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A triphenylamine-functionalized fluorescent organic polymer as a turn-on fluorescent sensor for Fe3+ ion with high sensitivity and selectivity

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Abstract

A triphenylamine-functionalized A3B2-type covalent organic polymer (TPA-COP) was synthesized by the palladium-catalyzed Sonogashira polycondensation reaction from tris(4-ethynylphenyl)amine and 4-bromo-N-(4-bromo-2-methoxybenzylidene)-2-methoxyaniline. The obtained polymer possessing amorphous structure and good thermal stability exhibited strong yellow–green luminescence with an emission band at 498 nm. It is worth noting that the polymer also shows selective turn-on fluorescence response to Fe3+ ion over a variety of other competing metal ions such as Na+, K+, Ca2+, Mg2+, Ba2+, Mn2+, Cr3+, Cu2+, Ni2+, Zn2+, Co2+, Al3+. The fluorescent detection limit of TPA-COP sensor for Fe3+ in solution was 4.3 × 10−7 M. Furthermore, the proposed sensing mechanism should result from complexation between tridentate-coordinated Schiff base sites and Fe3+ ion, which was further investigated by fluorescence titration, 1H NMR and IR measures, together with fluorescence lifetime analysis.

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References

  1. Li X, Gao X, Shi W, Ma H (2014) Design strategies for water-soluble small molecular chromogenic and fluorogenic probes. Chem Rev 114:590–659

    Article  Google Scholar 

  2. Goncalves MS (2009) Fluorescent labeling of biomolecules with organic probes. Chem Rev 109:190–212

    Article  Google Scholar 

  3. Wu D, Sedgwick AC, Gunnlaugsson T, Akkaya EU, Yoon J, James TD (2017) Fluorescent chemosensors: the past, present and future. Chem Soc Rev 46:7105–7123

    Article  Google Scholar 

  4. Pischel U (2007) Chemical approaches to molecular logic elements for addition and subtraction. Angew Chem Int Ed 46:4026–4040

    Article  Google Scholar 

  5. Han J, Burgess K (2009) Fluorescent indicators for intracellular pH. Chem Rev 110:2709–2728

    Article  Google Scholar 

  6. Burnworth M, Rowan SJ, Weder C (2007) Fluorescent sensors for the detection of chemical warfare agents. Chem Eur J 13:7828–7836

    Article  Google Scholar 

  7. Kim JS, Quang DT (2007) Calixarene-derived fluorescent probes. Chem Rev 107:3780–3799

    Article  Google Scholar 

  8. Xu Z, Xiao Y, Qian X, Cui J, Cui D (2005) Ratiometric and selective fluorescent sensor for Cu II based on internal charge transfer (ICT). Org Lett 7:889–892

    Article  Google Scholar 

  9. Wang JB, Qian XF, Cui JN (2006) Detecting Hg2+ Ions with an ICT fluorescent sensor molecule: remarkable emission spectra shift and unique selectivity. J Org Chem 71:4308–4311

    Article  Google Scholar 

  10. Goswami S, Das S, Aich K (2013) An ICT based highly selective and sensitive sulfur-free sensor for naked eye as well as fluorogenic detection of Hg2+ in mixed aqueous media. Tetra Lett 54:4620–4623

    Article  Google Scholar 

  11. Goswami S, Aich K, Das S, Das AK, Sarkar D, Panja S, Mondal TK, Mukhopadhyay SK (2013) A red fluorescence ‘off–on’ molecular switch for selective detection of Al3+, Fe3+ and Cr3+: experimental and theoretical studies along with living cell imaging. Chem Commun 49:10739–10741

    Article  Google Scholar 

  12. Lim NC, Schuster JV, Porto MC, Tanudra MA, Yao LL, Freake HC, Bruckner C (2005) Coumarin-based chemosensors for zinc(II): toward the determination of the design algorithm for CHEF-type and ratiometric probes. Inorg Chem 44:2018–2030

    Article  Google Scholar 

  13. Goswami S, Das S, Aich K, Sarkar D, Mondal TK, Quah CK, Fun HK (2013) CHEF induced highly selective and sensitive turn-on fluorogenic and colorimetric sensor for Fe3+. Dalton Trans 42:15113–15119

    Article  Google Scholar 

  14. Gunnlaugsson T, Davis AP, O’Brien JE, Glynn M (2002) Fluorescent sensing of pyrophosphate and bis-carboxylates with charge neutral PET chemosensors. Org Lett 4:2449–2452

    Article  Google Scholar 

  15. Vance DH, Czarnik AW (1994) Real-time assay of inorganic pyrophosphatase using a high-affinity chelation-enhanced fluorescence chemosensor. J Am Chem Soc 116:9397–9398

    Article  Google Scholar 

  16. Kim SK, Yoon J (2002) A new fluorescent PET chemosensor for fluoride ions dedicated to the memory of D. J Cram Chem Commun 7:770–771

    Article  Google Scholar 

  17. Nishizawa S, Yuichi KA, Teramae N (1999) Fluorescence sensing of anions via intramolecular excimer formation in a pyrophosphate-induced self-assembly of a pyrene-functionalized guanidinium receptor. J Am Chem Soc 121:9463–9464

    Article  Google Scholar 

  18. Wu JS, Zhou JH, Wang PF, Zhang XH, Wu SK (2005) New fluorescent chemosensor based on exciplex signaling mechanism. Org Lett 7:2133–2136

    Article  Google Scholar 

  19. Schazmann B, Alhashimy N, Diamond D (2006) Chloride selective calix[4]arene optical sensor combining urea functionality with pyrene excimer transduction. J Am Chem Soc 128:8607–8614

    Article  Google Scholar 

  20. Banerjee A, Sahana A, Guha S, Lohar S, Hauli I, Mukhopadhyay SK, Sanmartin Matalobos J, Das D (2012) Nickel(II)-induced excimer formation of a naphthalene-based fluorescent probe for living cell imaging. Inorg Chem 51:5699–5704

    Article  Google Scholar 

  21. Goswami S, Das S, Aich K, Pakhira B, Panja S, Mukherjee SK, Sarkar S (2013) A chemodosimeter for the ratiometric detection of hydrazine based on return of ESIPT and its application in live-cell imaging. Org Lett 15:5412–5415

    Article  Google Scholar 

  22. Dichtel WR, Serin JM, Edder C, FreChet JM, Matuszewski M, Tan LS, Ohulchanskyy TY, Prasad PN (2004) Singlet oxygen generation via two-photon excited FRET. J Am Chem Soc 126:5380–5381

    Article  Google Scholar 

  23. Albers AE, Okreglak VS, Chang CJ (2006) A FRET-based approach to ratiometric fluorescence detection of hydrogen peroxide. J Am Chem Soc 128:9640–9641

    Article  Google Scholar 

  24. Sreenath K, Allen JR, Davidson MW, Zhu L (2011) A FRET-based indicator for imaging mitochondrial zinc ions. Chem Commun 47:11730–11732

    Article  Google Scholar 

  25. Kwok RTK, Leung CWT, Lam JWY, Tang BZ (2015) Biosensing by luminogens with aggregation-induced emission characteristics. Chem Soc Rev 44:4228–4238

    Article  Google Scholar 

  26. Wang XS, Li L, Yuan DQ, Huang YB, Cao R (2017) Fast, highly selective and sensitive anionic metal-organic framework with nitrogen-rich sites fluorescent chemosensor for nitro explosives detection. J Hazard Mater 344:283–290

    Article  Google Scholar 

  27. Chen CH, Wang XS, Li L, Huang YB, Cao R (2018) Highly selective sensing of Fe3+ by an anionic metal-organic framework containing uncoordinated nitrogen and carboxylate oxygen sites. Dalton Trans 47:3452–3458

    Article  Google Scholar 

  28. Zhu H, Fan J, Wang B, Peng X (2015) Fluorescent MRI, and colorimetric chemical sensors for the first-row d-block metal ions. Chem Soc Rev 44:4337–4366

    Article  Google Scholar 

  29. Li L, Zhu Y, Zhou X, Brites CDS, Ananias D, Lin Z, Almeida Paz FA, Rocha J, Huang W, Carlos LD (2016) Visible-light excited luminescent thermometer based on single lanthanide organic frameworks. Adv Funct Mater 26:8677–8684

    Article  Google Scholar 

  30. Feng X, Ding X, Jiang D (2012) Covalent organic frameworks. Chem Soc Rev 41:6010–6022

    Article  Google Scholar 

  31. Ding SY, Wang W (2013) Covalent organic frameworks (COFs): from design to applications. Chem Soc Rev 42:548–568

    Article  Google Scholar 

  32. Rd TS, Joly GD, Swager TM (2007) Chemical sensors based on amplifying fluorescent conjugated polymers. J Chem Inf 38:1339–1386

    Google Scholar 

  33. Dalapati S, Jin S, Gao J, Xu Y, Nagai A, Jiang D (2013) An azine-linked covalent organic framework. J Am Chem Soc 135:17310–17313

    Article  Google Scholar 

  34. Guo L, Zeng X, Lan J, Yun J, Cao D (2017) Absorption competition quenching mechanism of porous covalent organic polymer as luminescent sensor for selective sensing Fe3+. Chemistryselect 2:1041–1047

    Article  Google Scholar 

  35. Guo L, Zeng X, Cao D (2016) Porous covalent organic polymers as luminescent probes for highly selective sensing of Fe3+ and chloroform: functional group effects. Sens Actuators B Chem 226:273–279

    Article  Google Scholar 

  36. Xiang Z, Cao D (2012) Synthesis of luminescent covalent organic polymers for detecting nitroaromatic explosives and small organic molecules. Macromol Rapid Commun 33:1184–1190

    Article  Google Scholar 

  37. Sang N, Zhan C, Cao D (2015) Highly sensitive and selective detection of 2,4,6-trinitrophenol using covalent-organic polymer luminescent probes. J Mater Chem A 3:92–96

    Article  Google Scholar 

  38. Guo L, Cao D, Yun J, Zeng X (2017) Highly selective detection of picric acid from multicomponent mixtures of nitro explosives by using COP luminescent probe. Sen. Actuators B Chem 243:753–760

    Article  Google Scholar 

  39. Das G, Biswal BP, Kandambeth S, Venkatesh V, Kaur G, Addicoat M, Heine T, Verma S, Banerjee R (2015) Chemical sensing in two dimensional porous covalent organic nanosheets. Chem Sci 6:3931–3939

    Article  Google Scholar 

  40. He S, Iacono ST, Budy SM, Dennis AE, Smith DW, Smith RC (2008) Photoluminescence and ion sensing properties of a bipyridyl chromophore-modified semifluorinated polymer and its metallopolymer derivatives. J Mater Chem 18:1970–1976

    Article  Google Scholar 

  41. Yan Z, Hu L, You J (2016) Sensing materials developed and applied for bio-active Fe3+ recognition in water environment. Anal Methods 8:5738–5754

    Article  Google Scholar 

  42. Simon T, Shellaiah M, Srinivasadesikan V, Lin CC, Ko FH, Sun KW, Lin MC (2016) A simple pyrene based AIEE active schiff base probe for selective naked eye and fluoresence off-on detection of trivalent cations with live cell application. Sens Actuators B Chem 231:18–29

    Article  Google Scholar 

  43. Kundu A, Hariharan PS, Prabakaran K, Anthony SP (2015) Developing new Schiff base molecules for selective colorimetric sensing of Fe3+ and Cu2+ metal ions: substituent dependent selectivity and colour change. Sens Actuators B Chem 206:524–530

    Article  Google Scholar 

  44. You GR, Park GJ, Lee SA, Ryu KY, Kim C (2015) Chelate-type Schiff base acting as a colorimetric sensor for iron in aqueous solution. Sens Actuators B Chem 215:188–195

    Article  Google Scholar 

  45. Gaute T, Torild W, Syverin L, Rolf V, Walter L (2002) Fractionation and determination of aluminum and iron in soil water samples using SPE cartridges and ICP-AES. Environ Sci Technol 36:5421–5425

    Article  Google Scholar 

  46. Oh JW et al (2013) Multisignaling metal sensor: optical, electrochemical, and electrochemiluminescent responses of cruciform-shaped alkynylpyrene for selective recognition of Fe3+. Sens Actuators B Chem 177:813–817

    Article  Google Scholar 

  47. Canfranc E, Abarca A, Sierra I, Marina ML (2001) Determination of iron and molybdenum in a dietetic preparation by flame AAS after dry ashing. J Pharm Biomed Anal 25:103–108

    Article  Google Scholar 

  48. Guo L, Cao D (2015) Color tunable porous organic polymer luminescent probes for selective sensing of metal ions and nitroaromatic explosives. J Mater Chem C 3:8490–8494

    Article  Google Scholar 

  49. He Y, Yu Z, He J, Zhang H, Liu Y, Lei B (2018) Ratiometric and selective fluorescent sensor for Fe(III) and bovineserum albumin based on energy transfer. Sens Actuators B Chem 262:228–235

    Article  Google Scholar 

  50. Saha UC, Dhara K, Chattopadhyay B, Mandal SK, Mondal S, Sen S, Mukherjee M, Van SS, Chattopadhyay P (2011) A new half-condensed Schiff base compound: highly selective and sensitive pH-responsive fluorescent sensor. Org Lett 13:4510–4513

    Article  Google Scholar 

  51. McDonald L, Wang J, Alexander N, Li H, Liu T, Pang Y (2016) Origin of water-induced fluorescence turn-on from a Schiff base compound: AIE or H-bonding promoted ESIPT. J Phys Chem B 120:766–772

    Article  Google Scholar 

  52. Wen K, Yu S, Huang Z, Chen L, Xiao M, Yu X, Pu L (2015) Rational design of a fluorescent sensor to simultaneously determine both the enantiomeric composition and the concentration of chiral functional amines. J Am Chem Soc 137:4517–4524

    Article  Google Scholar 

  53. Ding WH, Cao W, Zheng XJ, Fang DC, Wong WT, Jin LP (2013) A highly selective fluorescent chemosensor for Al(III) ion and fluorescent species formed in the solution. Inorg Chem 52:7320–7322

    Article  Google Scholar 

  54. Hwang IH, Choi YW, Kim KB, Park GJ, Lee JJ, Nguyen L, Noh I, Kim C (2016) A highly selective and sensitive fluorescent turn-on Al3+ chemosensor in aqueous media and living cells: experimental and theoretical studies. New J Chem 40:171–178

    Article  Google Scholar 

  55. Liu Z, He W, Guo Z (2013) Metal coordination in photoluminescent sensing. Chem Soc Rev 42:1568–1600

    Article  Google Scholar 

  56. Zhang M, Gao Y, Li M, Yu M, Li F, Li L, Zhu M, Zhang J, Yi T, Huang C (2007) A selective turn-on fluorescent sensor for Fe(III) and application to bioimaging. Tetra Lett 48:3709–3712

    Article  Google Scholar 

  57. Mao J, Wang L, Dou W, Tang X, Yan Y, Liu W (2007) Tuning the selectivity of two chemosensors to Fe(III) and Cr(III). Org Lett 9:4567–4570

    Article  Google Scholar 

  58. Lim NC, Pavlova SV, Bruckner C (2009) Squaramide hydroxamate-based chemidosimeter responding to iron(III) with a fluorescence intensity increase. Inorg Chem 48:1173–1182

    Article  Google Scholar 

  59. Weerasinghe AJ, Schmiesing C, Varaganti S, Ramakrishna G, Sinn E (2010) Single- and multiphoton turn-on fluorescent Fe(3+) sensors based on bis(rhodamine). J Phy Chem B 114:9413–9419

    Article  Google Scholar 

  60. He L, Liu C, Xin JH (2015) A novel turn-on colorimetric and fluorescent sensor for Fe3+ and Al3+ with solvent-dependent binding properties and its sequential response to carbonate. Sens Actuators B 213:181–187

    Article  Google Scholar 

  61. Jin X, Wang S, Yin W, Xu T, Jiang Y, Liao Q, Xia X, Liu J (2017) A highly sensitive and selective fluorescence chemosensor for Fe3+ based on rhodamine and its application in vivo imaging. Sens Actuators B Chem 247:461–468

    Article  Google Scholar 

  62. Yao D, Huang X, Guo F, Xie P (2018) A new fluorescent enhancement chemosensor for Al3+ and Fe3+ based on naphthyridine and benzothiazole groups. Sens Actuators B Chem 256:276–281

    Article  Google Scholar 

  63. Jiang JX, Su F, Trewin A, Wood CD, Niu H, Jones JTA, Khimyak YZ, Cooper AI (2008) Synthetic control of the pore dimension and surface area in conjugated microporous polymer and copolymer networks. J Am Chem Soc 130:7710–7720

    Article  Google Scholar 

  64. Bennett JS, Charles KL, Miner MR, Heuberger CF, Spina EJ, Bartels MF, Foreman T (2009) Ethyl lactate as a tunable solvent for the synthesis of aryl aldimines. Green Chem 11:166–168

    Article  Google Scholar 

  65. Shahnaz N, Banik B, Das P (2013) A highly efficient Schiff-base derived palladium catalyst for the Suzuki-Miyaura reactions of aryl chlorides. Tetra Lett 54:2886–2889

    Article  Google Scholar 

  66. Jie S, Zhang S, Sun W-H (2007) 2-Arylimino-9-phenyl-1,10-phenanthrolinyl- iron, -cobalt and -nickel complexes: synthesis, characterization and ethylene oligomerization behavior. Eur J Inorg Chem 35:5584–5598

    Article  Google Scholar 

  67. Shellaiah M, Wu YH, Singh A, Ramakrishnam Raju MV, Lin HC (2013) Novel pyrene- and anthracene-based Schiff base derivatives as Cu2+ and Fe3+ fluorescence turn-on sensors and for aggregation induced emissions. J Mater Chem A 1:1310–1318

    Article  Google Scholar 

  68. Goswami S, Aich K, Das AK, Manna A, Das S (2013) A naphthalimide–quinoline based probe for selective, fluorescence ratiometric sensing of trivalent ions. RSC Adv 3:2412–2416

    Article  Google Scholar 

  69. Li J, Wu Y, Song F, Wei G, Cheng Y, Zhu C (2012) A highly selective and sensitive polymer-based OFF–ON fluorescent sensor for Hg2+detection incorporating salen and perylenyl moieties. J Mater Chem 22:478–482

    Article  Google Scholar 

  70. Shortreed M, Kopelman R, Kuhn M, Hoyland B (1996) Fluorescent fiber-optic calcium sensor for physiological measurements. Anal Chem 68:1414–1418

    Article  Google Scholar 

  71. Shellaiah M, Ramakrishnam Raju MV, Singh A, Lin HC, Wei KH, Lin HC (2014) Synthesis of novel platinum complex core as a selective Ag+ sensor and its H-bonded tetrads self-assembled with triarylamine dendrimers for electron/energy transfers. J Mater Chem A 2:17463–17476

    Article  Google Scholar 

  72. Boonkitpatarakul K, Wang J, Niamnont N, Liu B, McDonald L, Pang Y, Sukwattanasinitt M (2015) Novel turn-on fluorescent sensors with mega stokes shifts for dual detection of Al3+ and Zn2+. ACS Sens 1:144–150

    Article  Google Scholar 

  73. Guo L, Wang M, Cao D (2018) A novel Zr-MOF as fluorescence turn-on probe for real-time detecting H2S gas and fingerprint identification. Small 14:1703822–1703828

    Article  Google Scholar 

  74. Wang M, Guo L, Cao D (2018) Amino-functionalized luminescent metal organic framework test paper for rapid and selective sensing of SO2 gas and its derivatives by luminescence turn-on effect. Anal Chem 90:3608–3614

    Article  Google Scholar 

  75. Wang M, Guo L, Cao D (2018) Metal-organic framework as luminescence turn-on sensor for selective detection of metal ions: absorbance caused enhancement mechanism. Sens Actuators B Chem 256:839–845

    Article  Google Scholar 

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 51703076) and the Excellent Young Teachers Program of Jilin University. Q. S. thanks the open projects in State Key Lab of Inorganic Synthesis and Preparative Chemistry, Jilin University.

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Authors and Affiliations

  1. College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun, 130012, People’s Republic of China

    Bixuan Guo, Qingwen Liu, Qing Su, Wanting Liu, Pengyao Ju & Qiaolin Wu

  2. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, 2699 Qianjin Street, Changchun, 130012, People’s Republic of China

    Guanghua Li

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  1. Bixuan Guo
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  2. Qingwen Liu
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Guo, B., Liu, Q., Su, Q. et al. A triphenylamine-functionalized fluorescent organic polymer as a turn-on fluorescent sensor for Fe3+ ion with high sensitivity and selectivity. J Mater Sci 53, 15746–15756 (2018). https://doi.org/10.1007/s10853-018-2726-1

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