高等学校化学学报 ›› 2013, Vol. 34 ›› Issue (6): 1339-1346.doi: 10.7503/cjcu20130110

• 分析化学 • 上一篇    下一篇

基于氢键作用的杯芳烃超分子识别乙醇的传感机理及分析应用

周婷, 曹忠, 戴云林, 曹婷婷, 何婧琳, 徐雷涛, 龙姝   

  1. 长沙理工大学化学与生物工程学院, 电力与交通材料保护湖南省重点实验室, 长沙 410004
  • 收稿日期:2013-01-30 出版日期:2013-06-10 发布日期:2013-05-03
  • 通讯作者: 曹忠,男,博士,教授,博士生导师,主要从事化学生物传感与超分子识别的研究.E-mail:zhongcao2004@163.com;何婧琳,女,博士,讲师,主要从事化学生物传感与核酸适配体分子识别的研究.E-mail:jinglin_he@163.com E-mail:zhongcao2004@163.com;jinglin_he@163.com
  • 基金资助:

    国家自然科学基金(批准号: 21275022, 21075011, 21105005)和国家科技支撑计划项目(批准号: 2012BAC17B01)资助.

Sensing Mechanism and Application for Recognition of Ethanol by Calixarene Supramolecules Based on Hydrogen Bonds Interaction

ZHOU Ting, CAO Zhong, DAI Yun-Lin, CAO Ting-Ting, HE Jing-Lin, XU Lei-Tao, LONG Shu   

  1. Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, School of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410004, China
  • Received:2013-01-30 Online:2013-06-10 Published:2013-05-03

摘要:

采用4种杯芳烃衍生物为吸附涂膜材料, 考察了涂膜石英晶体微天平(QCM)传感器对环境大气中微量乙醇气体的识别性能, 发现C-乙基杯[4]连苯三酚芳烃(3)是识别乙醇气体最有效的活性涂膜材料. 制备了C-乙基杯[4]连苯三酚芳烃·2CH3CH2OH(5)单晶体并进行X射线衍射结构解析, 发现其识别机制是基于超分子主体3与客体乙醇分子之间形成的C-H…π, O-H…π及O-H…O氢键作用. 当涂膜质量为24.70 μg 时, 涂膜QCM传感器对乙醇的响应最灵敏, 达到10.53 Hz/(mg·L-1). 分析了乙醇气体的吸附和解吸附动力学过程, 得到传感器对乙醇气体吸附和解吸附的初速度分别为-0.04600 Hz/s和0.03896 Hz/s. 该方法响应快, 具有选择性、 可逆性、 重现性和稳定性好的优点, 对乙醇样品测定的回收率为94.8% ~105.2%, 与气相色谱法的测定结果一致, 表明该方法可用于生活环境中乙醇气体的检测.

关键词: C-乙基杯[4]连苯三酚芳烃, 乙醇, 超分子识别, 氢键作用

Abstract:

Four calixarenederivatives were employed as adsorptive coating materials of quartz crystal microbalance(QCM) for the detection of ethanol gas in environmental atmosphere, indicating that C-ethylcalix[4]pirogallarene(3) was the most effectively active material to ethanol. The single crystal of complex C-ethylcalix[4]pirogallarene·2CH3CH2OH(5) was prepared and subjected to X-ray diffraction analysis, showing that the recognition mechanism was based on the formation of C-H…π, O-H…π and O-H…O hydrogen bonds interaction between the supramolecular host calixarene 3 and the guest ethanol molecule. When the coating mass of calixarene 3 was 24.70 μg, the coated QCM sensor possessed the highest sensitivity, which was 10.53 Hz/(mg·L-1). The kinetics processes for adsorption and desorption of ethanol on calixarene 3 have been examined, and the initial speeds of the adsorption and desorption processes for ethanol gas on cali-xarene 3 were obtained as -0.04600 Hz/s and 0.03896 Hz/s, respectively. With rapid test time, good selectivity, reversibility, reproducibility and stability, the calixarene 3 coated QCM sensor could be used for the detection of ethanol samples with a recovery of 94.8%-105.2%, which was in well consistent with those obtained by gas chromatography, showing its potential application on the determination of ethanol gas in living environment.

Key words: C-Ethylcalix[4]pirogallarene, Ethanol, Supramolecular recognition, Hydrogen bond interaction

中图分类号: