Development of Novel Spin-labeled Nucleosides which detect base-pairing

开发检测碱基配对的新型自旋标记核苷

• 批准号: 15590012
• 负责人: ASO Mariko
• 金额: $ 2.3万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15590012/
• 关键词: spin-labeled nucleoside; N-tert-butylaminoxyl; EPR; base pairing; hydrogen bonding; ESRスペクトル; pH依存症; N-tert-アミノキシルラジカル; イノシン; アデノシン; シチジン; グアノシン

We designed novel spin-labeled nucleosides, in which a spin source, an N-tert-butylaminoxyl radical, was directly attached to nucleobase. 2-N-tert-Butylaminoxyladenosine, 2-N-tert-butylaminoxylinosine, and 8-N-tert-butylaminoxylinosine, and 5-N-tert-butylaminoxylcytidine derivative were synthesized and thier stabilities and properties were studied by using electron peramagnetic resonance(EPR). It was of interest to investigate if EPR spectra of N-tert-butylaminoxylnucleosides changed upon formation of hydrogen bonding with complementary base. EPR spectra of O-silylated-5-N-tert-butylaminoxylcytidine in CH_2Cl_2 changed upon addition of O-silylated guanosine, which might form hydrogen bonds with the aminoxyl cytidine. 2-N-tert-Butylaminoxyladenosine was introduced into oligoncleotide and its EPR spectra were measured. The EPR spectrum of the obtained oligonucleotide showed three lines in phosphate buffer. The high line disappeared upon duplex formation with the complementary strand to show that the EPR spectra might give useful information on the structure of oligonucleotide. EPR spectra of 2-N-tert-butylaminoxylinosine showed pH dependency due to structural change of purine moiety

我们设计了一种新的自旋标记核苷，其中自旋源n-叔丁基氨基氧基直接附着在核碱基上。合成了2- n -叔丁基氨基氧基腺苷、2- n -叔丁基氨基氧基肌苷、8- n -叔丁基氨基氧基肌苷和5- n -叔丁基氨基氧基胞苷衍生物，并利用电子过磁共振（EPR）对其稳定性和性质进行了研究。研究n -叔丁基氨基氧基核苷与互补碱形成氢键后EPR谱是否发生变化。o -硅基化-5- n -叔丁基氨基氧基胞苷在CH_2Cl_2中加入o -硅基化鸟苷后，EPR光谱发生变化，鸟苷可能与氨基氧基胞苷形成氢键。将2- n -叔丁基氨基氧化腺苷引入寡糖肽中，测定了其EPR谱。所得寡核苷酸的EPR谱在磷酸缓冲液中显示三条谱线。当与互补链形成双链时，高线消失，表明EPR光谱可以提供有关寡核苷酸结构的有用信息。由于嘌呤部分的结构变化，2- n -叔丁基氨基氧化亚氨基甘氨酸的EPR谱表现出pH依赖性

项目成果

Synthetic studies and properties of N-tert-butylaminoxyl nucleosides

N-叔丁基氨氧基核苷的合成研究及性质

• 发表时间: 2003
• 期刊: Nucleic Acids Research Supplement 3
• 作者: M.Aso;T.Kaneko;M.Nakamura;Y.Matsui;N.Koga;H.Suemune
• 通讯作者: H.Suemune

Molecular design of novel spin-labeled nucleoside directly attached base moiety

新型自旋标记核苷直接连接碱基部分的分子设计

• 发表时间: 2004
• 期刊: Nucleic Acids Simposium Series 48
• 作者: T.Kaneko;T.Katsurabara;Y.Matsui;M.Aso;N.Koga;H.Suemune
• 通讯作者: H.Suemune

M.Aso et al.: "A simple and efficient method for synthesis of 5-substituted 2'-deoxyuridine nucleosides using metal-halogen exchange reaction of 5-iodo-2'-deoxyuridine sodium salt"Chemical Communications. 2. 1094-1095 (2003)

M.Aso 等人：“利用 5-碘-2-脱氧尿苷钠盐的金属-卤素交换反应合成 5-取代 2-脱氧尿苷核苷的简单有效的方法”化学通讯。

Synthetic studies and properties of N-tert-butylaminoxylnucleosides

N-叔丁基氨氧基核苷的合成研究及性质

• 发表时间: 2003
• 期刊: Nucleic Acids Research 3(Supplement)
• 作者: M.Aso;T.Kaneko;M.Nakamura;Y.Matsui;N.Koga;H.Suemune
• 通讯作者: H.Suemune

M.Aso et al.: "Synthetic studies and properties of N-tert-butylaminoxyl nucleosides"Nucleic Acids Research Supplement. 3. 9-10 (2003)

M.Aso 等人：“N-叔丁基氨氧基核苷的合成研究和性质”核酸研究增刊。