基于多胺配合物的酶中心模拟物荧光标记及其应用
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摘要
荧光成像技术是分子影像技术的一种,它具有灵敏度高、分辨率好、实时快速以及原位无损检测等优点,在临床医学和基础生命科学研究中具有重大的应用价值。采用对酶活性中心模拟物进行荧光标记的方法,可以实现对生物体中活性小分子和金属离子的高选择性识别与荧光成像,为反映金属离子和生物活性小分子在生命体中的真实存在状态及浓度分布提供了便利,同时也为研究生物体中的生理反应过程和致病机理提供了有效手段,成为近年来的热点研究内容之一。本论文采用与金属络合能力较强的多胺化合物为配体,传统的荧光染料为荧光标记物,构建了系列带有荧光标记的酶活性中心模拟物,并研究了其在生物活性小分子和金属离子识别与荧光成像中的应用。
1.构建了系列以传统荧光染料为荧光标记的铜酶活性中心模拟物,并研究了其在一氧化氮(NO)识别与荧光成像中的应用。CuFL2(以三(2-氨基乙基)胺(Tren)为配体)和CuFL3(以1,4,7,10-四氮杂环十二烷(cyclen)为配体)均采用罗丹明B为荧光标记基团,结合NO与Cu(Ⅱ)的氧化还原反应和罗丹明B的开环反应来识别NO。CuFL2和CuFL3均实现了对NO快速(30s内即产生荧光增强型响应)且高选择性的识别。其中CuFL2的荧光增强可达到700倍(荧光量子产率0.13),检测限达1nM(目前最低)；CuFL3的荧光量子产率达到0.16。两者均可应用于NO的细胞成像。CuFL5(以乙二胺为配体)引入1,8-萘酰亚胺作为荧光标记基团,利用反应后1,8-萘酰亚胺荧光的恢复和增强来识别NO。CuFL5同样实现了对NO迅速、高选择性且高灵敏度(检测限达1nM)的识别,并同样可应用于NO的细胞成像。较单纯的荧光增强型响应而言,比率型响应具有更广泛的应用价值。通过同时引入罗丹明和香豆素两种荧光基团,得到了一类带有两种荧光标记的铜酶活性中心模拟物CuFL6(以Tren为配体)。CuFL6可对NO产生比率型荧光响应,且具有良好的选择性。细胞成像显示,CuFL6可用于生物体内NO的比率成像。
2.基于FRET机理构建了带有双荧光标记的葡萄糖耐量因子(GTF)和CuZnSOD活性中心模拟物。将香豆素标记于谷胱甘肽分子作为GTF活性中心模拟物(FL7),罗丹明6G标记于葡萄糖分子作为底物(FL8),得到了用于Cr3+识别的探针体系FL7：FL8(1：2)。模拟GTF与底物的作用过程,该探针体系的两部分(FL7和FL8)可通过Cr3+连为一体,从而产生比率型荧光响应。利用这一方法探针体系实现了对Cr3+的高选择性识别,检测限达0.1ppm,并可应用于Cr3+的细胞成像。本文还构建了带有两种不同荧光标记的铜铜同核CuZnSOD活性中心模拟物CuFL1-im-CuFL9和CuFL2-im-CuFL9,以及铜锌异核CuZnSOD活性中心模拟物CuFL1-im-ZnFL9,为超氧负离子的识别与成像研究提供了一个新平台。
Fluorescence imaging, a kind of molecular imaging technology, with high sensitivity and good resolution, could detect substrate fast in real-time and in-situ with nondestructive, exhibiting high value in applications of clinical medicine and the research of basic life science. The high selective recognition and fluorescence imaging of biomolecules by labeling the models of enzyme acitivity centers could reflect the real existence and concentration distribution of the biomolecular and metal ion in organism, and were benefited to the research of the physiological reactions and pathogenesis, becoming one of the hot issues recently. In this paper, a series of labeled models of enzyme activity center, with polyamine (strong chelator of metal ions) as ligand and traditional fluorescence dyes as indicators, were designed and synthesized. Its applications in detection and fluorescence imaging of the biomolecular and metal ion were then investigated.
1. A series of models of copper enzyme activity center, labeling with the traditional fluorescence dyes were assembled, and its applications in detection and fluorescence imaging of nitric oxide (NO) were studied. By incorporating a Rhodamine B moiety as the fluorescent indicator, CuFL2(with tis(2-aminoethyl)amine (Tren) as the chelator) and CuFL3(with1,4,7,10-Tetraazacyclododecane (cyclen) as the chelator) was obtained as models of the copper enzyme activity center. They both gave a rapid (the fluorescence enhanced within30s) and high selective response toward NO through the ring-open of the rhodamine B moiety, causing by the reaction of NO and Cu(Ⅱ). Especially, CuFL2showed a700-fold fluorescence enhancement to NO (quantum yield0.13) with the detection limit of1nM, which is the best of the NO fluorescence sensors reported. And the quantum yield of CuFL3was0.16(detection limit1μM). Furthermore, they both could be applied to the NO imaging in vitro. By introducing1,8-naphthaleneimide as the luminescence unit, CuFL5with ethanediamine was synthesized as another model of copper enzyme activity center. The fluorescence was restoring by the reduction of Cu(Ⅱ) to Cu(Ⅰ), and enhanced by the generation of FL5-NO. CuFL5also exhibited a rapid (the fluorescence enhanced within30s), high selective and high sensitive (detection limit1nM) response to NO, and could also be applied to the NO imaging in vitro. Compared to the enhanced response, the ratio of two signals had more extensive value of application. Therefore, CuFL6(with Tren as the chelator) with both rhodamine and coumarin as the fluorescence unit was obtained as another model of copper enzyme activity center. It gave a fluorescence ratio response toward NO, which was specific. The cell imaging experiment proved that CuFL6could image NO through the fluorescence ratio changes.
2. The models of the activity center of glucose tolerance factor (GTF) and CuZnSOD, with two different fluorescent indicators, were constructed based on the FRET mechanism. The detection system FL7:FL8(1:2) of Cr3+was comprised by two parts:a coumarin-labeled glutathione as the model of GTF activity center (FL7), and a rhodamine-labeled glucose as the substrate (FL8). According to the reaction of GTF and glucose in organism, FL7and FL8could be connected together through Cr3+, leading to a ratio response toward Cr3+. It improved the selectivity toward Cr3+with the detection limit of0.1ppm, and be used in cell imaging of Cr3+. In this paper, two different Cu-Cu homonuclear complexes, CuFL1-im-CuFL9and CuFL2-im-CuFL9, and a Cu-Zn heteronuclear complex, CuFL1-im-ZnFL9, as the models of the CuZnSOD activity center with different labels was constructed.It provides a new platform for the research of super oxygen anion detection and imaging.
1.构建了系列以传统荧光染料为荧光标记的铜酶活性中心模拟物,并研究了其在一氧化氮(NO)识别与荧光成像中的应用。CuFL2(以三(2-氨基乙基)胺(Tren)为配体)和CuFL3(以1,4,7,10-四氮杂环十二烷(cyclen)为配体)均采用罗丹明B为荧光标记基团,结合NO与Cu(Ⅱ)的氧化还原反应和罗丹明B的开环反应来识别NO。CuFL2和CuFL3均实现了对NO快速(30s内即产生荧光增强型响应)且高选择性的识别。其中CuFL2的荧光增强可达到700倍(荧光量子产率0.13),检测限达1nM(目前最低)；CuFL3的荧光量子产率达到0.16。两者均可应用于NO的细胞成像。CuFL5(以乙二胺为配体)引入1,8-萘酰亚胺作为荧光标记基团,利用反应后1,8-萘酰亚胺荧光的恢复和增强来识别NO。CuFL5同样实现了对NO迅速、高选择性且高灵敏度(检测限达1nM)的识别,并同样可应用于NO的细胞成像。较单纯的荧光增强型响应而言,比率型响应具有更广泛的应用价值。通过同时引入罗丹明和香豆素两种荧光基团,得到了一类带有两种荧光标记的铜酶活性中心模拟物CuFL6(以Tren为配体)。CuFL6可对NO产生比率型荧光响应,且具有良好的选择性。细胞成像显示,CuFL6可用于生物体内NO的比率成像。
2.基于FRET机理构建了带有双荧光标记的葡萄糖耐量因子(GTF)和CuZnSOD活性中心模拟物。将香豆素标记于谷胱甘肽分子作为GTF活性中心模拟物(FL7),罗丹明6G标记于葡萄糖分子作为底物(FL8),得到了用于Cr3+识别的探针体系FL7：FL8(1：2)。模拟GTF与底物的作用过程,该探针体系的两部分(FL7和FL8)可通过Cr3+连为一体,从而产生比率型荧光响应。利用这一方法探针体系实现了对Cr3+的高选择性识别,检测限达0.1ppm,并可应用于Cr3+的细胞成像。本文还构建了带有两种不同荧光标记的铜铜同核CuZnSOD活性中心模拟物CuFL1-im-CuFL9和CuFL2-im-CuFL9,以及铜锌异核CuZnSOD活性中心模拟物CuFL1-im-ZnFL9,为超氧负离子的识别与成像研究提供了一个新平台。
Fluorescence imaging, a kind of molecular imaging technology, with high sensitivity and good resolution, could detect substrate fast in real-time and in-situ with nondestructive, exhibiting high value in applications of clinical medicine and the research of basic life science. The high selective recognition and fluorescence imaging of biomolecules by labeling the models of enzyme acitivity centers could reflect the real existence and concentration distribution of the biomolecular and metal ion in organism, and were benefited to the research of the physiological reactions and pathogenesis, becoming one of the hot issues recently. In this paper, a series of labeled models of enzyme activity center, with polyamine (strong chelator of metal ions) as ligand and traditional fluorescence dyes as indicators, were designed and synthesized. Its applications in detection and fluorescence imaging of the biomolecular and metal ion were then investigated.
1. A series of models of copper enzyme activity center, labeling with the traditional fluorescence dyes were assembled, and its applications in detection and fluorescence imaging of nitric oxide (NO) were studied. By incorporating a Rhodamine B moiety as the fluorescent indicator, CuFL2(with tis(2-aminoethyl)amine (Tren) as the chelator) and CuFL3(with1,4,7,10-Tetraazacyclododecane (cyclen) as the chelator) was obtained as models of the copper enzyme activity center. They both gave a rapid (the fluorescence enhanced within30s) and high selective response toward NO through the ring-open of the rhodamine B moiety, causing by the reaction of NO and Cu(Ⅱ). Especially, CuFL2showed a700-fold fluorescence enhancement to NO (quantum yield0.13) with the detection limit of1nM, which is the best of the NO fluorescence sensors reported. And the quantum yield of CuFL3was0.16(detection limit1μM). Furthermore, they both could be applied to the NO imaging in vitro. By introducing1,8-naphthaleneimide as the luminescence unit, CuFL5with ethanediamine was synthesized as another model of copper enzyme activity center. The fluorescence was restoring by the reduction of Cu(Ⅱ) to Cu(Ⅰ), and enhanced by the generation of FL5-NO. CuFL5also exhibited a rapid (the fluorescence enhanced within30s), high selective and high sensitive (detection limit1nM) response to NO, and could also be applied to the NO imaging in vitro. Compared to the enhanced response, the ratio of two signals had more extensive value of application. Therefore, CuFL6(with Tren as the chelator) with both rhodamine and coumarin as the fluorescence unit was obtained as another model of copper enzyme activity center. It gave a fluorescence ratio response toward NO, which was specific. The cell imaging experiment proved that CuFL6could image NO through the fluorescence ratio changes.
2. The models of the activity center of glucose tolerance factor (GTF) and CuZnSOD, with two different fluorescent indicators, were constructed based on the FRET mechanism. The detection system FL7:FL8(1:2) of Cr3+was comprised by two parts:a coumarin-labeled glutathione as the model of GTF activity center (FL7), and a rhodamine-labeled glucose as the substrate (FL8). According to the reaction of GTF and glucose in organism, FL7and FL8could be connected together through Cr3+, leading to a ratio response toward Cr3+. It improved the selectivity toward Cr3+with the detection limit of0.1ppm, and be used in cell imaging of Cr3+. In this paper, two different Cu-Cu homonuclear complexes, CuFL1-im-CuFL9and CuFL2-im-CuFL9, and a Cu-Zn heteronuclear complex, CuFL1-im-ZnFL9, as the models of the CuZnSOD activity center with different labels was constructed.It provides a new platform for the research of super oxygen anion detection and imaging.
引文
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