可同时比色检测硫离子和高半胱氨酸/半胱氨酸的化学探针的合成及应用  

Synthesis and Application of Colorimetric Probe for the Simultaneous Detection of Sulphion and Homocysteine/Cysteine in the Serum Samples

作　　者：夏玉婷 江波[1] 吴庆[1] 胡庆红[1] 袁泽利[1] XIA Yuting;JIANG Bo;WU Qing;HU Qinghong;YUAN Zeli(School of Pharmacy,Zunyi Medical University,Zunyi 563003,Chin)

机构地区：[1]遵义医学院药学院,遵义563003

出　　处：《高等学校化学学报》2018年第8期1647-1655,共9页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:81360471;81660975);教育部春晖计划(批准号:Z2016004)资助~~

摘　　要：合成了一个能同时检测硫离子(S2-)和高半胱氨酸/半胱氨酸(Hcy/Cys)的化学探针1,采用核磁共振波谱(NMR)、高分辨质谱(HRMS)、元素分析和傅里叶换红外光谱(FTIR)等表征了其分子结构,并通过高效液相色谱、质谱以及核磁滴定氢谱实验研究了探针1检测S2-和Hcy/Cys的机理.实验结果表明,探针1能同时对S2-和Hcy/Cys进行快速、高敏感性和选择性识别,并且是通过硫醇亲核反应识别的.在Tris-HCl缓冲溶液[10 mmol/L,p H=7.40,50%(体积分数)乙醇]中,探针1对S2-于552 nm处表现了显著的吸收强度增强并伴随溶液颜色由无色变为紫红色;对Hcy/Cys于552 nm处表现了特异的荧光增强,而对Cys的检测还可见溶液颜色由无色变为酒红色,据此制备了负载探针1的滤纸传感器用于比色检测S2-和Cys.此外,将探针1用于人血清的加标回收率测定,获得了较好的结果.A new but versatile probe 1 was developed,which can be used for simultaneous detection and discrimination of sulphion（ S2-） and homocysteine（ Hcy）/cysteine（ Cys）. 4-Bromine-1,8-naphthalenedicarboxylicanhydride was used as the starting material to prepare probe 1 by the reactions of condensation and Williamson ether synthesis. Meanwhile,probe 1 was characterized by means of1 H NMR,13 C NMR,HRMS,elemental analysis and FTIR spectra. The recognition mechanism of the colorimetric probe 1 responses to S2-and Hcy/Cys was verified by high performance liquid chromatography,mass spectrum and1 H NMR titration. A lot of detailed experiment results indicate that the colorimetric probe 1 responses of these three analytes are most likely the result of the thiol nucleophilic reaction. Probe 1 shows rapid,selective and sensitive response for these three analytes with unique absorbance enhancement at 552 nm for S2-and distinct fluorescent turn on signal changes at 552 nm for Hcy/Cys. At the same time,after reaction of probe 1 with S2-or Cys in Tris-HCl（ 10 mmol/L,p H= 7. 4,50% ethanol） buffer solution,the color of solution changed from colorless to purplered or wine,respectively. Therefore,probe 1 could be used to develop a colorimetric test kit for S2-and cysteine. The detection limits of probe 1 for S2-,Hcy and Cys were respectively determined as 8. 83×10-6,1. 26×10-6 and 7. 65×10-7 mol/L,indicating that the probe 1 has a good sensitivity for S2-and Hcy/Cys. In addition,the competitive experiments results show that the probe 1 is highly selective for S2-and Hcy/Cys over other competitive. Probe 1 could be used to detect S2-and Hcy/Cys in the serum samples with satisfactory results.

关 键 词：探针 比色检测 硫离子 高半胱氨酸/半胱氨酸 

分 类 号：O657[理学—分析化学]