高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (8): 1647-1655.doi: 10.7503/cjcu20170806

• 分析化学 • 上一篇    下一篇

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

夏玉婷, 江波, 吴庆, 胡庆红, 袁泽利()   

  1. 遵义医学院药学院, 遵义 563003
  • 收稿日期:2017-12-11 出版日期:2018-08-10 发布日期:2018-06-04
  • 作者简介:联系人简介: 袁泽利, 男, 教授, 主要从事有机小分子设计合成方面的研究. E-mail: zlyuan2002@126.com
  • 基金资助:
    国家自然科学基金(批准号: 81360471, 81660975)和教育部春晖计划(批准号: Z2016004)资助.

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

XIA Yuting, JIANG Bo, WU Qing, HU Qinghong, YUAN Zeli*()   

  1. School of Pharmacy, Zunyi Medical University, Zunyi 563003, China
  • Received:2017-12-11 Online:2018-08-10 Published:2018-06-04
  • Contact: YUAN Zeli E-mail:zlyuan2002@126.com
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.81360471, 81660975) and the “Chunhui” Plan Project of Ministry of Education, China(No.Z2016004).

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, pH=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.

关键词: 探针, 比色检测, 硫离子, 高半胱氨酸/半胱氨酸

Abstract:

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-naphthalenedicarboxy-licanhydride 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 of 1H NMR, 13C 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 and 1H 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, pH=7.4, 50% ethanol) buffer solution, the color of solution changed from colorless to purple-red 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.

Key words: Probe, Colorimetric detection, Sulphion, Homocysteine/cysteine

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