Development of cold-spray ionization mass spectrometry and its application to supramolecules and biomolecules

冷喷雾电离质谱的发展及其在超分子和生物分子中的应用

• 批准号: 13557198
• 负责人: YAMAGUCHI Kentaro
• 金额: $ 6.14万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13557198/
• 关键词: cold-spray; DNA; cluster ion; nucleoside; hydrogen bonding; electrospray; mass spectrometry; ionization; ヌクレオシド; コールドスプレーイオン化; 生体分子; クラスターイオン; 非共有性相互作用

A direct solution analysis method, cold-spray ionization (CSI) mass spectrometry (MS), a variant of electrospray (ESI) MS operating at low temperature (ca. -80 〜 10℃), allows facile and precise characterization of labile organic species, especially those in which non-covalent bonding interactions are prominent. We have applied this method to investigations of the solution structures of many labile organic species, including unstable reagents and reaction intermediates, asymmetric catalysts, supramolecules, and even primary biomolecules. Remarkable analytical results were obtained for highly ordered supramolecules using the CSI method. While conventional ESI is not applicable to these compounds because of their instability to heat and/or air, CSI affords multiply charged molecular ions with many solvent molecules attached. Investigation of the constitution of Grignard reagents in solution is extremely challenging, but CSI-MS allowed us to identify one of the key structures in THF solution. Recently, this method was adopted for investigations of the solution structures of primary biomolecules such as nucleosides, amino acids, sugars and lipids, revealing singly charged Na^+ adducts of large clusters (chain structures), presumably linked by non-covalent interactions, including hydrogen bonding and/or hydrophobic interactions.

一种直接溶液分析方法，冷喷雾电离（CSI）质谱（MS），电喷雾（ESI）MS的一种变体，在低温（约20 ℃）下操作。-80 ℃ ~ 10℃），可以方便和精确地表征不稳定的有机物种，特别是那些非共价键相互作用突出的物种。我们已经将这种方法应用于许多不稳定的有机物种，包括不稳定的试剂和反应中间体，不对称催化剂，超分子，甚至初级生物分子的溶液结构的调查。显着的分析结果，获得了高度有序的超分子使用CSI方法。虽然传统的ESI不适用于这些化合物，因为它们对热和/或空气不稳定，CSI提供了多电荷分子离子与许多溶剂分子连接。研究溶液中格利雅试剂的组成是极具挑战性的，但CSI-MS使我们能够识别THF溶液中的关键结构之一。最近，这种方法被用于研究核苷、氨基酸、糖和脂质等主要生物分子的溶液结构，揭示了大分子团簇的单电荷Na^+加合物（链状结构），推测它们通过非共价相互作用（包括氢键和/或疏水相互作用）连接在一起。

项目成果

Y. Kubota, S. Sakamoto, K. Yamaguchi, M. Fujita: "Guest-induced organization of an optimal receptor from a dynamic receptor library: Spectroscopic screening"PRNS. 99 (No.8). 4854-4856 (2002)

Y. Kubota、S. Sakamoto、K. Yamaguchi、M. Fujita：“来自动态受体库的最佳受体的客体诱导组织：光谱筛选”PRNS。

坂本 茂, 山口健太郎: "Low Tm DNA duplexes observation by cold-spray ionization mass spectrometry"Tetrahedron Letters. 44. 3341-3344 (2003)

Shigeru Sakamoto、Kentaro Yamaguchi：“通过冷喷雾电离质谱法观察低 Tm DNA 双链体”Tetrahedron Letters 44. 3341-3344 (2003)。

K. Nakatani, S. Hagihara, S. Sando, S. Sakamoto, K. Yamaguchi, C. Maesawa, I. Saito: "Induction of a Remarkable Conformational Change in a Human Telomeric Sequence by the Binding of Naphthyridine Dimer : Inhibition of the Elongation of a Telomeric Repeat

K. Nakatani、S. Hagihara、S. Sando、S. Sakamoto、K. Yamaguchi、C. Maesawa、I. Saito：“通过萘啶二聚体的结合诱导人类端粒序列发生显着的构象变化：抑制

M. Kunimura, S. Sakamoto, K. Yamaguchi: "Alkali Metal-Mediated Proline Aggregation in Solution Observed by Coldspray Ionization Mass Spectrometry"Organic Letters. 4(3). 347-350 (2002)

M. Kunimura、S. Sakamoto、K. Yamaguchi：“通过冷喷雾电离质谱法观察溶液中碱金属介导的脯氨酸聚集”有机快报。

坂本 茂, 中谷和彦, 齋藤 烈, 山口健太郎: "Formation and destruction of the guanine quartet solution observed by CSI-MS"Chem.Commun.. 788-789 (2003)

Shigeru Sakamoto、Kazuhiko Nakatani、Retsu Saito、Kentaro Yamaguchi：“CSI-MS 观察到的鸟嘌呤四联体溶液的形成和破坏”Chem.Commun.. 788-789 (2003)