新型阳离子型金属配合物和聚合物的合成、性质表征及与DNA的相互作用研究
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摘要
钌配合物由金属钌与配体两部分组成,具有刚性的八面体结构、良好的光热稳定性、较好的溶解性以及丰富的氧化还原性质等特点,因此在生物大分子识别、电化学发光、太阳能电池以及有机电致发光器件等领域都有广泛的应用前景。另一方面阳离子型共轭聚合物材料通常具有很好的荧光特性,尤其在生物大分子识别方面比小分子材料更有优势,表现在与生物大分子相互作用过程中电荷与能量可以沿着共轭高分子的刚性长链传递,能够显著地对相互作用的信号进行放大,所以这类材料在生物大分子的检测方面受到了人们的广泛关注,发展非常迅速。本论文设计合成了几种新型的阳离子型钌联吡啶配合物和聚双吡啶盐,研究了它们的性质以及与DNA的相互作用。
第一部分:设计合成了三种新型的钌联吡啶配合物,表征了其性能,研究了它们与DNA的相互作用。
首先,通过在具有优异的光物理及电化学性能的钌联吡啶配合物(Ru(bpy)_3~(2+))母体结构上引入一些具有特殊功能的基团,设计合成了三种阳离子型配合物012、015和016。然后,通过紫外可见光谱、荧光光谱及循环伏安法表征了这三种钌配合物的光物理以及电化学性能。实验结果表明这些钌配合物具有特征的MLCT跃迁以及稳定的氧化还原性质。接着,研究了这三种配合物的电致发光性能,其器件结构为ITO/PEDOT-PSS/complex/Al,器件发出纯正的红光,但发光效率极低,可能由于配合物的溶解度较差。最后,研究了这三种配合物与DNA的相互作用。通过考察DNA的加入量对三种配合物的紫外可见光谱、荧光光谱的影响,探讨了这三种配合物与DNA的结合模式、结合常数以及不同的配体类型和结构对二者之间相互作用的影响。
第二部分:设计合成了两种阳离子型聚双吡啶盐,表征了其性能,研究了它们与DNA相互作用。
首先,通过杯[4]芳烃二胺衍生物与双嗡盐逐步聚合制备了两种新型的聚双吡啶盐。这种聚双吡啶盐的结构特征在于:1)双吡啶盐结构单元作为荧光基团,由于其带有正电荷,大大提高了聚合物的亲水性,而且能够与DNA上带有负电荷的磷酸根形成静电相互作用;2)杯[4]芳烃结构单元具有良好的脂溶性,结构柔性,可以灵活地适应DNA分子二级结构的多样性。然后,利用核磁共振光谱、红外光谱、元素分析等分析手段对聚合物的结构进行了确定。接着,对它们的热性能、结晶度以及溶解性进行了表征,实验结果表明:这两种聚合物在N2和空气中均表现出很好的热稳定性;它们在常见有机溶剂中也显示出很好的溶解性。采用紫外可见光谱和荧光光谱的方法研究了这两种聚合物溶液的光谱性质,考察了实验条件比如激发波长,溶剂极性等对聚合物光谱性质的影响。最后,通过荧光滴定法和透射电子显微镜法等手段研究了这两种聚合物与DNA的相互作用,结果表明这类聚合物对DNA有浓缩作用,其主要的驱动力可能是静电相互作用。
Ruthenium complexes composed by Ru and legends have many excellent characteristics such as good photothermal stability, good solubility, rich redox properties and the rigid octahedral structure and so on. Thus, such complexes have a wide application in many fields, such as organic semiconductor materials, electrochemical luminescence, solar cells and light-emitting devices etc. On the other hand, recently, using cationic conjugated polymers as sensors for DNA have attracted great attention due to several important advantages, such as signal amplification, easy fabrication into devices, and combination of different outputs. Therefore, this thesis aimed to study on the synthesis, characterization and interaction with DNA of several ruthenium complexes and novel poly (pyridinium salt)s.
Part I: Three ruthenium bipyridyl complexes were synthesized, which exhibited excellent physical and electrochemical properties. Their photophysical and electrochemical properties of the three complexes were characterized by means of UV-vis, FL spectra and cyclic voltammetric (CV) techniques. The results showed that these complexes have unique MLCT process and stable redox properties. Moreover, we studied the electroluminescent properties of the three complexes. The simple device for each complex was prepared with the structure of ITO/PEDOT-PSS/complex/Al, and pure red light emission was obtained with very low luminescent efficiency. Finally, the interaction of these complexes with calf thymus DNA was investigated by the spectrum titration method. Based on these results, interaction model between the complexes and DNA as well as the influence of complex structure on the interaction were discussed.
Part II: Novel poly (pyridinium salt)s were synthesized by stepwise polymerization of the calix[4]arene diamine with the dipyrylium. The features of these poly (pyridinium salt)s are as following: 1) dipyridinium salts units as fluorescent groups. These positively charged poly (pyridinium salt)s has good hydrophilicity, and can interact with negatively charged DNA; 2) calix[4]arene units as recognition site, which can interact with counter ion of Na+ of DNA, while their structural flexibility will facilitate the corresponding polymer to dissolve in various organic solvents and will facilitate polymers to adjust their structure to meet the shape adaptability with the secondary structure of biological macromolecules. Poly (pyridinium salt)s were synthesized and characterized by NMR, FTIR and elemental analyses. Their thermal properties, crystallization and solubility were also characterized. Their optical properties in solution were investigated by UV-vis and photoluminescence spectroscopy. The effct of the experimental factors such as excitation wavelength and the polarity of solvent on fluorescent emission spectra of polymers was studied in detail. Finally, the interaction between the two polymers and DNA are investigated through PL titration and transmission electron microscopy (TEM). It was found that these polymers could contract DNA. The electrostatic interactions of the positively charged polymer with the negatively charged DNA should be one of predominant driving forces.
第一部分:设计合成了三种新型的钌联吡啶配合物,表征了其性能,研究了它们与DNA的相互作用。
首先,通过在具有优异的光物理及电化学性能的钌联吡啶配合物(Ru(bpy)_3~(2+))母体结构上引入一些具有特殊功能的基团,设计合成了三种阳离子型配合物012、015和016。然后,通过紫外可见光谱、荧光光谱及循环伏安法表征了这三种钌配合物的光物理以及电化学性能。实验结果表明这些钌配合物具有特征的MLCT跃迁以及稳定的氧化还原性质。接着,研究了这三种配合物的电致发光性能,其器件结构为ITO/PEDOT-PSS/complex/Al,器件发出纯正的红光,但发光效率极低,可能由于配合物的溶解度较差。最后,研究了这三种配合物与DNA的相互作用。通过考察DNA的加入量对三种配合物的紫外可见光谱、荧光光谱的影响,探讨了这三种配合物与DNA的结合模式、结合常数以及不同的配体类型和结构对二者之间相互作用的影响。
第二部分:设计合成了两种阳离子型聚双吡啶盐,表征了其性能,研究了它们与DNA相互作用。
首先,通过杯[4]芳烃二胺衍生物与双嗡盐逐步聚合制备了两种新型的聚双吡啶盐。这种聚双吡啶盐的结构特征在于:1)双吡啶盐结构单元作为荧光基团,由于其带有正电荷,大大提高了聚合物的亲水性,而且能够与DNA上带有负电荷的磷酸根形成静电相互作用;2)杯[4]芳烃结构单元具有良好的脂溶性,结构柔性,可以灵活地适应DNA分子二级结构的多样性。然后,利用核磁共振光谱、红外光谱、元素分析等分析手段对聚合物的结构进行了确定。接着,对它们的热性能、结晶度以及溶解性进行了表征,实验结果表明:这两种聚合物在N2和空气中均表现出很好的热稳定性;它们在常见有机溶剂中也显示出很好的溶解性。采用紫外可见光谱和荧光光谱的方法研究了这两种聚合物溶液的光谱性质,考察了实验条件比如激发波长,溶剂极性等对聚合物光谱性质的影响。最后,通过荧光滴定法和透射电子显微镜法等手段研究了这两种聚合物与DNA的相互作用,结果表明这类聚合物对DNA有浓缩作用,其主要的驱动力可能是静电相互作用。
Ruthenium complexes composed by Ru and legends have many excellent characteristics such as good photothermal stability, good solubility, rich redox properties and the rigid octahedral structure and so on. Thus, such complexes have a wide application in many fields, such as organic semiconductor materials, electrochemical luminescence, solar cells and light-emitting devices etc. On the other hand, recently, using cationic conjugated polymers as sensors for DNA have attracted great attention due to several important advantages, such as signal amplification, easy fabrication into devices, and combination of different outputs. Therefore, this thesis aimed to study on the synthesis, characterization and interaction with DNA of several ruthenium complexes and novel poly (pyridinium salt)s.
Part I: Three ruthenium bipyridyl complexes were synthesized, which exhibited excellent physical and electrochemical properties. Their photophysical and electrochemical properties of the three complexes were characterized by means of UV-vis, FL spectra and cyclic voltammetric (CV) techniques. The results showed that these complexes have unique MLCT process and stable redox properties. Moreover, we studied the electroluminescent properties of the three complexes. The simple device for each complex was prepared with the structure of ITO/PEDOT-PSS/complex/Al, and pure red light emission was obtained with very low luminescent efficiency. Finally, the interaction of these complexes with calf thymus DNA was investigated by the spectrum titration method. Based on these results, interaction model between the complexes and DNA as well as the influence of complex structure on the interaction were discussed.
Part II: Novel poly (pyridinium salt)s were synthesized by stepwise polymerization of the calix[4]arene diamine with the dipyrylium. The features of these poly (pyridinium salt)s are as following: 1) dipyridinium salts units as fluorescent groups. These positively charged poly (pyridinium salt)s has good hydrophilicity, and can interact with negatively charged DNA; 2) calix[4]arene units as recognition site, which can interact with counter ion of Na+ of DNA, while their structural flexibility will facilitate the corresponding polymer to dissolve in various organic solvents and will facilitate polymers to adjust their structure to meet the shape adaptability with the secondary structure of biological macromolecules. Poly (pyridinium salt)s were synthesized and characterized by NMR, FTIR and elemental analyses. Their thermal properties, crystallization and solubility were also characterized. Their optical properties in solution were investigated by UV-vis and photoluminescence spectroscopy. The effct of the experimental factors such as excitation wavelength and the polarity of solvent on fluorescent emission spectra of polymers was studied in detail. Finally, the interaction between the two polymers and DNA are investigated through PL titration and transmission electron microscopy (TEM). It was found that these polymers could contract DNA. The electrostatic interactions of the positively charged polymer with the negatively charged DNA should be one of predominant driving forces.
引文
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