激发态分子内质子转移荧光探针的研究进展

doi:10.11944/j.issn.1000-0518.2018.01.170328

摘要/Abstract

摘要：

荧光探针凭借其选择性好、灵敏度高、响应时间快、易于操作和检测限低等优点得到了广泛的关注。激发态分子内质子转移(ESIPT)化合物具有特殊的激发态光物理过程,其显著的光物理性质是有较高的荧光量子产率及大的斯托克斯位移。对于荧光分子而言,较大的斯托克斯位移可以减少自吸收和由内滤效应产生的干扰,增强分子的耐光性,有利于荧光的发射。本文对ESIPT荧光探针检测离子(包括金属阳离子和阴离子)、中性小分子和生物大分子的研究进展进行阐述,并对ESIPT荧光分子的存在问题和应用前景进行评述。

关键词: 激发态分子内质子转移, 金属阳离子, 阴离子, 中性小分子, 生物大分子, 荧光探针

Abstract:

Fluorescent probes are gaining more and more attention because of their high selectivity, sensitivity, fast response, simple operation and low detection limit. Compounds based on excited state intramolecular proton transfer(ESIPT) have special excited state photophysical properties, such as high fluorescence quantum yield and large Stokes shift. For fluorescent molecules, the larger Stokes shift can reduce the interference caused by self-absorption and internal filtration, and enhance light-fastness of the molecules and facilitate the emitting of fluorescence. In this review, we summarized these ESIPT fluorescent probes from the classification of targets. The targets for detection were divided into ions(including metal cations and anions), neutral small molecules and biological macromolecules. The existing problems and application prospects of fluorescent molecules based on ESIPT were commented.

Key words: sexcited state intramolecular proton transfer, metal cations, anions, neutral small molecule, biological macromolecule, fluorescence probes

王德佳, 徐勇前, 孙世国, 李红娟. 激发态分子内质子转移荧光探针的研究进展[J]. 应用化学, 2018, 35(1): 1-20.

WANG Dejia, XU Yongqian, SUN Shiguo, LI Hongjuan. Advanced in Fluorescent Probes Based on Excited State Intramolecular Proton Transfer[J]. Chinese Journal of Applied Chemistry, 2018, 35(1): 1-20.

参考文献

[1]	Lee M H,Kim J S,Sessler J L. Small Molecule-based Ratiometric Fluorescence Probes for Cations, Anions, and Biomolecules[J]. Chem Soc Rev,2015,44(13):4185-4191.
[2]	Berezin M Y,Achilefu S. Fluorescence Lifetime Measurements and Biological Imaging[J]. Chem Rev,2010,110(5):2641-2684.
[3]	Wu J S,Liu W M,Ge J C,et al.New Sensing Mechanisms for Design of Fluorescent Chemosensors Emerging in Recent Years[J]. Chem Soc Rev,2011,40(7):3483-3495.
[4]	Kwon J E,Park S Y. Advanced Organic Optoelectronic Materials:Harnessing Excited-State Intramolecular Proton Transfer(ESIPT) Process[J]. Adv Mater,2011,23(32):3615-3642.
[5]	Hsieh C C,Jiang C M,Chou P T. Recent Experimental Advances on Excited-State Intramolecular Proton Coupled Electron Transfer Reaction[J]. Acc Chem Res,2010,43(10):1364-1374.
[6]	Tang K C,Chang M J,Lin T Y,et al.Fine Tuning the Energetics of Excited-State Intramolecular Proton Transfer(ESIPT):White Light Generation in a Single ESIPT System[J]. J Am Chem Soc,2011,133(44):17738-17745.
[7]	Luxami V,Kumar S. Molecular Half-subtractor Based on 3,3'-Bis(1H-benzimidazolyl-2-yl)[1,1']binaphthalenyl-2,2'-diol[J]. New J Chem,2008,32(12):2074-2079.
[8]	HU Rui,GUO Xudong,YANG Guoqiang. Investigation on the Property of the ESIPT Compounds and Its Application as Fluorescence Chemical Sensor[J]. Imag Sci Photochem,2013,31(5):335-348(in Chinese). 胡睿,郭旭东,杨国强. 激发态分子内质子转移化合物的性能及作为荧光化学传感器的应用研究[J]. 影像科学与光化学,2013,31(5):335-348.
[9]	Wang J F,Li Y B,Patel N G,et al.A Single Molecular Probe for Multi-analyte(Cr3+, Al3+ and Fe3+) Detection in Aqueous Medium and Its Biological Application[J]. Chem Commun,2014,50(82):12258-12261.
[10]	Chu Q H,Medvetz D A,Pang Y. A Polymeric Colorimetric Sensor with Excited-State Intramolecular Proton Transfer for Anionic Species[J]. Chem Mater,2007,19(26):6421-6429.
[11]	Ma J,Zhao J Z,Yang P,et al.New Excited State Intramolecular Proton Transfer(ESIPT) Dyes Based on Naphthalimide and Observation of Long-lived Triplet Excited States[J]. Chem Commun,2012,48(78):9720-9722.
[12]	Yang P,Zhao J Z,Wu W H,et al.Accessing the Long-lived Triplet Excited States in Bodipy-conjugated 2-(2-Hydroxyphenyl) Benzothiazole/Benzoxazoles and Applications as Organic Triplet Photosensitizers for Photooxidations[J]. J Org Chem,2012,77(14):6166-6178.
[13]	Kim T I,Kang H J,Han G,et al.A Highly Selective Fluorescent ESIPT Probe for the Dual Specificity Phosphatase MKP-6[J]. Chem Commun,2009,39:5895-5897.
[14]	Hu R,Feng J,Hu D H,et al.A Rapid Aqueous Fluoride Ion Sensor with Dual Output Modes[J]. Angew Chem Int Ed,2010,49(29):4915-4918.
[15]	Li X,Tao R R,Hong L J,et al.Visualizing Peroxynitrite Fluxes in Endothelial Cells Reveals the Dynamic Progression of Brain Vascular Injury[J]. J Am Chem Soc,2015,137(38):12296-12303.
[16]	Sinha S,Chowdhury B,Ghosh P. A Highly Sensitive ESIPT-based Ratiometric Fluorescence Sensor for Selective Detection of Al3+[J]. Inorg Chem,2016,55(18):9212-9220.
[17]	Tang L J,Shi J Z,Huang Z L,et al.An ESIPT-based Fluorescent Probe for Selective Detection of Homocysteine and Its Application in Live-Cell Imaging[J]. Tetrahedron Lett,2016,57(47):5227-5231.
[18]	Klymchenko A S,Shvadchak V V,Yushchenko D A,et al.Excited-State Intramolecular Proton Transfer Distinguishes Microenvironments in Singleand Double-stranded DNA[J]. J Phys Chem B,2008,112(38):12050-12055.
[19]	Dziuba D,Postupalenko V Y,Spadafora M,et al.A Universal Nucleoside with Strong Two-band Switchable Fluorescence and Sensitivity to the Environment for Investigating DNA Interactions[J]. J Am Chem Soc,2012,134(24):10209-10213.
[20]	Kenfack C A,Klymchenko A S,Duportail G,et al.Ab Initio Study of the Solvent H-Bonding Effect on ESIPT Reaction and Electronic Transitions of 3-Hydroxychromone Derivatives[J]. Phys Chem Chem Phys,2012,14(25):8910-8918.
[21]	Paul B K,Guchhait N. 1-Hydroxy-2-naphthaldehyde:A Prospective Excited-State Intramolecular Proton Transfer(ESIPT) Probe with Multi-faceted Applications[J]. J Lumin,2012,132(8):2194-2208.
[22]	Hadjoudis E,Mavridis I M. Photochromism and Thermochromism of Schiff Bases in the Solid State:Structural Aspects[J]. Chem Soc Rev,2004,33(9):579-88.
[23]	Han D Y,Kim J M,Kim J H,et al.ESIPT-based Anthraquinonylcalix[4]crown Chemosensor for In3+[J]. Tetrahedron Lett,2010,51(15):1947-1951.
[24]	Schmidtke S J,Underwood D F,Blank D A. Following the Solvent Directly During Ultrafast Excited State Proton Transfer[J]. J Am Chem Soc,2004,126(28):8620-8621.
[25]	Chien T C,Dias L G,Arantes G M,et al.1-(2-Quinolyl)-2-naphthol:A New Intra-Intermolecular Photoacid Photobase Molecule[J]. J Photochem Photobiol A,2008,194(1):37-48.
[26]	SakaiK I,Takahashi S,Kobayashi A,et al. Excited State Intramolecular Proton Transfer(ESIPT) in Six-coordinated Zinc(Ⅱ)-Quinoxaline Complexes with Ligand Hydrogen Bonds:Their Fluorescent Properties Sensitive to Axial Positions[J]. Dalton Trans,2010,39(8):1989-1995.
[27]	ZHANG Peng,ZHANG Youming,LIN Qi,et al.Principle and the Research Progress of Fluorescent Chemosensors for Cations Recognition[J]. Chinese J Org Chem,2014,37(7):1300-1321(in Chinese). 张鹏,张有明,林奇,等. 金属离子响应型荧光传感分子的设计原理及研究进展[J]. 有机化学,2014,37(7):1300-1321.
[28]	Gao M,Yu F B,Lv C J,et al.Fluorescent Chemical Probes for Accurate Tumor Diagnosis and Targeting Therapy[J]. Chem Soc Rev,2017,46(8):2237-2271.
[29]	Sinkeldam R W,Greco N J,Tor Y. Fluorescent Analogs of Biomolecular Building Blocks:Design, Properties, and Applications[J]. Chem Rev,2010,110(5):2579-2619.
[30]	Xu Y Q,PangY. Zn2+-Triggered Excited-State Intramolecular Proton Transfer:A Sensitive Probe with Near-infrared Emission from Bis(benzoxazole) Derivative[J]. Dalton Trans,2011,40(7):1503-1509.
[31]	Huang L Y,Gu B,Su W,et al.Proton Donor Modulating ESIPT-based Fluorescent Probes for Highly Sensitive and Selective Detection of Cu2+[J]. RSC Adv,2015,5(93):76296-76301.
[32]	Chen X Q,Pradhan T H,Wang F,et al.Fluorescent Chemosensors Based on Spiroring-opening of Xanthenes and Related Derivatives[J]. Chem Rev,2012,112(3):1910-1956.
[33]	Xu Y Q,Xiao L L,Zhang Y F,et al.Substituent Effect on Fluorophores Instead of Ionophores:Its Implication in Highly Selective Fluorescent Probes for Zn2+ over Cd2+[J]. RSC Adv,2014,4(10):4827-4830.
[34]	Xu Y Q,Xiao L L,Sun S G,et al.Switchable and Selective Detection of Zn2+ or Cd2+ in Living Cells Based on 3'-O-substituted Arrangement of Benzoxazole-derived Fluorescent Probes[J]. Chem Commun,2014,50(56):7514-7516.
[35]	Gale P A,Caltagirone C. Anion Sensing by Small Molecules and Molecular Ensembles[J]. Chem Soc Rev,2015,44(13):4212-4227.
[36]	Ashton T D,Jolliffe K A,Pfeffer F M. Luminescent Probes for the Bioimaging of Small Anionic Species in Vitro and in Vivo[J]. Chem Soc Rev,2015,44(14):4547-4595.
[37]	Wu Y K,Peng X J,Fan J L,et al.Fluorescence Sensing of Anions Based on Inhibition of Excited-State Intramolecular Proton Transfer[J]. J Org Chem,2007,72(1):62-70 .
[38]	Goswami S,Manna A,Paul S,et al.Resonance-assisted Hydrogen Bonding Induced Nucleophilic Addition to Hamper ESIPT:Ratiometric Detection of Cyanide in Aqueous Media[J]. Chem Commun,2013,49(28):2912-2914.
[39]	Porel M,Ramalingam V,Domaradzki M E,et al.Chloride Sensing via Suppression of Excited State Intramolecular Proton Transfer in Squaramides[J]. Chem Commun,2013,49(16):1633-1635.
[40]	Chen W H,Xing Y,Pang Y. A Highly Selective Pyrophosphate Sensor Based on ESIPT Turn-on in Water[J]. Org Lett,2011,13(6):1362-1365.
[41]	Sedgwick A C,Sun X L,Kim G,et al.Boronate Based Fluorescence(ESIPT) Probe for Peroxynitrite[J]. Chem Commun,2016,52(83):12350-12352.
[42]	Pan Y M,Huang J,Han Y F. A New ESIPT-based Fluorescent Probe for Highly Selective and Sensitive Detection of HClO in Aqueous Solution[J]. Tetrahedron Lett,2017,58(13):1301-1304.
[43]	Xiao L L,Sun S G,Pei Z C,et al.A Ga3+ Self-assembled Fluorescent Probe for ATP Imaging in Vivo[J]. Biosens Bioelectron,2015,65:166-170.
[44]	Chen X Q,Zhou Y,Peng X J,et al.Fluorescent and Colorimetric Probes for Detection of Thiols[J]. Chem Soc Rev,2010,39(6):2120-2135.
[45]	Fernandez A,Vendrell M. Smart Fluorescent Probes for Imaging Macrophage Activity[J]. Chem Soc Rev,2016,45(5):1182-1196.
[46]	Xiao L L,Tu J,Sun S G,et al.A Fluorescent Probe for Hydrazine and Its in Vivo Applications[J]. RSC Adv,2014,4(79):41807-41811.
[47]	Chen Z,Zhong X X,Qu W B,et al.A Highly Selective HBT-based “Turn-On” Fluorescent Probe for Hydrazine Detection and Its Application[J]. Tetrahedron Lett,2017,58(26):2596-2601.
[48]	Zhang D,Yang Z H,Li H J,et al.A Simple Excited-State Intramolecular Proton Transfer Probe Based on a New Strategy of Thiol-azide Reaction for the Selective Sensing of Cysteine and Glutathione[J]. Chem Commun,2016,52(4):749-752.
[49]	Goswami S,Manna A,Paul S,et al.A Turn On ESIPT Probe for Rapid and Ratiometric Fluorogenic Detection of Homocysteine and Cysteine in Water with Live Cell-Imaging[J]. Tetrahedron Lett,2014,55(2):490-494.
[50]	Liu X J,Tian H H,Yang L,et al.A Sensitive and Selective Fluorescent Probe for the Detection of Hydrogen Peroxide with a Red Emission and a Large Stokes Shift[J]. Sens Actuators B,2018,255:1160-1165.
[51]	Li G P,Zhu D J,Liu Q,et al.Rapid Detection of Hydrogen Peroxide Based on Aggregation Induced Ratiometric Fluorescence Change[J]. Org Lett,2013,15(4):924-927.
[52]	Wang L Q,Zang Q G,Chen W S,et al.A Ratiometric Fluorescent Probe with Excited-State Intramolecular Proton Transfer for Benzoyl Peroxide[J]. RSC Adv,2013,3(23):8674-8676.
[53]	Deng B B,Ren M G,Kong X Q,et al.An ESIPT Based Fluorescent Probe for Imaging Hydrogen Sulfide with a Large Turn-On Fluorescence Signal[J]. RSC Adv,2016,6(67):62406-62410.
[54]	Chen L Y,Wu D,Lim C S,et al.A Two-photon Fluorescent Probe for Specific Detection of Hydrogen Sulfide Based on a Familiar ESIPT Fluorophore Bearing AIE Characteristics[J]. Chem Commun,2017,53(35):4791-4794.
[55]	Yushchenko D A,Fauerbach J A,Thirunavukkuarasu S,et al.Fluorescent Ratiometric MFC Probe Sensitive to Early Stages of α-Synuclein Aggregation[J]. J Am Chem Soc,2010,132(23):7860-7861.