Studies on Novel Syntheses of Fluorecent Tripodal Hexadentate Iigands and Than Application to fluorescent Probes for Microscopic Observation of Cells

本计画主要研究新型二齿及六齿萤光配体的合成及其在细胞显微观察萤光探针中的应用。1.合成了一个新的荧光双齿配体（a）：3-羟基-4（1H）-吡啶酮直接连接到喹喔啉上。2.合成了一个新的荧光双齿配体（B）6-（2 '，3'-二羟基苄基）氨基-2，3-二吗啉基喹喔啉。3.合成了一个C-6位带有L-脯氨酸残基的手性喹喔啉（c）。4.合成了一个在C-6和C-8位上带有二芳基取代基的咪唑并吡嗪（d）。6.双齿配体（a）与Fe（III）、Al（III）、Ga（III）和Cr（III）形成3：1络合物。通过静态猝灭的Perrin模型，金属络合物的形成有效地猝灭了荧光。 ...更多信息 结果表明，Fe（Ⅲ）对Al（Ⅲ）的猝灭效率为：Fe（Ⅲ）>>Al（Ⅲ）>Ga（M）>Cr（Ⅲ）。用N-苯甲酰基去甲苯胺B去除Fe（III），荧光恢复。7.在双齿配体（B）的情况下，在碱性条件下观察到一个独特的吸收带，这是由于分子内电荷从邻苯二酚部分转移到不带电的喹喔啉。8.用手性喹喔啉（c）衍生化吗诺芬、布洛芬和2-苯基丙酸，得到非对映异构体，在反相HPLC上在16 min内明显分离，在S/N=5时检测限为5 pmol/10 μL进样体积。9.与鲁米诺相比，咪唑吡嗪（d）对超氧化物显示出足够的灵敏度，似乎能够检测超氧化物。咪唑并嗪（d）具有pH依赖性双峰化学发光。咪唑并吡嗪（d）的这些性质使我们能够将其应用于同时检测生物系统中的两个并发事件，超氧化物评价和pH滴定。少

In this project, we investigated syntheses of novel fluorescent bidentate and hexadentate ligands and their application to the fluorescent probes for microscopic observation of cells. The following points became dear.1.Anew fluorescent bidentate ligand (a), 3-hydroxy-4(1H)-pyridinone directly attached to quinoxaline, was synthesized. 2.Anew fluorescent bidentate ligand (b), 6-(2',3'-dihydroxybenzyl)amino-2,3-dimorpholino quinoxaline, was synthesized. 3.A chiral quinoxaline (c) bearing the L-praline residue at C-6 position was synthesized. 4.A fluorescent imidazopyrazine (d) bearing diaryl substituents at C-6 and C-8 positions was synthesized 5.Unfortunately, the desired fluorescent tripodal hexadentate ligands could not be obtained owing to the insolubility of synthetic intermediates. 6.The bidentate ligand (a) formed 3:1 complexes with Fe(III), Al(III), Ga(III), and Cr(III). The fluorescence was efficiently quenched by the metal complex formation via the Perrin model of static quenchi … More ng, the quenching efficiency being in order of Fe(III)>>Al(III)>Ga(M)>Cr(III). The fluorescence was recoverd by removal of Fe(III) with N-benzoyl desfenioxamine B. 7.In case of bidentate ligand (b), a unique absorption band due to the intramolecular charge transfer from the catechol moiety to electro-defident quinoxaline was observed under basic conditions. 8.The derivatization of mcemic naproxen, ibuprofen, and 2 phenylpropionic acid with chiral quinoxaline (c) afforded the diastereomers, which were dearly separated within 16 min on reversed phase HPLC with a detection limit of 5 pmol/10 μL injection volume at S/N=5. 9.Imidazopyrazine (d) showed enough sensitivity to superoxide in comparison with luminol and appears to be capable of superoxide detection. Further, imidazopytazine (d) exhibited the pH dependent bimodal chemiluminescence. These properties of imidazopyrazine(d) allows us to apply it for simultaneous detection of the two concurrent events, superoxide evaluation and pH titration, in biological systems. Less