强酸性环境中氧氟沙星的质子化模型研究

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (9): 1747.

强酸性环境中氧氟沙星的质子化模型研究

李慧珍^1,2, 刘少轩¹, 华小辉¹, 潘庆华¹, 杨展澜¹, 高秀香¹, 朱曦³, 徐怡庄¹, 吴瑾光¹

1. 稀土材料化学及应用国家重点实验室, 北京大学化学与分子工程学院, 北京分子科学国家实验室, 北京 100871;
2. 河南师范大学化学与环境科学学院, 新乡 453007;
3. 北京大学第三临床医院危重医学科, 北京 100191

收稿日期:2010-01-22 出版日期:2010-09-10 发布日期:2010-09-10
通讯作者: 徐怡庄，男，博士，副教授，主要从事分子光谱研究. E-mail: xyz@pku.edu.cn
基金资助:
国家自然科学基金(批准号: 50673005, 20671007, 50973003)和北京大学先进技术研究院培育项目资助.

Studies on the Protonation Structure of Ofloxacin in Concentrated Sulfuric Acid Solutions

LI Hui-Zhen^1,2, LIU Shao-Xuan¹, HUA Xiao-Hui¹, PAN Qing-Hua¹, YANG Zhan-Lan¹, GAO Xiu-Xiang¹, ZHU Xi³, XU Yi-Zhuang^1*, WU Jin-Guang¹

1. State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing National Laboratory for Molecular Sciences, Beijing 100871, China;
2. College of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007, China;
3. Department of Critical Care Unit, Third Hospital of Peking University, Beijing 100191, China

Received:2010-01-22 Online:2010-09-10 Published:2010-09-10
Contact: XU Yi-Zhuang. E-mail: xyz@pku.edu.cn
Supported by:
国家自然科学基金(批准号: 50673005, 20671007, 50973003)和北京大学先进技术研究院培育项目资助.

摘要/Abstract

摘要： 利用核磁共振波谱技术研究了不同浓度硫酸溶液中氧氟沙星(OFL)的¹H, ¹⁹F和¹³C核磁共振谱, 对不同硫酸浓度引起的δ_H, δ_F, δ_C和J_FC耦合常数的变化进行比较分析, 由此推测其结构状态. 综合¹H, ¹⁹F和¹³C核磁共振谱特点及其变化, 提出OFL分子在强酸性环境中N_1′被进一步质子化的结构模型. 在浓硫酸溶液中, N_1′ 被进一步质子化, 并与F₉形成氢键(N_1′—H⁺┈F₉), 该结构使分子的共轭程度大幅降低, 导致其荧光发射波长、荧光激发波长及紫外吸收波长均发生蓝移. 硫酸溶液中氧氟酸和甲基氧氟沙星的荧光光谱行为进一步证明了OFL分子在浓硫酸溶液中质子化模型的合理性.

关键词: 氧氟沙星, 喹诺酮, 核磁共振, 质子化

Abstract: Systematic NMR spectroscopic investigation on ofloxacin(OFL) in concentrated sulfuric acid solution was carried out via ¹⁹F NMR, ¹H NMR and ¹³C NMR experiments. Complete assignment on ¹⁹F NMR, ¹H NMR and ¹³C NMR of ofloxacin in sulfuric acid solutions were obtained. The chemical shift of H, F, C, and the J_FC of OFL molecule in sulfuric acid solutions of different concentrations were found to be very helpful for the identification the protonation structure of OFL molecule. According to the variation of the chemical shift of H, F, C, and the J_FC of OFL molecule in sulfuric acid solutions of different concentrations, we propose that the N_1′ is further protonated in concentrated sulfuric acid solutions. Additionally, a new hydrogen bond(N_1′—H⁺┈F₉) forms and the structure can be stabilized by a five-member ring and the conjugate system is distorted by the five-member ring. As a result, the emission peak, excitation peak in fluorescent spectra and absorption peak in UV spectra of OFL exhibit blue-shifted significantly. In addition, the proposed protonation structure was further supported by spectroscopic behavior of oxygen-fluorine acid and methyl-ofloxacin.

Key words: Ofloxacin, Quinolone, NMR, Protonation

TrendMD:

李慧珍, 刘少轩, 华小辉, 潘庆华, 杨展澜, 高秀香, 朱曦, 徐怡庄, 吴瑾光. 强酸性环境中氧氟沙星的质子化模型研究. 高等学校化学学报, 2010, 31(9): 1747.

LI Hui-Zhen, LIU Shao-Xuan, HUA Xiao-Hui, PAN Qing-Hua, YANG Zhan-Lan, .... Studies on the Protonation Structure of Ofloxacin in Concentrated Sulfuric Acid Solutions. Chem. J. Chinese Universities, 2010, 31(9): 1747.

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