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。 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
References
[1]
1 Gomes A. ; Fernandes E. ; Lima J. L. F. C. J. Biochem. Biophys. Methods 2005, 65 (2), 45. doi: 10.1016/j.jbbm.2005.10.003
[2]
5 Yuan L. ; Wang L. ; Agrawalla B. K. ; Park. S. J% Zhu H. ; Sivaraman B. ; Peng J. J. ; Xu Q. H. ; Chang Y. T. J. Am. Chem. Soc. 2015, 137, 5930. doi: 10.1021/jacs.5b00042
[3]
6 Xu Q. ; Heo C. H. ; Kim G. ; Lee H.W. ; Kim H. M. ; Yoon J. Angew. Chem. Int. Ed. 2015, 54, 4890. doi: 10.1002/anie.201500537
[4]
20 Ding H. J. ; Sun J. ; Zhang Y. J. ; Wang C. K. Chem. Phys. Lett. 2014, 591, 142. doi: 10.1016/j.cplett.2013.11.015
[5]
26 Liu Z. D. ; Xu H. J. ; Chen S. S. ; Sheng L. Q. ; Zhang H. ; Hao F. Y. ; Su P. F. ; Wang W. L. Spectrochim. Acta A 2015, 149, 8. doi: 10.1016/j.saa.2015.04.019
[6]
27 Torawane P. ; Tayade K. ; Bothra S. ; Sahoo S. K. ; Singh N. ; Borse A. ; Kuwar A. Sens. Actuators B 2016, 222, 562. doi: 10.1016/j.snb.2015.08.104
[7]
3 Li X. H. ; Zhang G. X. ; Ma H. M. ; Zhang D. Q. ; Li J. ; Zhu D. B. J. Am. Chem. Soc. 2004, 126 (37), 11543. doi: 10.1021/ja0481530
[8]
4 Cui L. L. ; Zhou D. H. ; Li M. M. Acta Phys. -Chim. Sin 2013, 29 (4), 745. doi: 10.3866/PKU.WHXB201302064
21 Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 09, Revision A.01; Gaussian Inc.: Wallingford, CT, 2009.
[16]
22 Aidas K. ; Angeli C. Bak K. L., et al. WIREs Comput. Mol. Sci. 2014, 4, 269. doi: 10.1002/wcms.1172
[17]
23 Zhang Y. J. ; Zhang Q. Y. ; Ding H. J. ; Song X. N. ; Wang C. K. Chin. Phys. B 2015, 24 (2), 023301. doi: 10.1088/1674-1056/24/2/023301
[18]
24 Wang X. M. ; Wang X. H. ; Feng Y. ; Zhu M. Z. ; Yin H. ; Guo Q. X. ; Meng X. M. Dalton Trans. 2015, 44 (14), 6613. doi: 10.1039/C5DT00012B
[19]
25 Wu J. S. ; Liu W. M. ; Zhuang X. Q. ; Wang F. ; Wang P. F. ; Tao S. L. ; Zhang X. H. ; Wu S. K. ; Lee S. T. Org. Lett. 2007, 9 (1), 33. doi: 10.1021/ol062518z
[20]
2 Fink M. P. Curr. Opin. Crit. Care. 2002, 8 (1), 6. doi: 10.1097/00075198-200202000-00002
[21]
7 Pattison D. I. ; Davies M. J. Chem. Res. Toxicol. 2001, 14 (10), 1453. doi: 10.1021/tx0155451
[22]
8 O'Brien P. J. Chem. Biol. Inter. 2000, 129 (2), 113. doi: 10.1016/S0009-2797(00)00201-5
[23]
9 Podrez E. A. ; Abu-Soud H. M. ; Hazen S. L. Free Radical Biol. Med. 2000, 28 (12), 1717. doi: 10.1016/S0891-5849(00)00229-X
[24]
11 Xiao H. D. ; Xin K. ; Dou H. F. ; Yin G. ; Quan Y.W. ; Wang R. Y. Chem. Commun. 2015, 51, 1442. doi: 10.1039/C4CC07411D
[25]
12 Setsukinai K. ; Urano Y. ; Kakinuma K. ; Majima H. J. ; Nagano T. J. Biol. Chem. 2003, 278 (5), 3170. doi: 10.1074/jbc.M209264200
[26]
13 Takats Z. ; Koch K. J. ; Cooks R. G. Analyt. Chem. 2001, 73 (18), 4522. doi: 10.1021/ac010338r
[27]
14 Yang W. J. ; Zhang Y. J. ; Wang C. K. Acta Phys. -Chim. Sin. 2015, 31 (12), 2303. doi: 10.3866/PKU.WHXB201510233
[28]
17 Yin H. J. ; Zhang B. C. ; Yu H. Z. ; Zhu L. ; Feng Y. ; Zhu M.Z. ; Guo Q. X. ; Meng X. M. J. Org. Chem. 2015, 80, 4306. doi: 10.1021/jo502775t
[29]
18 Ning P. ; Jiang J. C. ; Li L. C. ; Wang S. X. ; Yu H. Z. ; Feng Y. ; Zhu M. Z. ; Zhang B. C. ; Yin H. ; Guo Q. X. ; Meng X. M. Biosens. Bioelectron. 2016, 77, 921. doi: 10.1016/j.bios.2015.10.061
[30]
19 Li D. X. ; Feng Y. ; Lin J. Z. ; Chen M. ; Wang S. X. ; Wang X. ; Sheng H. T. ; Shao Z. L. ; Zhu M. Z. ; Meng X. M. Sens. Actuators B 2016, 222, 483. doi: 10.1016/j.snb.2015.08.098
