School of Materials Science and Engineering, University of Jinan, Jinan 250022, Shandong, China.
School of Materials Science and Engineering, University of Jinan, Jinan 250022, Shandong, China.
Talanta. 2018 May 1;181:118-124. doi: 10.1016/j.talanta.2017.12.062. Epub 2017 Dec 22.
Two 3-hydroxyflavone derivatives as one- and two-photon fluorescent chemosensors for cysteine (Cys) and homocysteine (Hcy) were synthesized. The recognition properties and mechanism of the chemosensors for Cys and Hcy were investigated systematically. The experiment results indicate that 3-hydroxyflavone compound 1 (6-bromo-2-(9-ethyl-9H-carbazol-3-yl)-3-hydroxy-chromen-4-one) after the addition of nickel ions exhibits good recognition properties for Cys and Hcy with fluorescence enhancement and 65nm absorption peak blue shift based on nickel displacement reaction mechanism. The detection limits (DL) with fluorescence as detected signal are 4.06 × 10µM (Cys, linear range of 10-80µM) and 5.8 × 10µM (Hcy, linear range of 10-100µM), respectively. But acrylate substituted 3-hydroxyflavone compound 2 (4-oxo-2-(4-diethylamino-phenyl)-4H-chromen-3-yl acrylate) can specially identify Cys with fluorescence turn-on (DL = 1.87 × 10µM, linear range of 4-22µM) based on Cys leading to acrylate hydrolysis mechanism and succedent excited-state intramolecular proton transfer process of 3-hydroxyflavone compound. Then Cys and Hcy biological thiols can be recognized at one time by these two 3-hydroxyflavone derivatives. The bioimaging experiment indicates that both the compounds can be successfully applied to the detection of Cys/Hcy in living cells and compound 2 also can be applied to bioimaging Cys in zebrafish by one- and two-photon fluorescence mode. Then these two compounds have a potential in the application of biological sample analysis.
两种 3-羟基黄酮衍生物作为一种和双光子荧光化学传感器用于半胱氨酸（Cys）和同型半胱氨酸（Hcy）的检测。系统研究了化学传感器对 Cys 和 Hcy 的识别特性和机制。实验结果表明，3-羟基黄酮化合物 1（6-溴-2-（9-乙基-9H-咔唑-3-基）-3-羟基色满-4-酮）在加入镍离子后，基于镍取代反应机制，对 Cys 和 Hcy 表现出良好的荧光增强和 65nm 吸收峰蓝移的识别性能。以荧光为检测信号的检测限（DL）分别为 4.06×10µM（Cys，线性范围为 10-80µM）和 5.8×10µM（Hcy，线性范围为 10-100µM）。但是，丙烯酰胺取代的 3-羟基黄酮化合物 2（4-氧代-2-（4-二乙氨基苯基）-4H-色满-3-基丙烯酰胺）可以基于 Cys 导致丙烯酰胺水解机制和随后的 3-羟基黄酮化合物的激发态分子内质子转移过程，以荧光开启（DL=1.87×10µM，线性范围为 4-22µM）的方式特异性识别 Cys。然后，这两种 3-羟基黄酮衍生物可以同时识别 Cys 和 Hcy 两种生物硫醇。生物成像实验表明，这两种化合物都可以成功地应用于活细胞中 Cys/Hcy 的检测，并且化合物 2 也可以通过单光子和双光子荧光模式应用于斑马鱼中 Cys 的生物成像。然后，这两种化合物在生物样品分析的应用中具有潜力。
