Citation: WANG Feng-Jiao, ZHOU Dan-Hong, ZUO Shi-Ying, CAO Jian-Fang, PENG Xiao-Jun. Theoretical Calculations on the PET Property of BODIPY Fluorescent pH Probes[J]. Acta Physico-Chimica Sinica, ;2012, 28(07): 1645-1650. doi: 10.3866/PKU.WHXB201205083 shu

Theoretical Calculations on the PET Property of BODIPY Fluorescent pH Probes

1.
1. Institute of Chemistry for Functionalized Materials, College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, Liaoning Province, P. R. China;
2. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, Liaoning Province, P. R. China

Received Date: 17 March 2012
Available Online: 8 May 2012
Fund Project: 精细化工国家重点实验室(大连理工大学)开放课题基金(KF0907)资助项目 (大连理工大学)开放课题基金(KF0907)

4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) fluorescent pH probes are fluorescent sensors and switchers based on photo-induced electron transfer (PET) mechanism. From experimental studies, different substituents on the amino nitrogen are known to result in variable photo sensitivities. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations are used to optimize the structures of six different BODIPY probe molecules with different substituted amines, and to study their exited states. In the ground state, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the probe molecules are located on the π and π^* orbitals of the BODIPY dye, and the lone pair electrons from the amino nitrogen form the HOMO-1 orbital. In the first exited state, for the probes with two substituent groups on the amino nitrogen, the HOMO-1→ LUMO transition has a smaller emission energy than that of the HOMO→LUMO transition in the BODIPY host, which may induce the PET effect and quench the fluorescence. After the geometry optimization of the exited states, irrespective of whether one or two groups are linked on the amino nitrogen, the orbital symmetry of the nitrogen atom changes from sp³→sp², and the lone pair electrons occupy the p orbital situated between the HOMO and LUMO of BODIPY, resulting in the PET effect. The calculated results are in od agreement with the experimental results.
- Time-dependent density functional theory,
- BODIPY dye,
- pH fluorescent probe,
- Photo-induced electron transfer
1. [1]
  
  (1) Hirano, T.; Kikuchi, K.; Urano, Y.; Nagano, T. J. Am. Chem. Soc. 2002, 124, 6555. doi: 10.1021/ja025567p
2. [2]
  (2) Guo, B. C.; Peng, X. J.; Cui, A. J.;Wu, Y. K.; Tian, M. Z.;Zhang, L. Z.; Chen, X. Q.; Gao, Y. L. Dyes and Pigments 2007,73 (2), 206. doi: 10.1016/j.dyepig.2005.11.007
3. [3]
  (3) Gareis, T.; Huber, C.;Wolfbeis, O. S.; Daub. J. Chem. Commun.1997, 1717.
4. [4]
  (4) Kollmannsberger, M.; Gareis, T.; Heinl, S.; Breu, J.; Daub, J.Angew. Chem. Int. Edit. 1997, 36, 1333. doi: 10.1002/anie.199713331
5. [5]
  (5) Baki, C. N.; Akkaya, E. U. J. Org. Chem. 2001, 66, 1512. doi: 10.1021/jo005706q
6. [6]
  (6) Baruah, M.; Qin,W.; Basaric′, N.; Borggraeve,W. M. D.; Boens,N. J. Org. Chem. 2005, 70, 4152. doi: 10.1021/jo0503714
7. [7]
  (7) Qin,W.; Baruah, M.; Borggraeve,W. M. D.; Boens, N.J. Photochem. Photobiol. A 2006, 183, 190. doi: 10.1016/j.jphotochem.2006.03.015
8. [8]
  (8) Wu, Y.; Peng, X.; Guo, B.; Fan, J. L.; Zhang, Z. C.;Wang, J. Y.;Cui, A. J.; Gao, Y. L. Organic & Biomolecular Chemistry 2005,3 (8), 1387. doi: 10.1039/b501795e
9. [9]
  (9) de Silva, S. A.; Loo, K. C.; Amorelli, B.; Pathirana, S. L.;Nyakirangáni, M.; Dharmasena, M.; Demarais, S.; Dorcley, B.;Pullay, P.; Salih, Y. A. J. Mater. Chem. 2005, 15 (27-28), 2791.doi: 10.1039/b502865e
10. [10]
  (10) Pond, S. J. K.; Tsutsumi, O.; Rumi, M.; Kwon, O.; Zojer, E.;Bredas, J. L.; Marder, S. R.; Perry, J.W. J. Am. Chem. Soc.2004, 126 (30), 9291. doi: 10.1021/ja049013t
11. [11]
  (11) Pearson, A. J.; Xiao,W. J. Org. Chem. 2003, 68 (13), 5369. doi: 10.1021/jo030060y
12. [12]
  (12) Tian, M. Z.; Peng, X. J.; Fan, J. L.;Wu, Y. K. Chin. J. Anal. Chem. 2006, 34, S283. [田茂忠, 彭孝军, 樊江莉, 吴云扣. 分析化学, 2006, 34, S283.]
13. [13]
  (13) Tian, M. Z.; Peng, X. J.; Feng, F.; Meng, S. M.; Fan, J. L.; Sun,S. G. Dyes and Pigments 2009, 81, 58. doi: 10.1016/j.dyepig.2008.09.004
14. [14]
  (14) Tian, M. Z. Study of BODIPY and Rhodamine FluorescentProbes for Cations. Ph.D. Dissertation, Dalian University ofTechnology, Dalian, 2007. [田茂忠. BODIPY 和罗丹明类阳离子荧光探针的研究[D]. 大连: 大连理工大学, 2007.]
15. [15]
  (15) Chen, Y. T.;Wang, H. L.;Wan, L.; Bian, Y. H.; Jiang, J. H.J. Org. Chem. 2011, 76, 3774. doi: 10.1021/jo200050a
16. [16]
  (16) Zhang, X.; Chi, L. N.; Ji, S. M.;Wu, Y. B.; Song, P.; Han, K. L.;Guo, H. M.; James, T. D.; Zhao, J. Z. J. Am. Chem. Soc. 2009,131, 17452. doi: 10.1021/ja9060646
17. [17]
  (17) Han, F.; Chi, L.; Liang, X.; Ji, S.; Liu, S.; Zhou, F.;Wu, Y.; Han,K.; Zhao, J.; James, T. D. J. Org. Chem. 2009, 74, 1333. doi: 10.1021/jo8025669
18. [18]
  (18) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 09,Revision A.02; Gaussian Inc.:Wallingford, CT, 2009.
19. [19]
  (19) Hohenberg, P.; Kohn,W. Phys. Rev. B 1964, 136, 864. doi: 10.1103/PhysRev.136.B864
20. [20]
  (20) Kohn,W.; Sham, L. J. Phys. Rev. A 1965, 140, 1133.
21. [21]
  (21) Lee, C.; Yang,W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/PhysRevB.37.785
22. [22]
  (22) Reed, A. E.; Curtiss, L. A.;Weinhold, F. Chem. Rev. 1988, 88 (6), 899. doi: 10.1021/cr00088a005
23. [23]
  (23) Petersila, M.; ssmann, U. J.; Gross, E. K. U. Phys. Rev. Lett.1966, 76, 1212.
24. [24]
  (24) Jamorski, C.; Caskla, M. E.; Salahub, D. R. J. Chem. Phys.1996, 104, 5134. doi: 10.1063/1.471140
1. [1]
  Tingting Yu , Si Chen , Lianglong Sun , Tongtong Shi , Kai Sun , Xin Wang . Comprehensive Experimental Design for the Photochemical Synthesis, Analysis, and Characterization of Difluoropyrroles. University Chemistry, 2024, 39(11): 196-203. doi: 10.3866/PKU.DXHX202401022
2. [2]
  Qi Wang , Yicong Gao , Feng Lu , Quli Fan . Preparation and Performance Characterization of the Second Near-Infrared Phototheranostic Probe: A New Design and Teaching Practice of Polymer Chemistry Comprehensive Experiment. University Chemistry, 2024, 39(11): 342-349. doi: 10.12461/PKU.DXHX202404141
3. [3]
  Tengjiao Wang , Tian Cheng , Rongjun Liu , Zeyi Wang , Yuxuan Qiao , An Wang , Peng Li . Conductive Hydrogel-based Flexible Electronic System: Innovative Experimental Design in Flexible Electronics. University Chemistry, 2024, 39(4): 286-295. doi: 10.3866/PKU.DXHX202309094
4. [4]
  Jie Li , Huida Qian , Deyang Pan , Wenjing Wang , Daliang Zhu , Zhongxue Fang . Efficient Synthesis of Anethaldehyde Induced by Visible Light. University Chemistry, 2024, 39(4): 343-350. doi: 10.3866/PKU.DXHX202310076
5. [5]
  Tianlong Zhang , Jiajun Zhou , Hongsheng Tang , Xiaohui Ning , Yan Li , Hua Li . Virtual Simulation Experiment for Laser-Induced Breakdown Spectroscopy (LIBS) Analysis. University Chemistry, 2024, 39(6): 295-302. doi: 10.3866/PKU.DXHX202312049
6. [6]
  Yonghui ZHOU , Rujun HUANG , Dongchao YAO , Aiwei ZHANG , Yuhang SUN , Zhujun CHEN , Baisong ZHU , Youxuan ZHENG . Synthesis and photoelectric properties of fluorescence materials with electron donor-acceptor structures based on quinoxaline and pyridinopyrazine, carbazole, and diphenylamine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 701-712. doi: 10.11862/CJIC.20230373
7. [7]
  Jiakun BAI , Ting XU , Lu ZHANG , Jiang PENG , Yuqiang LI , Junhui JIA . A red-emitting fluorescent probe with a large Stokes shift for selective detection of hypochlorous acid. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1095-1104. doi: 10.11862/CJIC.20240002
8. [8]
  Jinlong YAN , Weina WU , Yuan WANG . A simple Schiff base probe for the fluorescent turn-on detection of hypochlorite and its biological imaging application. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1653-1660. doi: 10.11862/CJIC.20240154
9. [9]
  Tao Cao , Fang Fang , Nianguang Li , Yinan Zhang , Qichen Zhan . Green Synthesis of p-Hydroxybenzonitrile Catalyzed by Spinach Extracts under Red-Light Irradiation: Research and Exploration of Innovative Experiments for Pharmacy Undergraduates. University Chemistry, 2024, 39(5): 63-69. doi: 10.3866/PKU.DXHX202309098
10. [10]
  Jinfu Ma , Hui Lu , Jiandong Wu , Zhongli Zou . Teaching Design of Electrochemical Principles Course Based on “Cognitive Laws”: Kinetics of Electron Transfer Steps. University Chemistry, 2024, 39(3): 174-177. doi: 10.3866/PKU.DXHX202309052
11. [11]
  Jia Yao , Xiaogang Peng . Theory of Macroscopic Molecular Systems: Theoretical Framework of the Physical Chemistry Course in the Chemistry “101 Plan”. University Chemistry, 2024, 39(10): 27-37. doi: 10.12461/PKU.DXHX202408117
12. [12]
  Jizhou Liu , Chenbin Ai , Chenrui Hu , Bei Cheng , Jianjun Zhang . 六氯锡酸铵促进钙钛矿太阳能电池界面电子转移及其飞秒瞬态吸收光谱研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2402006-. doi: 10.3866/PKU.WHXB202402006
13. [13]
  Xiaoning TANG , Shu XIA , Jie LEI , Xingfu YANG , Qiuyang LUO , Junnan LIU , An XUE . Fluorine-doped MnO₂ with oxygen vacancy for stabilizing Zn-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1671-1678. doi: 10.11862/CJIC.20240149
14. [14]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
15. [15]
  Yan ZHAO , Xiaokang JIANG , Zhonghui LI , Jiaxu WANG , Hengwei ZHOU , Hai GUO . Preparation and fluorescence properties of Eu³⁺-doped CaLaGaO₄ red-emitting phosphors. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1861-1868. doi: 10.11862/CJIC.20240242
16. [16]
  Jianye Kang , Xinyu Yang , Xuhao Yang , Jiahui Sun , Yuhang Liu , Shutao Wang , Wenlong Song . Carbon dots-enhanced pH-responsive lubricating hydrogel based on reversible dynamic covalent bondings. Chinese Chemical Letters, 2024, 35(5): 109297-. doi: 10.1016/j.cclet.2023.109297
17. [17]
  Shuang Li , Jiayu Sun , Guocheng Liu , Shuo Zhang , Zhong Zhang , Xiuli Wang . A new Keggin-type polyoxometallate-based bifunctional catalyst for trace detection and pH-universal photodegradation of phenol. Chinese Chemical Letters, 2024, 35(8): 109148-. doi: 10.1016/j.cclet.2023.109148
18. [18]
  Rui Wang , He Qi , Haijiao Zheng , Qiong Jia . Light/pH dual-responsive magnetic metal-organic frameworks composites for phosphorylated peptide enrichment. Chinese Chemical Letters, 2024, 35(7): 109215-. doi: 10.1016/j.cclet.2023.109215
19. [19]
  Yan Liu , Yang Wang , Jiayi Zhu , Xuxian Su , Xudong Lin , Liang Xu , Xiwen Xing . Employing pH-responsive RNA triplex to control CRISPR/Cas9-mediated gene manipulation in mammalian cells. Chinese Chemical Letters, 2024, 35(9): 109427-. doi: 10.1016/j.cclet.2023.109427
20. [20]
  Tongyu Zheng , Teng Li , Xiaoyu Han , Yupei Chai , Kexin Zhao , Quan Liu , Xiaohui Ji . A DIY pH Detection Agent Using Persimmon Extract for Acid-Base Discoloration Popularization Experiment. University Chemistry, 2024, 39(5): 27-36. doi: 10.3866/PKU.DXHX202309107

Get Citation

PDF

XML

Metrics

PDF Downloads(1119)
Abstract views(2774)
HTML views(23)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142