水杨醛衍生物激发态下的质子转移过程及在荧光探针领域的应用

doi:10.7503/cjcu20160680

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (3): 448.doi: 10.7503/cjcu20160680

水杨醛衍生物激发态下的质子转移过程及在荧光探针领域的应用

李学颖¹, 陈延明¹, 崔娜¹, 张万宇¹, 王志明^1,²()

1. 沈阳工业大学石油化工学院, 辽阳 111003
2. 香港科技大学深圳研究院, 深圳 518000

收稿日期:2016-09-26 出版日期:2017-03-10 发布日期:2017-02-23
作者简介:联系人简介: 王志明, 男, 博士, 副教授, 主要从事光电功能材料研究. E-mail: wangzhm1983@163.com
基金资助:
国家自然科学基金(批准号: 51673118)和深圳市科技计划项目(批准号: JCYC20160428150429072)资助.

Excited State Intramolecular Proton Transfer of Salicylaldehyde Derivatives and Its Application in Fluorescent Probe Field^†

LI Xueying¹, CHEN Yanming¹, CUI Na¹, ZHANG Wanyu¹, WANG Zhiming^1,^2,^*()

1. School of Petrochemical Engineering, Shenyang University of Technology, Liaoyang 111003, China;
2. Shenzhen Research Institute, Hong Kong University of Science & Technology, Shenzhen 518057, China;

Received:2016-09-26 Online:2017-03-10 Published:2017-02-23
Contact: WANG Zhiming E-mail:wangzhm1983@163.com
Supported by:
† Supported by the National Natural Science Foundation of China(No.51673118) and the Science and Technology Plan of Shenzhen, China(No.JCYC20160428150429072).

摘要/Abstract

摘要：

从电子结构控制理论出发, 通过在酚羟基对位引入吸电子取代基团稳定水杨醛中激发态的酮式构象, 制备了目标化合物5-对氰基苯基-水杨醛(CN-SA). 光谱测试结果显示, CN-SA表现出典型的ESIPT态荧光分子特性, 而且辐射跃迁过程的酮式分配比例显著提高, 荧光强度和颜色变化明显. CN-SA的荧光光谱不但能够对外围溶剂环境进行选择性识别, 而且对溶解和聚集过程(聚集效应)及外围氢键形成能力的变化(pH效应和阴离子效应)等具有特异性响应, 其变化可以定量表达. CN-SA仅通过结构微调即实现醇-酮构象的显著变化, 可作为一个简单的多重刺激响应型荧光探针.

关键词: 激发态分子内质子转移, 水杨醛, 刺激-响应, 荧光探针, 醇酮转换

Abstract:

According to the electronic structure control theory, the electron withdrawing substituent was introduced to the para-positon of phenol hydroxyl group to stable the ketone conformation, and the target compound, 2-hydroxy-5-(4-cyanophenyl)-benzaldehyde(CN-SA), was prepared. Series of spectral tests show that, CN-SA not only shows the typical excited state intramolecular proton transfer(ESIPT) fluorescence characteristics, but also significantly increases the ketone distribution proportion in radiation transition process, so that the fluorescence intensity and color change visibly. CN-SA not only exhibites selective recognition for the external solvent environment, but also has specific response and quantitative analysis ability for aggregation process(aggregation effect) and the hydrogen bond formation ability following environmental changes(pH effect and anions effect). With little structure tuning, CN-SA could realize alcohol and ketone conformation distribution changes and can be used as a simple multiple stimulation-responsive fluorescence probe.

Key words: Excited state intramolecular proton transfer(ESIPT), Salicylaldehyde, Stimulation-response, Fluorescent probe, Enol-ketone switching

中图分类号:

O644

TrendMD:

李学颖, 陈延明, 崔娜, 张万宇, 王志明. 水杨醛衍生物激发态下的质子转移过程及在荧光探针领域的应用. 高等学校化学学报, 2017, 38(3): 448.

LI Xueying, CHEN Yanming, CUI Na, ZHANG Wanyu, WANG Zhiming. Excited State Intramolecular Proton Transfer of Salicylaldehyde Derivatives and Its Application in Fluorescent Probe Field^†. Chem. J. Chinese Universities, 2017, 38(3): 448.

图/表 8

Fig.1 Structures of SB(A) and SAA(B)

Scheme 1 Transformation from Enol form to ketone form of ESIPT (1) and (3) Enol-form; (2) and (4) ketone-form.

Fig.2 Absorption spectra(A) and emission spectra(B) of CN-SA in different solvent

Fig.3 PL spectra of CN-SA in mixture with different water volume fractions(A) and I/I0-fw versus plot of CN-SA(B) I0 is the PL intensity in pure THF solution. Inset: fluorescence images at fw=0 and 60%.

Fig.4 Absorption spectra(A) and PL spectra(B) of CN-SA in different pH buffers and I/I0-pH plot for CN-SA(C) I0 is the PL intensity at pH=7.0.

Fig.5 Transformation mechanism of CN-SA in different pH buffers

Fig.6 Absorption spectra(A) and PL spectra(B) of CN-SA solution after adding different anions

Fig.7 PL spectra of CN-SA after adding different concentrations of SO42-(λex=340 nm)(A) and PL intensity trend of CN-SA after adding different concentrations of SO42-(B)

参考文献 20

[1]	Li C., Zhang Y., Hu J., Cheng J., Liu S., Angew. Chem. Int. Ed., 2010, 49, 5120—5124
[2]	Chi Z., Zhang X., Xu B., Zhou X., Ma C., Zhang Y., Liu S., Xu J., Chem. Soc. Rev., 2012, 41, 3878—3896
[3]	Stich M. I. J., Fischer L. H., Wolfbeis O. S., Chem. Soc. Rev., 2010, 39, 3102—3114
[4]	Chen F., Zhang J., Wan X., Chem. Eur. J., 2012, 18, 4558—4567
[5]	Levitt J. A., Kuimova M. K., Yahioglu G., Chung P. H., Suhling K., Phillip D., J. Phys. Chem. C, 2009, 113, 11634—11646
[6]	Niu C., Zhao L., Fang T. , Deng X., Ma H., Zhang J., Na N., Han J., Ouyang J., Langmuir,2014, 30, 2351—2359
[7]	Xiang J. F., Yi P. G., Yu X. Y., Chen J., Hao Y. L., Ren Z. Y., Chem. J. Chinese Universities, 2015, 36(4), 654—659
	(向俊峰, 易平贵, 于贤勇, 陈建, 郝艳雷, 任志勇.高等学校化学学报, 2015, 36(4), 654—659)
[8]	Wei R., Song P., Tong A., J. Phys. Chem. C, 2013, 117, 3467—3474
[9]	Peng L., Zhou Z., Wang X., Wei R., Li K., Xiang Y., Tong A., Anal. Chim. Acta, 2014, 829, 54—59
[10]	Wang Z., Gui C., Zhao E., Wang J., Li X., Qin A., Zhao Z., Yu Z., Tang B. Z., ACS Appl. Mater. Interfaces, 2016, 8, 10193—10200
[11]	Smith M.B., March J., March’s Advanced Organic Chemistry, the First Edition, Translated by Li Y. M. , Chemical Industry Press, Beijing, 2009
	(李艳梅[译]艳梅[译]. 高等有机化学反应、机理与结构, 第一版, 北京: 化学工业出版社, 2009)
[12]	Dick B., Ernsting N. P., J. Phys. Chem., 1987, 91, 4261—4265
[13]	Kwon J. E., Park S. Y., Adv. Mater., 2011, 23, 3615—3642
[14]	Mei J, LeungN. L. C., Kwok R. T. K., Lam J. W. Y., Tang B. Z., Chem. Rev., 2015, 115, 11718—11940
[15]	KwokR. T. K., Leung C.W. T., Lam J. W. Y., Tang B. Z., Chem. Soc. Rev., 2015, 44, 4228—4238
[16]	Wang Z., Nie H., Yu Z., Qin A., Zhao Z., Tang B. Z., J. Mater. Chem. C, 2015, 3, 9103—9111
[17]	Liang F. H., Wang D., Ma P. Y, Wang X. H., Chem. Res. Chinese Universities, 2015, 31(5), 724—729
[18]	Kong F., Meng X., Chu R., Xu K., Tang B., Chem. Commun., 2015, 51, 6925—6927
[19]	Yang W. L., Li Q., Wei T. B., Zhang Y. M., Lin Q. Shi B. B., Zhang P., Chem. Res. Chinese Universities, 2013, 29(2), 236—238
[20]	Yeh J. T., Chen W., Liu S., Wu S., New J. Chem., 2014, 38, 4434—4439
	(Ed.:S, Z, M)

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水杨醛衍生物激发态下的质子转移过程及在荧光探针领域的应用

Excited State Intramolecular Proton Transfer of Salicylaldehyde Derivatives and Its Application in Fluorescent Probe Field^†

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水杨醛衍生物激发态下的质子转移过程及在荧光探针领域的应用

Excited State Intramolecular Proton Transfer of Salicylaldehyde Derivatives and Its Application in Fluorescent Probe Field†

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Excited State Intramolecular Proton Transfer of Salicylaldehyde Derivatives and Its Application in Fluorescent Probe Field^†