氟离子荧光探针的研究进展

doi:10.11949/j.issn.0438-1157.20150954

摘要/Abstract

摘要：

氟离子是电负性最强、离子半径最小的阴离子,是一个强路易斯碱,在化学、生物学、医学和军事等方面都具有重要作用。适量的氟化物摄入人体可以预防龋齿、治疗骨质疏松症,但是过量的摄入会导致氟斑牙、氟骨症、尿石症以及癌症等疾病,因此氟离子的识别与检测具有重要意义。化学荧光探针具有选择性好、灵敏度高、方便快捷、成本低廉等优点,近年来化学研究者设计合成了大量的氟离子荧光探针。根据识别机理不同,氟离子荧光探针主要划分为3种:氢键型、路易斯酸受体型、氢键和路易斯酸混合型。综述了近年来不同类型的氟离子荧光探针的研究进展,总结了氢键型和路易斯酸型氟离子荧光探针的优缺点,对未来氟离子荧光探针的研究方向进行了展望。

关键词: 氟离子, 荧光探针, 染料, 分子工程, 阴离子识别, 化学分析, 生物成像, 分子生物学

Abstract:

Fluoride ions play an important role in many chemical, biological, medical and military processes because of strongest electronegativity, the smallest ion radius, and strong Lewis base. Low levels of fluoride ions have shown to be effective for prevention of dental caries and treatment of osteoporosis. But high concentration of fluoride intake is harmful to human body. It may cause dental fluorosis, skeletal fluorosis, urolithiasis and diseases such as cancers. Therefore, the recognition and detection of fluoride ions is of great significance. Fluoride fluorescent probes have attracted a wide spread attention due to its high selectivity and sensitivity, speediness and convenience, low cost, etc. In recent years, the researchers designed and synthesized a large number of fluorescent probes for fluoride ions. According to detection mechanism, fluorescent probes for fluoride ions mainly contained three types: 1) the hydrogen bond type; 2) Lewis acid style; and 3) the hydrogen bond and Lewis acid mixed. In this paper, the research progress of different types of fluorescent probes for fluoride ions respectively was reviewed, the advantages and disadvantages of different types were summed up, and the future research of fluorescent probes for fluoride ions was prospected.

Key words: fluoride, fluorescence probe, dye, molecular engineering, recognition of anions, chemical analysis, bio-imaging, molecular biology

中图分类号:

TQ618.5

张世玲, 彭孝军. 氟离子荧光探针的研究进展[J]. 化工学报, 2016, 67(1): 191-201.

ZHANG Shiling, PENG Xiaojun. Research progress on fluorescent probes for fluoride ions[J]. CIESC Journal, 2016, 67(1): 191-201.

参考文献 52

[1]	吴振. 萘酰亚胺类氟离子荧光化学传感器的合成与识别研究[D]. 武汉:湖北大学, 2012.WU Z. The synthesis and study of 1,8-naphthalimide fluorescent chemsensors for fluoride ion[D]. Wuhan: Hubei University, 2012.
[2]	吴云扣. 阴离子荧光识别中的氢键及质子转移研究[D]. 大连:大连理工大学, 2007.WU Y K. Fluorescence anion sensing based on hydrogen bonding and proton transfer[D]. Dalian: Dalian University of Technology, 2007.
[3]	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]. The Journal of Organic Chemistry, 2007, 72(1): 62-70. DOI: 10.1021/jo061634c.
[4]	THIAGARAJAN V, RAMAMURTHY P, THIRUMALAI D, et al. A novel colorimetric and fluorescent chemosensor for anions involving PET and ICT pathways [J]. Organic Letters, 2005, 7(4): 657-660. DOI: 10.1021/ol047463k.
[5]	DUKE R M, GUNNLAUGSSON T. 3-Urea-1,8-naphthalimides are good chemosensors: a highly selective dual colorimetric and fluorescent ICT based anion sensor for fluoride [J]. Tetrahedron Letters, 2011, 52(13): 1503-1505. DOI:10.1016/j.tetlet.2011.01.099.
[6]	RAJAMALLI P, PRASAD E. Low molecular weight fluorescent organogel for fluoride ion detection [J]. Organic Letters, 2011, 13(14): 3714-3717. DOI: 10.1021/ol201325j.
[7]	CHENG F, BONDER E M, JÄKLE F. Electron-deficient triarylborane block copolymers: synthesis by controlled free radical polymerization and application in the detection of fluoride ions [J]. Journal of the American Chemical Society, 2013, 135(46): 17286-17289. DOI: 10.1021/ja409525j.
[8]	QU Y, HUA J L, TIAN H. Colorimetric and ratiometric red fluorescent chemosensor for fluoride ion based on diketopyrrolopyrrole [J]. Organic Letters, 2010, 12(15): 3320-3323. DOI: 10.1021/ol101081m.
[9]	SARAVANAN C, EASWARAMOORTHI S, HSIOW C, et al. Benzoselenadiazole fluorescent probes-near-ir optical and ratiometric fluorescence sensor for fluoride ion [J]. Organic Letters, 2014, 16(2): 354-357. DOI: 10.1021/ol403082p.
[10]	SIVARAMAN G, CHELLAPPA D. Rhodamine based sensor for naked-eye detection and live cell imaging of fluoride ions [J]. Journal of Materials Chemistry B, 2013, 1(42): 5768-5772. DOI: 10.1039/C3TB21041C.
[11]	MAHAPATRA A K, MAJI R, MAITI K, et al. Ratiometric sensing of fluoride and acetate anions based on a BODIPY-azaindole platform and its application to living cell imaging [J]. Analyst, 2014, 139(1): 309-317. DOI: 10.1039/C3AN01663C.
[12]	LIN C I, SELVI S, FANG J M, et al. Pyreno[2,1-b]pyrrole and bis (pyreno [2,1-b] pyrrole) as selective chemosensors of fluoride ion: a mechanistic study [J]. The Journal of Organic Chemistry, 2007, 72(9): 3537-3542. DOI: 10.1021/jo070169w.
[13]	SUI B L, KIM B, ZHANG Y W, et al. Highly selective fluorescence turn-on sensor for fluoride detection [J]. ACS Applied Materials & Interfaces, 2013, 5(8): 2920-2923. DOI: 10.1021/am400588w.
[14]	PENG X J, WU Y K, FAN J L, et al. Colorimetric and ratiometric fluorescence sensing of fluoride: tuning selectivity in proton transfer [J]. The Journal of Organic Chemistry, 2005, 70(25): 10524-10531. DOI: 10.1021/jo051766q.
[15]	MADHU S, RAVIKANTH M. Boron-dipyrromethene based reversible and reusable selective chemosensor for fluoride detection [J]. Inorganic Chemistry, 2014, 53(3): 1646-1653. DOI: 10.1021/ic402767j.
[16]	YONG X, SU M J, WANG W, et al. A naked-eye chemosensor for fluoride ions: a selective easy-to-prepare test paper [J]. Organic & Biomolecular Chemistry, 2013, 11(14): 2254-2257. DOI: 10.1039/C3OB27131E.
[17]	WANG Q G, XIE Y S, DING Y B, et al. Colorimetric fluoride sensors based on deprotonation of pyrrole-hemiquinone compounds [J]. Chemical Communications, 2010, 46(21): 3669-3671. DOI: 10.1039/C001509A.
[18]	ZHENG X J, ZHU W C, LIU D, et al. Highly selective colorimetric/fluorometric dual-channel fluoride ion probe, and its capability of differentiating cancer cells [J]. ACS Applied Materials & Interfaces, 2014, 6(11): 7996-8000. DOI: 10.1021/am501546h.
[19]	GHOSH D, RHODES S, HAWKINS K. A simple and effective 1,2,3-triazole based “turn-on” fluorescence sensor for the detection of anions [J]. New Journal of Chemistry, 2015, 39(1): 295-303. DOI: 10.1039/C4NJ01411A.
[20]	LIU R Y, GAO Y, ZHANG Q B. A fluorescent probe based on hydroxylnaphthalene 2-cyanoacrylate: fluoride ion detection and its bio-imaging in live cells [J]. New Journal of Chemistry, 2014, 38(7): 2941-2945. DOI: 10.1039/C4NJ00018H.
[21]	YUAN M S, WANG Q, WANG W J, et al. Truxene-cored π-expanded triarylborane dyes as single-and two-photon fluorescent probes for fluoride [J]. Analyst, 2014, 139(6): 1541-1549. DOI: 10.1039/C3AN02179C.
[22]	SWAMY K M K, LEE Y J, LEE H N, et al. A new fluorescein derivative bearing a boronic acid group as a fluorescent chemosensor for fluoride ion [J]. The Journal of Organic Chemistry, 2006, 71(22): 8626-8628. DOI: 10.1021/jo061429x.
[23]	GUO Z Q, SHIN I, YOON J. Recognition and sensing of various species using boronic acid derivatives [J]. Chemical Communications, 2012, 48(48): 5956-5967. DOI: 10.1039/C2CC31985C.
[24]	XU Z C, KIM S K, HAN S J, et al. Ratiometric fluorescence sensing of fluoride ions by an asymmetric bidentate receptor containing a boronic acid and imidazolium group [J]. European Journal of Organic Chemistry, 2009, 2009(18): 3058-3065. DOI: 10.1002/ejoc.200900120.
[25]	CAO J, ZHAO C C, FENG P, et al. A colorimetric and ratiometric NIR fluorescent turn-on fluoride chemodosimeter based on BODIPY derivatives: high selectivity via specific Si—O cleavage [J]. RSC Advances, 2012, 2(2): 418-420. DOI: 10.1039/C1RA00942G.
[26]	CAO J, ZHAO C C, ZHU W H. A near-infrared fluorescence chemodosimeter for fluoride via specific Si—O cleavage [J]. Tetrahedron Letters, 2012, 53(16): 2107-2110. DOI:10.1016/j.tetlet.2012.02.051.
[27]	IM H G, KIM H Y, CHOI M G, et al. Reaction-based dual signaling of fluoride ions by resorufin sulfonates [J]. Organic & Biomolecular Chemistry, 2013, 11(18): 2966-2971. DOI: 10.1039/C3OB00040K.
[28]	LI L, JI Y Z, TANG X J. Quaternary ammonium promoted ultra selective and sensitive fluorescence detection of fluoride ion in water and living cells [J]. Analytical Chemistry, 2014, 86(20): 10006-10009. DOI: 10.1021/ac503177n.
[29]	ROY A, KAND D, SAHA T, et al. Pink fluorescence emitting fluoride ion sensor: investigation of the cascade sensing mechanism and bioimaging applications [J]. RSC Advances, 2014, 4(64): 33890-33896. DOI: 10.1039/C4RA06933A.
[30]	SOKKALINGAM P, LEE C. Highly sensitive fluorescence “turn-on” indicator for fluoride anion with remarkable selectivity in organic and aqueous media [J]. The Journal of Organic Chemistry, 2011, 76(10): 3820-3828. DOI: 10.1021/jo200138t.
[31]	GU J A, MANI V, HUANG S T. Design and synthesis of ultrasensitive off-on fluoride detecting fluorescence probe via autoinductive signal amplification [J]. Analyst, 2015, 140(1): 346-352. DOI: 10.1039/C4AN01723D.
[32]	DHANUNJAYARAO K, MUKUNDAM V, VENKATASUBBAIAH K. A highly selective ratiometric detection of F-based on excited-state intramolecular proton-transfer (imidazole) materials [J]. Journal of Materials Chemistry C, 2014, 2(40): 8599-8606. DOI: 10.1039/C4TC01711K.
[33]	ROY A, KAND D, SAHA T, et al. A cascade reaction based fluorescent probe for rapid and selective fluoride ion detection [J]. Chemical Communications, 2014, 50(41): 5510-5513. DOI: 10.1039/C4CC01665C.
[34]	KE B W, CHEN W X, NI N T. A fluorescent probe for rapid aqueous fluoride detection and cell imaging [J]. Chemical Communications, 2013, 49(25): 2494-2496. DOI: 10.1039/C2CC37270C.
[35]	JO M, LIM J, MILJANI? O Š. Selective and sensitive fluoride detection through alkyne cruciform desilylation [J]. Organic Letters, 2013, 15(14): 3518-3521. DOI: 10.1021/ol401120a.
[36]	RAO M R, MOBIN S M, RAVIKANTH M. Boron-dipyrromethene based specific chemodosimeter for fluoride ion [J]. Tetrahedron, 2010, 66(9): 1728-1734. DOI:10.1016/j.tet.2009.12.039.
[37]	LU H, WANG Q H, LI Z F, et al. A specific chemodosimeter for fluoride ion based on a pyrene derivative with trimethylsilylethynyl groups [J]. Organic & Biomolecular Chemistry, 2011, 9(12): 4558-4562. DOI: 10.1039/C1OB05164D.
[38]	FU L, JIANG F L, FORTIN D, et al. A reaction-based chromogenic and fluorescent chemodosimeter for fluoride anions [J]. Chemical Communications, 2011, 47(19): 5503-5505. DOI: 10.1039/C1CC10784D.
[39]	BUCKLAND D, BHOSALE S V, LANGFORD S J. A chemodosimer based on a core-substituted naphthalene diimide for fluoride ion detection [J]. Tetrahedron Letters, 2011, 52(16): 1990-1992. DOI:10.1016/j.tetlet.2011.02.080.
[40]	KIM D, SINGHA S, WANG T, et al. In vivo two-photon fluorescent imaging of fluoride with a desilylation-based reactive probe [J]. Chemical Communications, 2012, 48(82): 10243-10245. DOI: 10.1039/C2CC35668F.
[41]	WANG C Y, YANG S, YI M, et al. Graphene oxide assisted fluorescent chemodosimeter for high-performance sensing and bioimaging of fluoride ions [J]. ACS Applied Materials & Interfaces, 2014, 6(12): 9768-9775. DOI: 10.1021/am502142d.
[42]	BHALLA V, SINGH H, KUMAR M. Facile cyclization of terphenyl to triphenylene: a new chemodosimeter for fluoride ions [J]. Organic Letters, 2010, 12(3): 628-631. DOI: 10.1021/ol902861b.
[43]	HOU P, CHEN S, WANG H B, et al. An aqueous red emitting fluorescent fluoride sensing probe exhibiting a large Stokes shift and its application in cell imaging [J]. Chemical Communications, 2014, 50(3): 320-322. DOI: 10.1039/C3CC46630B.
[44]	PENG Y, DONG Y M, DONG M, et al. A selective, sensitive, colorimetric, and fluorescence probe for relay recognition of fluoride and Cu(Ⅱ) ions with “off-on-off” switching in ethanol-water solution [J]. The Journal of Organic Chemistry, 2012, 77(20): 9072-9080. DOI: 10.1021/jo301548v.
[45]	DONG M, PENG Y, DONG Y M, et al. A selective, colorimetric, and fluorescent chemodosimeter for relay recognition of fluoride and cyanide anions based on 1,1'-binaphthyl scaffold [J]. Organic Letters, 2012, 14(1): 130-133. DOI: 10.1021/ol202926e.
[46]	YEH J T, VENKATESAN P, WU S P. A highly selective turn-on fluorescent sensor for fluoride and its application in imaging of living cells [J]. New Journal of Chemistry, 2014, 38(12): 6198-6204. DOI: 10.1039/C4NJ01486C.
[47]	KIM T, SWAGER T. A fluorescent self-amplifying wavelength-responsive sensory polymer for fluoride ions [J]. Angewandte Chemie International Edition, 2003, 42(39): 4803-4806. DOI:10.1002/anie.200352075.
[48]	ZHANG S L, FAN J L, ZHANG S Z, et al. Lighting up fluoride ions in cellular mitochondria using a highly selective and sensitive fluorescent probe [J]. Chemical Communications, 2014, 50(90): 14021-14024. DOI: 10.1039/C4CC05094K.
[49]	KE I, MYAHKOSTUPOV M, CASTELLANO F N, et al. Stibonium ions for the fluorescence turn-on sensing of F- in drinking water at parts per million concentrations [J]. Journal of the American Chemical Society, 2012, 134(37): 15309-15311. DOI: 10.1021/ja308194w.
[50]	HIRAI M, GABBAÏ F P. Lewis acidic stiborafluorenes for the fluorescence turn-on sensing of fluoride in drinking water at ppm concentrations [J]. Chemical Science, 2014, 5(5): 1886-1893. DOI: 10.1039/C4SC00343H.
[51]	ZHAO Q, LI F Y, LIU S J, et al. Highly selective phosphorescent chemosensor for fluoride based on an iridium(Ⅲ) complex containing arylborane units [J]. Inorganic Chemistry, 2008, 47(20): 9256-9264. DOI: 10.1021/ic800500c.
[52]	XU S Y, SUN X L, GE H B, et al. Synthesis and evaluation of a boronate-tagged 1,8-naphthalimide probe for fluoride recognition [J]. Organic & Biomolecular Chemistry, 2015, 13(14): 4143-4148. DOI: 10.1039/C4OB02267J.