Highly Sensitive TM-mode ENDOR and its Biological Applications

高灵敏TM模式ENDOR及其生物应用

• 批准号: 04640443
• 负责人: YAMAUCHI Jun
• 金额: $ 1.41万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04640443/
• 关键词: ENDOR; TM-mode cavity; flat ESR cell; sterical hindrance; NO scavenger; Wurster's blue cation radical; nitroxide radical; benzophenone anion radical; TMモードキャビティ; ENDOR Tmモードキャティ; テトラメチルイミダゾリン; TRIPLE

In order to accomplish a high sensitive ENDOR spectrometer and its development into biological systems, we examined electronis circuits and a cavity therein. In particular, a TM mode-type ENDOR cavity was precisely checked and newly produced by repeating actual observations using several of the typical organic radicals. We finally obtained high loaded Q-value amounting to more than 3000, which essentially contributes ro the high sensitivity and low signal-to-noise ratio.Systems investigated were sterically hindeered 2-methylbenzophenone anion radical, nitric oxide (NO) scavebger 4,4,5,5-tetramethyl imidazoline-1,3-oxyl, Wurster's blue cation radical and so forth. In the sterically hindered system, there are lot of non-equivalent protons resulting in broad ESR lines. In our case we could resolve 8-9 lines which allowed perfect ESR analysis, and a hindered rotation mechanism was discussed in detail. ^1H- and ^<14>N-ENDOR spectra of NO-trapping scavenger revealed an important role of NO in the biological systems. In addition, it was established that a flat cell combined with the TM-mode cavity is powerful to study the biological important radicals, which sometimes cause low Q-value and therefore low sensitivity in ENDOR.

为了实现高灵敏度的ENDOR谱仪及其在生物系统中的应用，我们对电子线路及其空腔进行了研究。特别是，TM模式型ENDOR腔被精确地检查，并通过使用几种典型的有机自由基重复实际观察而新产生。研究了空间位阻的2-甲基二苯甲酮阴离子自由基、一氧化氮（NO）清除剂4，4，5，5-四甲基咪唑啉-1，3-氧自由基、Wurster蓝阳离子自由基等体系。在空间位阻体系中，存在大量的非等效质子，导致ESR谱线较宽。在我们的例子中，我们可以解决8-9线，允许完美的ESR分析，并详细讨论了受阻旋转机制。NO捕获剂的^1H-和^<14>N-ENDOR光谱揭示了NO在生物系统中的重要作用。此外，它是建立一个扁平的细胞结合TM模式腔是强大的研究生物重要的自由基，有时会导致低Q值，因此在ENDOR的灵敏度低。

项目成果

山内淳 他: "Antiferrowagnetic Long-Rauge Ordering of Organic Free Radicals" Mol.Cryst.Liq.Crysy.233. 97-104 (1993)

Jun Yamauchi 等人：“有机自由基的反铁磁性长距离排序”Mol.Cryst.Liq.Crysy.233 (1993)。

J.Yamauchi et al.: "ESR and ENDOR studies of the 2-methyl benzophenone anion radical" Bull.Chem.Soc.Jpn.66. 2505-2509 (1993)

J.Yamauchi 等人：“2-甲基二苯甲酮阴离子自由基的 ESR 和 ENDOR 研究”Bull.Chem.Soc.Jpn.66。

J.Yamauchi et al.: "Magnetic Interactions of Organic Free Radicals under High Pressure" New Functionality Materials. C. 555-560 (1993)

J.Yamauchi等人：“高压下有机自由基的磁相互作用”新功能材料。

山内 淳 他: "ESR and ENDOR Studies of the 2-Methylbenzophenone Anion Radical" Bull.Chem.Soc.Jpn.66. 2505-2509 (1993)

Jun Yamauchi 等人：“2-甲基二苯甲酮阴离子自由基的 ESR 和 ENDOR 研究”Bull.Chem.Soc.Jpn.66 (1993)。

T.Sugimoto et al.: "Biradical Character of a Closed-Shell Heteroaromatic Quinone" J.Amer.Chem.Soc.114. 1893-1895 (1992)

T.Sugimoto 等人：“闭壳杂芳香醌的双自由基特征”J.Amer.Chem.Soc.114。