridazine and pyrimidine oriented in the liquid crystal. The two closely resonating carbons in pyrimidine are better resolved in the present study compared to the earlier work [H.S. Vinay Deepak, Anu Joy, N. Suryaprakash, Determination of natural abundance 15N-1H and 13C-1H dipolar couplings of molecules in a strongly orienting media using two-dimensional inverse experiments, Magn. Reson. Chem. 44 (2006) 553-565].     

Inverse polarization transfer for detecting in vivo 13C magnetization transfer effect of specific enzyme reactions in 1H spectra

The wide chemical shift dispersion and long T(1) of (13)C have allowed determination of in vivo magnetization transfer effects caused by aspartate aminotransferase and lactate dehydrogenase reactions using (13)C magnetic resonance spectroscopy. In this report, we demonstrate that these effects can be observed in the proton spectra by transferring the equilibrium magnetization of (13)C via the one-bond scalar coupling between (13)C and (1)H using an inverse insensitive nuclei enhanced by polarization transfer-based heteronuclear polarization transfer method. This inverse method allows a combination of the advantages of the long (13)C T(1) for maximum magnetization transfer and the high sensitivity of proton detection. The feasibility of this in vivo inverse polarization transfer approach was evaluated for detecting the (13)C magnetization transfer effect of aspartate aminotransferase and lactate dehydrogenase reactions from a 72.5-microl voxel in the rat brain at 11.7 T.     

Multiple-spin analysis of chemical-shift-selective (13C, 13C) transfer in uniformly labeled biomolecules

Chemical-shift-selective (13C, 13C) polarization transfer is analyzed in uniformly labeled biomolecules. It is shown that the spin system dynamics remain sensitive to the distance of interest and can be well reproduced within a quantum-mechanical multiple-spin analysis. These results lead to a general approach on how to describe chemical-shift-selective transfer in uniformly labeled systems. As demonstrated in the case of ubiquitin, this methodology can be used to detect long-range distance constraints in uniformly labeled proteins.     

High resolution C nuclear magnetic resonance spectra for symmetrical orthodihalobenzenes including long-range CH couplings

Analysis of high resolution ¹³C NMR spectra for symmetrical orthodihalobenzenes have provided all long-range ¹³CH coupling values in orthodichloro-, dibromo-, and diiodobenzene. Furthermore, since the analyses were sensitive to the sign of the coupling constants, the relative signs of these long-range ¹³CH couplings have been determined from unique spectral fits. The substituent effects on the chemical shifts in this series of compounds appear to be additive. The ¹³CH couplings are compared with coupling values in other compounds and are shown to be related to substituent electronegativity. The absolute magnitude of the ¹³CH couplings for these halogen-substituted compounds are larger than those observed in benzene, with but one exception. In all cases, three-bonded ¹³CH couplings are found to be larger than the two-bond values.     

J-modulated ADEQUATE (JM-ADEQUATE) experiment for accurate measurement of carbon-carbon coupling constants

A new method for the accurate determination of carbon-carbon coupling constants is described. The method is based on a modified ADEQUATE experiment, where a J-modulated spin-echo sequence precedes the ADEQUATE pulse scheme. The J-modulation and scaling of carbon-carbon couplings is based on simultaneous incrementation of 13C chemical shift and coupling evolution periods. The time increment for the homonuclear carbon-carbon coupling evolution can be suitably scaled with respect to the corresponding increment for the chemical shift evolution. Typically a scaling factor of 2 to 3 is employed for the measurement of one-bond coupling constants, while multiplication by a factor of 10 to 15 is applied when small long-range couplings are determined. The same pulse scheme with coupling evolution period optimized for one-bond or long-range couplings allows the determination of the corresponding carbon-carbon coupling constants. The splittings of the ADEQUATE crosspeaks in the F1 dimension yield the appropriately multiplied coupling constants.     

Recoupled long-range C-H dipolar dephasing in solid-state NMR,and its use for spectral selection of fused aromatic rings

This work introduces a simple new solid-state 13C NMR method for distinguishing various types of aromatic residues, e.g. those of lignin from fused rings of charcoal. It is based on long-range dipolar dephasing, which is achieved by recoupling of long-range C-H dipolar interactions, using two 1H 180 degrees pulses per rotation period. This speeds up dephasing of unprotonated carbon signals approximately threefold compared to standard dipolar dephasing without recoupling and thus provides much more efficient differential dephasing. It also reduces the effects of spinning-speed dependent effective proton-proton dipolar couplings on the heteronuclear dephasing. Signals of unprotonated carbons with two or more protons at a two-bond distance dephase to <3% within less than 0.9 ms, significantly faster than those of aromatic sites separated from the nearest proton by three or more bonds. Differential dephasing among different unprotonated carbons is demonstrated in a substituted anthraquinone and 3-methoxy benzamide. The data yield a calibration curve for converting the dephasing rates into estimated distances from the carbon to the nearest protons. This can be used for peak assignment in heavily substituted or fused aromatic molecules. Compared to lignin, slow dephasing is observed for the aromatic carbons in wood charcoal, and even slower for inorganic carbonate. Direct 13C polarization is used on these structurally complex samples to prevent loss of the signals of interest, which by design originate from carbons that are distant from protons and therefore crosspolarize poorly. In natural organic matter such as humic acids, this combination of recoupled dipolar dephasing and direct polarization at 7-kHz MAS enables selective observation of signals from fused rings that are characteristic of charcoal.     

(1)H-Detected IPAP DEPT-INADEQUATE and IPAP RINEPT-INADEQUATE for the measurement of long-range carbon-carbon coupling constants

The sensitivity of cryoprobes, which are rapidly becoming available, have brought about the possibility of measurement of (13)C, (13)C coupling constants at the natural abundance of (13)C using tens rather than hundreds of milligrams of compounds. This relatively recent development lays the foundation for a more routine use of the (13)C, (13)C long-range coupling constants in the conformational analysis of molecules. We have designed novel (1)H-detected INADEQUATE experiments optimized for long-range (13)C, (13)C correlations and the measurement of long-range coupling constants. These experiments incorporate refocusing of (1)J(CH) coupling constants prior to the formation of DQ coherences and (1)H-decoupling during the long carbon-carbon evolution intervals. Such modifications significantly enhance their performance over (1)H-detected INADEQUATE experiments currently in use for mapping the one-bond (13)C, (13)C correlations. (1)H or (13)C polarization is used a starting point in long-range correlation (1)H-detected IPAP DEPT-INADEQUATE or RINEPT-INADEQUATE experiments. These correlation experiments were modified yielding in-phase (IP) or antiphase (AP) (13)C, (13)C doublets in F(1). Procedures were developed for their editing yielding accurate values of small (13)C, (13)C coupling constants. The methods are illustrated using mono- and disaccharide samples and compared with related (13)C-detected experiments by means of the measurement of interglycosidic (13)C, (13)C coupling constants of a disaccharide.     

Backbone and side chain assignment strategies for multiply labeled membrane peptides and proteins in the solid state

We demonstrate that the SPECIFIC CP technique can be used to obtain heteronuclear correlation (HETCOR) spectra of peptide backbones with greater efficiency than conventional HETCOR methods. We show that similar design principles can be employed to achieve selective homonuclear polarization transfer mediated through dipolar or scalar couplings. Both approaches are demonstrated in a tripeptide with uniform 15N and 13C labeling, and with uniform 15N labeling and natural abundance 13C. In other applications, the high efficiency of the heteronuclear SPECIFIC CP transfer allows discrimination of single amide signals in the 248-residue membrane protein bacteriorhodopsin (bR). In particular, variations are detected in the ordering of the Ala81-Arg82 peptide bond among the photocycle intermediates of bR and SPECIFIC CP is used to correlate 15N and 13C signals from the three Val-Pro peptide bonds.