一种用于检测硫化氢和生物硫醇化学传感器的合成与应用  

Synthesis of a chemosensor and its application in H_2S and biothiols detection

作　　者：夏玉婷 江波 胡庆红 袁泽利 Xia Yuting , Jiang Bo , Hu Qinghong , Yuan Zeli(Department of Inorganic Chemistry, School of Pharmacy, Zunyi Medical University, Zunyi Guizhou 563099, Chin)

机构地区：[1]遵义医学院药学院无机化学教研室,贵州遵义563099

出　　处：《遵义医学院学报》2018年第1期1-8,共8页Journal of Zunyi Medical University

基　　金：国家自然科学基金资助项目(NO:81360471;81660975);贵州省国际合作项目(NO:[2012]7036)

摘　　要：目的开发新的用于在血清样品中检测硫化氢和生物硫醇(高半胱氨酸、半胱氨酸和谷胱甘肽)的化学传感器。方法以1,8-萘二甲酸酐为原料,经缩合、威廉姆森成醚反应制备得到目标传感器L,并经NMR、HRMS、FT-IR等分析手段确证其分子结构,通过高效液相色谱、质谱以及核磁滴定氢谱实验研究传感器L检测H_2S和生物硫醇的机理。最后经紫外-可见光谱和荧光光谱研究其检测硫化氢和生物硫醇的性能。结果 L为预期目标化学传感器分子。在Tris-HCl缓冲液(10 mM,pH 7.40,50%乙醇,v/v)中,L能同时对H_2S和生物硫醇快速、高敏感性和选择性识别。对H_2S的检测在576 nm处别表现了显著的吸收强度增强并伴随溶液颜色由无色变为酒红色,而对还原谷胱甘肽在426 nm处有显著的吸收强度变化;对高/半胱氨酸的检测于543 nm处表现了特异的荧光增强,而对半胱氨酸的检测还可见溶液颜色由无色变为橙色。识别机理研究表明L是通过硫醇亲核反应识别H_2S和生物硫醇。将L应用于血清的加样回收率也得到满意的结果。结论制备的L是一个简单高效的反应型传感器,可成功应用于血清样品中H_2S和生物硫醇的检测。Objective To synthesize the novel chemosensor for the detection of H_2S and biothiols [homocysteine（ Hcy）,cysteine（ Cys） and glutathione（ GSH） ]in the serum samples. Methods The 1,8-Naphthalenedicarboxylicanhydride was used as the starting material to prepare L by reactions of condensation and Williamson ether synthesis. Meanwhile,L was characterized by NMR,HRMS and FT-IR spectra. The recognition mechanism of the chemosensor L response to H_2S and biothiols was verified by three experiment methods（ high performance liquid chromatography,mass spectrum and ~1H NMR titration） in this work. Its properties for labeling H_2S and biothiols were investigated by UV-vis and fluorescence spectroscopy. Results L was successfully synthesized. L showed rapid,selective and sensitive response for these four analytes with unique absorbance enhancement at 426 nm and 576 nm for GSH and H_2S,respectively. And there was a distinct fluorescent signal changed at 543 nm for Hcy/Cys. At the same time,after the reaction between L and H_2S or Cys in Tris-HCl（ pH 7. 40,50% ethanol,v/v） buffer solution,the color of solution changed from colourless to wine red or orange-yellow,respectively.Therefore,H_2S and cysteine could be detected by naked eyes by chemosensor L. In addition,a lot of detailed experiment results indicated that the colorimetric chemosensor L response of these four analytes was most likely the result of the thiol nucleophilic reaction. Conclusion L was a simple and efficient reaction-based chemosensor for the detection of H_2S and biothiols in the serum samples with satisfactory results.

关 键 词：比色检测 传感器 硫化氢 高/半胱氨酸 谷胱甘肽 

分 类 号：R917[医药卫生—药物分析学]