物理化学学报 >> 2016, Vol. 32 >> Issue (12): 2913-2920.doi: 10.3866/PKU.WHXB201609301

论文 上一篇    下一篇

基于咔唑的双光子荧光次氯酸根探针光学性质及响应机理

王昕,张玉瑾,王传奎*()   

  • 收稿日期:2016-06-06 发布日期:2016-11-30
  • 通讯作者: 王传奎 E-mail:ckwang@sdnu.edu.cn
  • 基金资助:
    国家自然科学基金(11404193);山东省自然科学基金(ZR2014AM026);和山东省泰山学者资助项目

Optical Properties and Responsive Mechanism of Carbazole-Based Two-Photon Fluorescent Probes for the Detection of Hypochlorite

Xin WANG,Yu-Jin ZHANG,Chuan-Kui WANG*()   

  • Received:2016-06-06 Published:2016-11-30
  • Contact: Chuan-Kui WANG E-mail:ckwang@sdnu.edu.cn
  • Supported by:
    The project was supported by the National Natural Science Foundation of China(11404193);Natural Science Foundation of Shandong Province,China(ZR2014AM026);and Taishan Scholar Project of Shandong Province, China

摘要:

采用含时密度泛函理论与响应函数理论相结合的方法,研究了两种实验室新合成的水溶性双光子荧光次氯酸根(ClO-)探针分子HCH和HCM的单光子吸收、双光子吸收和荧光发射性质。计算结果表明,HCH和HCM分子与ClO-反应后,生成物的光吸收和光发射性质均发生明显变化,相应的吸收和发射峰位都发生了明显蓝移,荧光强度展现出明显的增强。另外,两探针分子都具有较大的双光子吸收截面,且与ClO-反应后,生成物的双光子吸收截面值显著增加,因此两分子均可作为性能优良的双光子荧光探针分子。此外,通过分析HCH和HCM分子与ClO-反应前后的Mulliken电荷布居情况,从理论上证实了该系列荧光探针分子的识别机理是C=N异构化。

关键词: 荧光探针, 双光子吸收, 次氯酸根, C=N异构化

Abstract:

The one- and two-photon absorption and emission properties of the two newly synthesized watersoluble two-photon fluorescent probes (HCH and HCM) for the detection of ClO- were investigated using timedependent density functional theory in combination with response theory. Dramatic changes in the photophysical properties of the molecules following reaction with ClO- were predicted. The photoabsorption and photoemission peaks for both compounds were clearly blue shifted, while the emission intensities were enhanced. Both probes were also found to have large two-photon cross sections. Importantly, in the presence of ClO- the two-photon cross section of the molecules increased significantly, which indicated that both HCH and HCM should be good two-photon fluorescent probes for sensing ClO-. The responsive mechanism of the probes was explored by analyzing the molecular Mulliken charge population, which was attributed to C=N isomerization.

Key words: Fluorescent probe, Two-photon absorption, ClO-, C=N isomerization

MSC2000: 

  • O644