物理化学学报 >> 2011, Vol. 27 >> Issue (11): 26822682-2690..doi: 10.3866/PKU.WHXB20111132

光化学和辐射化学 上一篇    下一篇

竹红菌乙素镁、锌配位聚合物的光物理和光生物性质

郭创龙, 欧植泽, 高云燕, 王中丽, 金和林, 李海霞   

  1. 西北工业大学理学院, 空间应用物理与化学教育部重点实验室, 西安 710072
  • 收稿日期:2011-07-19 修回日期:2011-08-31 发布日期:2011-10-27
  • 通讯作者: 欧植泽, 高云燕 E-mail:ouzhize@nwpu.edu.cn; gaoyunyan@nwpu.edu.cn
  • 基金资助:

    国家自然科学基金(21073143), 教育部“春晖计划”基金(Z2009-1-71002, Z2009-1-71006)和西北工业大学基础研究基金(JC200822,JC20100239)资助项目

Photophysical and Photobiological Properties of Coordination Polymers of Hypocrellin B Complexes Containing Magnesium and Zinc

GUO Chuang-Long, OU Zhi-Ze, GAO Yun-Yan, WANG Zhong-Li, JIN He-Lin, LI Hai-Xia   

  1. Key Laboratory of Space, Applied Physics and Chemistry, Ministry of Education, School of Science, Northwestern Polytechnical University, Xi'an 710072
  • Received:2011-07-19 Revised:2011-08-31 Published:2011-10-27
  • Contact: OU Zhi-Ze, GAO Yun-Yan E-mail:ouzhize@nwpu.edu.cn; gaoyunyan@nwpu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21073143),“Chunhui Project ”of the Ministry of Education of China (Z2009-1-71002, Z2009-1-71006) and Northwestern Polytechnical University Foundation for Fundamental Research, China (JC200822, JC20100239).

摘要: 竹红菌乙素(HB)能与Mg2+和Zn2+形成重复单元数为5-20的配位聚合物(Mg2+-HB, Zn2+-HB), 利用紫外-可见(UV-Vis)吸收光谱, 傅里叶变换红外(FTIR)光谱, 核磁共振氢谱(1H NMR)对其进行了表征. Mg2+-HB 和Zn2+-HB 的单重态氧量子产率分别为HB 的1.2 倍和0.42 倍. 瞬态吸收实验表明: 氧气能够猝灭Mg2+-HB 和Zn2+-HB 的三重态, 其效率可超过96%. 系间窜越效率(ФT)和将能量传递给氧气并能产生单重态氧的三重态光敏剂的比例(fΔT)对HB及其金属配合物的单重态氧量子产率有较大影响. 电子自旋共振(EPR)实验结果表明:Mg2+-HB和Zn2+-HB产生半醌负离子自由基的能力较弱, 进而降低了Mg2+-HB和Zn2+-HB光敏产生超氧负离子自由基的能力. 紫外-可见吸收光谱与小牛胸腺脱氧核糖核酸(CT DNA)熔链温度实验表明: Mg2+-HB和Zn2+-HB可通过静电作用与DNA结合. 有氧条件下, Mg2+-HB, HB和Zn2+-HB 对小牛胸腺DNA的光敏损伤效率分别为32%, 25%和22%. 活性氧猝灭实验表明Mg2+-HB主要通过单重态氧光敏损伤DNA.

关键词: 竹红菌乙素, 配位聚合物, 单重态氧, 超氧负离子自由基, DNA光损伤

Abstract: Hypocrellin B (HB) can chelate with Mg2+ and Zn2+ ions to form the coordination complexes Mg2+-HB and Zn2+-HB, which consist of 5-22 repeat units. The structures of these two complexes are characterized by ultraviolet-visible (UV-Vis) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and 1H nuclear magnetic resonance (1H NMR). The relative quantum yields of singlet oxygen (1O2) for Mg2+-HB and Zn2+-HB are 1.2 and 0.42 times as high as that of HB, respectively. Transient absorption spectra results indicate that O2 is able to quench the triplet excited state of Mg2+-HB and Zn2+-HB with an efficiency higher than 96% . The intersystem crossing efficiency (ΦT) and the fraction of triplet states quenched by O2 that yield 1O2 (fΔT) are considered to be essential for the singlet oxygen quantum yields of HB and its complexes. Electron paramagnetic resonance (EPR) results suggest that Mg2+-HB and Zn2+-HB have a weak ability to generate a semiquinone anion radical, which reduces the generation of the superoxide anion radical (O2·-) by Mg2+-HB and Zn2+-HB. The results of the UV-Vis spectra and the deoxyribonucleic acid (DNA) melting temperature experiments indicate that Mg2+-HB and Zn2+-HB bind with calf thymus (CT) DNA in an electrostatic interaction mode. Under aerobic conditions, the efficiencies of photoinduced damage to CT DNA by Mg2+-HB, HB, and Zn2+-HB are found to be 32%, 25%, and 22%, respectively. The reactive oxygen quencher experiments indicate that singlet oxygen is the main component generated by Mg2+-HB that damages CT DNA.

Key words: Hypocrellin B, Coordination polymer, Singlet oxygen, Superoxide anion radical, DNA photodamage

MSC2000: 

  • O641