竹红菌乙素镁、锌配位聚合物的光物理和光生物性质

引用本文: 郭创龙, 欧植泽, 高云燕, 王中丽, 金和林, 李海霞. 竹红菌乙素镁、锌配位聚合物的光物理和光生物性质[J]. 物理化学学报, 2011, 27(11): 2682-2690. doi: 10.3866/PKU.WHXB20111132 shu

Citation: GUO Chuang-Long, OU Zhi-Ze, GAO Yun-Yan, WANG Zhong-Li, JIN He-Lin, LI Hai-Xia. Photophysical and Photobiological Properties of Coordination Polymers of Hypocrellin B Complexes Containing Magnesium and Zinc[J]. Acta Physico-Chimica Sinica, 2011, 27(11): 2682-2690. doi: 10.3866/PKU.WHXB20111132 shu

竹红菌乙素镁、锌配位聚合物的光物理和光生物性质

基金项目:
国家自然科学基金(21073143) (21073143)

教育部&ldquo

春晖计划&rdquo

基金(Z2009-1-71002, Z2009-1-71006) (Z2009-1-71002, Z2009-1-71006)

西北工业大学基础研究基金(JC200822,JC20100239)资助项目 (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(Ф_T)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(f_Δ^T)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:

English

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

1.
Key Laboratory of Space, Applied Physics and Chemistry, Ministry of Education, School of Science, Northwestern Polytechnical University, Xi'an 710072
Received Date: 19 July 2011
Available Online: 27 October 2011
Fund Project:
国家自然科学基金(21073143)

教育部&ldquo

春晖计划&rdquo

基金(Z2009-1-71002, Z2009-1-71006)

西北工业大学基础研究基金(JC200822,JC20100239)资助项目

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 (Φ_T) and the fraction of triplet states quenched by O₂ that yield ¹O₂ (f_Δ^T) 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:

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沈阳化工大学材料科学与工程学院沈阳 110142

竹红菌乙素镁、锌配位聚合物的光物理和光生物性质

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

竹红菌乙素镁、锌配位聚合物的光物理和光生物性质

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs