铱、铂配合物磷光探针的设计、合成及其在传感和成像中的应用
发布时间：2018-11-21 14:51
【摘要】：磷光过渡金属配合物因其优良的光物理性质,引起了研究者的广泛关注。基于铱、铂、钌等的磷光过渡金属配合物具有高的发光效率、易调节的激发波长和发射波长(覆盖了整个可见光区域甚至近红外)、大的斯托克斯位移(通常大于5000 cm-1)以及较长的发光寿命等特点。大的斯托克斯位移使其容易区分激发和发射从而减少自吸收过程,而较长的发射寿命(通常为几百纳秒到几十微秒)使其能够利用时间分辨技术来消除背景荧光的干扰。以上这些性质使磷光过渡金属配合物非常适合用于生物或化学传感材料,在本论文中,我们旨在发展新的磷光过渡金属配合物材料并研究其光物理性质及对目标分析物的响应性。我们设计合成了3种具有聚集诱导发光增强效应的铂配合物,并实现了在活细胞成像中的应用;此外,我们进一步设计合成了一种猝灭型的次氯酸根磷光探针,实现了对次氯酸根离子的磷光检测。主要研究内容如下:1、聚集诱导磷光发射铂配合物的设计、合成、光物理性质及在细胞成像中的应用在前期工作基础上,我们进一步将给电子或吸电子取代基引入席夫碱配体中,合成了三种新型的席夫碱铂配合物,利用1H NMR对其结构进行了表征,对配合物ppyPtN-Ph F5的单晶结构做了X-射线分析,并对其光物理性质进行了研究。室温下,这三种配合物在溶液中是不发光的,在固体状态下却表现出很强的磷光发射,最大量子效率达到0.39。其中给电子甲氧基的引入对最大发射峰的位移影响不大,而吸电子取代基五氟苯基的引入使配合物的发射红移。此外,我们利用具有核壳结构的介孔二氧化硅纳米粒子作为探针载体,将ppyPtN-Ph M吸附到介孔二氧化硅纳米硅球中,形成纳米磷光生物探针Pt1@MSN。纳米磷光生物探针Pt1@MSN具有较低的生物毒性可以实现对活细胞中胞浆的成像,具有较好的成像效果。2、含对氨基苯酚醚基团的磷光铱配合物的合成及其对次氯酸根离子的响应性我们将对氨基苯酚醚基团引入到铱配合物的环金属配体中,设计合成了一种新型的次氯酸根离子的磷光探针Ir1。利用1H NMR和质谱对其结构进行了表征,并对其光物理性质进行了研究,配合物Ir1最大发射峰位于521 nm,呈现黄绿光发射。随次氯酸根离子的加入,配合物Ir1中的对氨基苯酚醚基团会以4-亚氨基环己烷-2,5-二烯酮脱去,配合物Ir1的磷光发射逐渐减弱,直至猝灭,实现了对次氯酸根离子的“Turn-off”型检测。此外,配合物Ir1对次氯酸根离子具有较好的选择性。
[Abstract]:Phosphorescent transition metal complexes have attracted much attention due to their excellent photophysical properties. Phosphorescence transition metal complexes based on iridium, platinum and ruthenium have high luminescence efficiency, easy to adjust excitation and emission wavelengths (covering the entire visible region and even near infrared). Large Stokes shift (usually more than 5000 cm-1) and longer luminescence lifetime. The large Stokes shift makes it easy to distinguish between excitation and emission, thus reducing the self-absorption process, while the longer emission lifetime (usually hundreds of nanoseconds to tens of microseconds) enables it to eliminate background fluorescence interference by using time-resolved techniques. These properties make phosphorescent transition metal complexes very suitable for use in biological or chemical sensing materials. We aim to develop new phosphorescent transition metal complex materials and study their photophysical properties and responsiveness to target analytes. We designed and synthesized three kinds of platinum complexes with aggregation induced luminescence enhancement effect and realized their applications in living cell imaging. In addition, we further designed and synthesized a quenched hypochlorite phosphorescence probe to detect hypochlorite ion. The main research contents are as follows: 1. The design, synthesis, photophysical properties and application in cell imaging of the aggregation induced phosphorescent platinum complex are based on the previous work. Three new Schiff base platinum complexes were synthesized by introducing electron donor or electron absorbent substituents into Schiff base ligands. Their structures were characterized by 1H NMR, and the single crystal structure of ppyPtN-Ph F5 was characterized by X-ray analysis. The photophysical properties are also studied. At room temperature, these complexes are not luminescent in solution, but exhibit strong phosphorescence emission in solid state. The maximum quantum efficiency is 0.39. The introduction of electron methoxy has little effect on the shift of the maximum emission peak, while the introduction of electron absorbing substituted pentafluorophenyl makes the emission red shift of the complex. In addition, we used mesoporous silica nanoparticles with core-shell structure as probe carrier to adsorb ppyPtN-Ph M onto mesoporous silica nanospheres to form nano-phosphorescence biological probe Pt1@MSN.. The nano-phosphorescence biological probe Pt1@MSN has low biotoxicity, which can realize the imaging of cytoplasm in living cells, and has a better imaging effect. Synthesis of Phosphoiridium complexes containing p-Aminophenol Ether Group and their responsiveness to hypochlorite Ions We introduced p-aminophenol ether groups into the cyclic metal ligands of iridium complexes. A novel phosphor probe Ir1. for hypochlorite ion was designed and synthesized. The structure and photophysical properties of the complex were characterized by 1H NMR and mass spectrometry. The maximum emission peak of the complex Ir1 was located at 521 nm,. With the addition of hypochlorite ion, the p-aminophenol ether group in the complex Ir1 was removed by 4-iminocyclohexane-2o 5-dienone, and the phosphorescence emission of the complex Ir1 decreased gradually until quenching. The determination of hypochlorite ion by "Turn-off" type was realized. In addition, the complex Ir1 has good selectivity for hypochlorite ion.
【学位授予单位】：南京邮电大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;O657.3
本文编号：2347294
[Abstract]:Phosphorescent transition metal complexes have attracted much attention due to their excellent photophysical properties. Phosphorescence transition metal complexes based on iridium, platinum and ruthenium have high luminescence efficiency, easy to adjust excitation and emission wavelengths (covering the entire visible region and even near infrared). Large Stokes shift (usually more than 5000 cm-1) and longer luminescence lifetime. The large Stokes shift makes it easy to distinguish between excitation and emission, thus reducing the self-absorption process, while the longer emission lifetime (usually hundreds of nanoseconds to tens of microseconds) enables it to eliminate background fluorescence interference by using time-resolved techniques. These properties make phosphorescent transition metal complexes very suitable for use in biological or chemical sensing materials. We aim to develop new phosphorescent transition metal complex materials and study their photophysical properties and responsiveness to target analytes. We designed and synthesized three kinds of platinum complexes with aggregation induced luminescence enhancement effect and realized their applications in living cell imaging. In addition, we further designed and synthesized a quenched hypochlorite phosphorescence probe to detect hypochlorite ion. The main research contents are as follows: 1. The design, synthesis, photophysical properties and application in cell imaging of the aggregation induced phosphorescent platinum complex are based on the previous work. Three new Schiff base platinum complexes were synthesized by introducing electron donor or electron absorbent substituents into Schiff base ligands. Their structures were characterized by 1H NMR, and the single crystal structure of ppyPtN-Ph F5 was characterized by X-ray analysis. The photophysical properties are also studied. At room temperature, these complexes are not luminescent in solution, but exhibit strong phosphorescence emission in solid state. The maximum quantum efficiency is 0.39. The introduction of electron methoxy has little effect on the shift of the maximum emission peak, while the introduction of electron absorbing substituted pentafluorophenyl makes the emission red shift of the complex. In addition, we used mesoporous silica nanoparticles with core-shell structure as probe carrier to adsorb ppyPtN-Ph M onto mesoporous silica nanospheres to form nano-phosphorescence biological probe Pt1@MSN.. The nano-phosphorescence biological probe Pt1@MSN has low biotoxicity, which can realize the imaging of cytoplasm in living cells, and has a better imaging effect. Synthesis of Phosphoiridium complexes containing p-Aminophenol Ether Group and their responsiveness to hypochlorite Ions We introduced p-aminophenol ether groups into the cyclic metal ligands of iridium complexes. A novel phosphor probe Ir1. for hypochlorite ion was designed and synthesized. The structure and photophysical properties of the complex were characterized by 1H NMR and mass spectrometry. The maximum emission peak of the complex Ir1 was located at 521 nm,. With the addition of hypochlorite ion, the p-aminophenol ether group in the complex Ir1 was removed by 4-iminocyclohexane-2o 5-dienone, and the phosphorescence emission of the complex Ir1 decreased gradually until quenching. The determination of hypochlorite ion by "Turn-off" type was realized. In addition, the complex Ir1 has good selectivity for hypochlorite ion.
【学位授予单位】：南京邮电大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;O657.3
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2 Hao-Ran Xu;Kun Li;Shu-Yan Jiao;Ling-Ling Li;Sheng-Lin Pan;Xiao-Qi Yu;;Tetraphenylethene based zinc complexes as fluorescent chemosensors for pyrophosphate sensing[J];Chinese Chemical Letters;2015年07期
3 成珊;刘淑娟;周丽霞;许文娟;赵强;黄维;;基于重金属配合物的阳离子磷光化学传感器[J];化学进展;2011年04期
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