DEVELOPMENT OF NEW NMR TECHNIQUES AND THEIR APPLICATION TO STRUCTURAL ANALYSIS OF NATURAL PRODUCTS

新核磁共振技术的开发及其在天然产物结构分析中的应用

• 批准号: 06556019
• 负责人: SETO Haruo
• 金额: $ 9.22万
• 依托单位: INSTITUTE OF MOLECULAR AND CELLULAR BIOSCIENCES,UNIVERSITY OF TOKYO
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06556019/
• 关键词: decoupled-HMBC; D-HMBC; MolSkop; TANGO-HMBC; analysis of stereo-structures by computer calculation; プロモインドシン; スタキボシン; プロモチオシン; ゲニンチオシン; セコスリキサイド; コンピュータによる立体構造解析

In this project, we have investigated the applications of a new NMR technique called decoupled-HMBC (D-HMBC) developed by our group to structural analysis of complicated natural products. In addition, we have carried out analysis of stereo-structures by computer calculations using a newly developed software program (MolSkop) by the JEOL group.As a result, D-HMBC has turned out to be an excellent method to observe small long-range ^<13>C-^1H couplings, which can not be detected by hitherto available techniques. In addition, we have improved the data processing procedures ; ood NMR spectra with improved signal to noise ratio were obtained when data processing was made by the phase sensitive mode of the t2 axis data and by power mode of the t1 axis data.Comparison of this new technique (D-HMBC) with the pulse field gradiet (PGF) technique has revealed that PFG is superior to D-HMBC in most cases, but when the signal intensities were considerably affected by J-modulation caused by ^1H-^1H spin couplings, D-HMBC gave better results and so a method of choice in such situation. In this project, we have established experimental conditions for obtaining good D-HMBC spectra. This technique has been implemented to commercially available NMR instruments is now being used by some groups.We have improved the MolSkop software program and proved that it is a useful method to structural analysis of complicated polycyclic systems.In addition, we have recently developed a new technique called TANGO-D-HMBC,which is quite useful for detecting ^<13>C-^<13>C couplings separed by two bonds. Such kinds of long-range ^<13>C-^<13>C couplings were hardly observed by other methods. This pulse sequence is quite useful for datailed analysis of the ^<13>C- labeling pattern with microbial products formed by arrangement of the carbon skeleton.

在这个项目中，我们研究了我们课题组开发的一种名为去耦合HMBC(D-HMBC)的新的核磁共振技术在复杂天然产物结构分析中的应用。此外，我们还使用JEOL小组新开发的软件程序(MolSkop)对立体结构进行了计算机计算分析。结果表明，D-HMBC是观察小的长程^&lt；13&gt；C-^1H耦合的一种很好的方法，这是迄今为止可用的技术无法检测到的。此外，我们还改进了数据处理程序，用T2轴数据的相敏模式和T1轴数据的功率模式进行数据处理，得到了信噪比得到改善的OID核磁共振谱。通过与脉冲场梯度(PGF)技术的比较发现，在大多数情况下，脉冲磁场梯度(D-HMBC)技术优于D-HMBC技术，但当信号强度受到^1H-^1H自旋耦合引起的J调制的影响时，D-HMBC的结果更好，因此是这种情况下的一种选择方法。在本项目中，我们为获得良好的D-HMBC光谱建立了实验条件。这项技术已经被应用于商业核磁共振仪器，现在正在被一些小组使用。我们改进了MolSkop软件程序，证明它是一种有用的方法来分析复杂的多环体系的结构。此外，我们最近开发了一种新的技术，称为Tango-D-HMBC，它对于检测由两个键分开的^&lt；13&gt；C-^&gt；C偶合非常有用。这种长程耦合很难用其他方法观察到。该脉冲序列对于通过碳骨架排列形成的微生物产物的^&lt；13&gt；C-标记模式的数据分析非常有用。

项目成果

K. Ogawa, M. Nakamura, H. Seto et al.: "Stachybocins, novel endothelin receptor antagonists, produced by Stachybotrys sp. M6222. II. Structure determination of stachybocins A, B and C." J. Antibiotics. 48. 1396-1400 (1995)

K. Okawa、M. Nakamura、H. Seto 等人：“Stachybocins，新型内皮素受体拮抗剂，由 Stachybotrys sp. M6222 产生。II. Stachybocins A、B 和 C 的结构测定。”

B.-S.Yun and H.Seto: "Promoinducin, a novel thiopeptide produced by Streptomyces sp. SF2741." Biosci.Biotech.Biochem.59. 876-880 (1995)

B.-S.Yun 和 H.Seto：“Promoinducin，一种由链霉菌 SF2741 产生的新型硫肽。”

B.-S.Yun,H.Seto et al.: "Microbial metabolites with tipA promoter inducing activity.II.Geninthiocin,a novel thiopeptide produced by Streptomyces sp." J.Antibiotics. 47. 969-975 (1994)

B.-S.Yun、H.Seto 等人：“具有tipA启动子诱导活性的微生物代谢物。II.Geninthiocin，一种由链霉菌属产生的新型硫肽。”

B.-S.Yun, T.Hidaka, K.Furihata and H.Seto: "Promothiocins A and B,novel thiopeptides with a tipA promoter inducing activity produced by streptomyces sp. SF2741." J.Antibiot. 47. 510-514 (1994)

B.-S.Yun、T.Hidaka、K.Furihata 和 H.Seto：“Promothiocins A 和 B，新型硫肽，具有由链霉菌 SF2741 产生的tipA启动子诱导活性。”

K. Shin-ya, S. Shimizu, H. Seto et al.: "Novel neuronal cell protecting substances, aestivopho enins A and B, produced by Streptomyces purpeofuscus." J. Antibiotics. 48. 1378-1381 (1995)

K. Shin-ya、S. Shimizu、H. Seto 等人：“新型神经元细胞保护物质，aestivopho enins A 和 B，由 Streptomyces purpeofuscus 产生。”