Dual responsive spiropyran-ended poly(N-vinyl caprolactam) for reversible complexation with metal ions

  • Zhouxiaoshuang Yang
  • Feng Wang
  • Hui LiuEmail author


With the spiropyran-containing compound as the initiator, dual responsive spiropyran-ended poly(N-vinyl caprolactam) (SP-PNVCL) was synthesized by atom transfer radical polymerization. The structure of the resulting polymer was characterized by 1H NMR and gel permeation chromatography, and the polymer had both reversible light-responsive and thermo-sensitive behaviors. Metal ions could be bound between merocyanine formed by photoisomerization of spiropyran and the amino group of N-vinyl caprolactam unit through synergetic coordination. The complexation of SP-PNVCL with several metal ions was investigated by UV-Vis absorption spectroscopy, and it was found that SP-PNVCL might be used as a potential recognition probe for Fe2+, accompanied by obvious color change from colorless to brown by naked eye. The detection limit and photo-reversible recyclable behaviors of SP-PNVCL for Fe2+ were also investigated in details. The kind of spiropyran-ended poly(N-vinyl caprolactam) had great application potential in environment protection and biological area.


N-vinyl caprolactam Spiropyran Dual responsive Complexation Metal ions 



This work was financially supported by National Natural Science Foundation of China (Grant No. 21376271) and the Hunan Provincial Science and Technology Plan Project, China (Grant No. 2016TP1007). Hui Liu also thanked for the help in testing from Advanced Research Center, Central South University.

Compliance with ethical standards

Conflict of interest

The authors declare no competing financial interest.

Supplementary material

10965_2019_1747_MOESM1_ESM.docx (593 kb)
ESM 1 (DOCX 593 kb)


  1. 1.
    Sui BL, Tang SM, Liu TH, Kim BS, Belfield KD (2014) Novel BODIPY-based fluorescence turn-on sensor for Fe3+ and its bioimaging application in living cells. ACS Appl Mater Inter 6:18408–18412CrossRefGoogle Scholar
  2. 2.
    Kagit R, Yildirim M, Ozay O, Yesilot S, Ozay H (2014) Phosphazene based multicentered naked-eye fluorescent sensor with high selectivity for Fe3+ ions. Inorg Chem 53:2144–2151CrossRefGoogle Scholar
  3. 3.
    Santiago AA, Ibarra-Palos A, Cruz-Morales JA, Sierra JM, Abatal K (2018) Synthesis, characterization, and heavy metal adsorption properties of sulfonated aromatic polyamides. High Perform Polym 30:591–601CrossRefGoogle Scholar
  4. 4.
    Jia YY, Wang L, Ma L, Yang ZG (2018) Speciation analysis of six arsenic species in marketed shellfish: extraction optimization and health risk assessment. Food Chem 244:311–316CrossRefGoogle Scholar
  5. 5.
    Fu L, Shi SY, Chen XQ (2018) Accurate quantification of toxic elements in medicine food homologous plants using ICP-MS/MS. Food Chem 245:692–697CrossRefGoogle Scholar
  6. 6.
    Cui HQ, Liu H, Chen S, Wang RM (2015) Synthesis of amphiphilic spiropyran-based random copolymer by atom transfer radical polymerization for Co2+ recognition. Dyes Pigments 115:50–57CrossRefGoogle Scholar
  7. 7.
    Urek SK, Francic N, Turel M, Lobnik A (2013) Sensing heavy metals using mesoporous-based optical chemical sensors. J Nanomater:501320Google Scholar
  8. 8.
    Lechuga LM (2015) Optical biochemical and chemical sensors. Anal Bioanal Chem 404:2795–2796CrossRefGoogle Scholar
  9. 9.
    Hussein MA, Alam MM, Alenazi NA, Alamry KA, Asiri AM, Rahman MM (2018) Nanocomposite based functionalized Polyethersulfone and conjugated ternary ZnYCdO nanomaterials for the fabrication of selective Cd2+ sensor probe. J Polym Res 25:262CrossRefGoogle Scholar
  10. 10.
    Ullah N, Mansha M, Khan I, Qurashi A (2018) Nanomaterial-based optical chemical sensors for the detection of heavy metals in water: recent advances and challenges. Trac-Trend Anal Chem 100:155–166CrossRefGoogle Scholar
  11. 11.
    Otsuki J, Akasaka T, Araki K Molecular switches for electron and energy transfer processes based on metal complexes. Coordin. Chem. Rev 252:32–56CrossRefGoogle Scholar
  12. 12.
    Wang F, Tang JT, Liu H, Yu GP, Zou YP (2019) Self-assembled polymeric micelles as amphiphilic particulate emulsifiers for controllable Pickering emulsions. Mater Chem Front 3:356–364CrossRefGoogle Scholar
  13. 13.
    Wang F, Yu XY, Yang ZXS, Duan H, Zhang ZJ, Liu H (2018) Dual pH- and light-responsive amphiphilic random copolymer nanomicelles as particulate emulsifiers to stabilize the oil/water interface. J Phys Chem C 122:18995–19003CrossRefGoogle Scholar
  14. 14.
    Wang F, Liu H (2018) Dual-functional emulsifying/antifogging coumarin-containing polymeric micelle. J Phys Chem C 122:3434–3442CrossRefGoogle Scholar
  15. 15.
    Li LX, Lu B, Zhang Y, Xing XD, Wu XY, Liu ZL (2015) Multi-sensitive copolymer hydrogels of N-isopropylacrylamide with several polymerizable azobenzene-containing monomers. J Polym Res 22:176CrossRefGoogle Scholar
  16. 16.
    Szymanski W, Beierle JM, Kistemaker HAV, Velema WA, Feringa BL (2013) Reversible photocontrol of biological systems by the incorporation of molecular photoswitches. Chem Rev 113:6114–6178CrossRefGoogle Scholar
  17. 17.
    Bao LH, Sun JX, Li Q (2014) Synthesis and properties of waterborne polyurethane containing spiropyran groups. J Polym Res 21:575CrossRefGoogle Scholar
  18. 18.
    Natali M, Aakeroey C, Desper J, Giordani S (2010) The role of metal ions and counterions in the switching behavior of a carboxylic acid functionalized spiropyran. Dalton T 39:8269–8277CrossRefGoogle Scholar
  19. 19.
    Chernyshev AV, Voloshin NA, Metelitsa AV, Tkachev VV, Aldoshin SM, Solov'eva E, Rostovtseva I, Minkin VI (2013) Metal complexes of new photochromic chelator: structure, stability and photodissociation. J Photoch Photobio A 265:1–9CrossRefGoogle Scholar
  20. 20.
    Paramonov SV, Lokshin V, Fedorova OA (2011) Spiropyran, chromene or spirooxazine ligands: insights into mutual relations between complexing and photochromic properties. J Photoch Photobio C 12:209–236CrossRefGoogle Scholar
  21. 21.
    Suzuki T, Kawata Y, Kahata S, Kato T (2003) Photo-reversible Pb2+-complexation of insoluble poly(spiropyran methacrylate-co-perfluorohydroxy methacrylate) in polar solvents. Chem Commun (16):2004–2005Google Scholar
  22. 22.
    Suzuki T, Hirahara Y, Bunya K, Shinozaki H (2010) Photo-reversible and selective Cu2+ complexation of a spiropyran-carrying sulfobetaine copolymer in saline solution. J Mater Chem 20:2773–2779CrossRefGoogle Scholar
  23. 23.
    Fries K, Samanta S, Orski S, Locklin J (2008) Reversible colorimetric ion sensors based on surface initiated polymerization of photochromic polymers. Chem Commun (47):6288–6290Google Scholar
  24. 24.
    Fries KH, Driskell JD, Samanta S, Locklin J (2010) Spectroscopic analysis of metal ion binding in spiropyran containing copolymer thin films. Anal Chem 82:3306–3314CrossRefGoogle Scholar
  25. 25.
    Fries KH, Driskell JD, Sheppard GR, Locklin J (2011) Fabrication of spiropyran-containing thin film sensors used for the simultaneous identification of multiple metal ions. Langmuir 27:12253–12260CrossRefGoogle Scholar
  26. 26.
    Fries KH, Sheppard GR, Bilbrey JA, Locklin J (2014) Tuning chelating groups and comonomers in spiropyran-containing copolymer thin films for color-specific metal ion binding. Polym Chem 5:2094–2102CrossRefGoogle Scholar
  27. 27.
    Connal LA, Franks GV, Qiao GG (2010) Photochromic, metal-absorbing honeycomb structures. Langmuir 26:10397–10400CrossRefGoogle Scholar
  28. 28.
    Dunne A, Delaney C, McKeon A, Nesterenko P, Paull B, Benito-Lopez F, Diamond D, Flores L (2018) Micro-capillary coatings based on spiropyran polymeric brushes for metal ion binding, detection, and release in continuous flow. Sensors 18:1083CrossRefGoogle Scholar
  29. 29.
    Xie BQ, Qiu ZS, Huang WA, Cao J, Zhong HY (2013) Characterization and aqueous solution behavior of novel thermo-associating polymers. J Macromol Sci A 50:230–237CrossRefGoogle Scholar
  30. 30.
    Cortez-Lemus NA, Licea-Claverie A (2016) Poly(N-vinylcaprolactam), a comprehensive review on a thermoresponsive polymer becoming popular. Prog Polym Sci 53:1–51CrossRefGoogle Scholar
  31. 31.
    Mohammed MN, Bin Yusoh K, Shariffuddin JHBH (2018) Poly(N-vinyl caprolactam) thermoresponsive polymer in novel drug delivery systems: a review. Mater Express 8:21–34CrossRefGoogle Scholar
  32. 32.
    Ventura C, Byrne R, Audouin F, Heise A (2011) Atom transfer radical polymerization synthesis and photoresponsive solution behavior of spiropyran end-functionalized polymers as simplistic molecular probes. J Polym Sci Pol Chem 49:3455–3463CrossRefGoogle Scholar
  33. 33.
    Nakahara Y, Nakamura J, Shirotani N, Kimura K (2012) Synthesis of amphiphilic copolymers bearing a spirobenzopyran moiety at the end group and their photoresponsive micellar behaviors in water. Chem Lett 41:1142–1144CrossRefGoogle Scholar
  34. 34.
    Shen HJ, Zhou M, Zhang Q, Keller A, Shen Y (2015) Zwitterionic light-responsive polymeric micelles for controlled drug delivery. Colloid Polym Sci 293:1685–1694CrossRefGoogle Scholar
  35. 35.
    Wang F, Xu WS, Ouyang YS, Zhang LL, Liu H (2018) Reversible crosslinking terpolymer shell-based mesoporous silica nanoparticles as on-off nanocarriers for pyrene-releasing application. J Taiwan Inst Chem E 91:578–587CrossRefGoogle Scholar
  36. 36.
    Zakharova MI, Coudret C, Pimienta V, Micheau JC, Sliwa M, Poizat O, Buntinx G, Delbaere S, Vermeersch G, Metelitsa AV, Voloshin N, Minkin VI (2011) Kinetic modelling of the photochromism and metal complexation of a spiropyran dye: application to the co(II)-spiroindoline-diphenyloxazolebenzopyran system. Dyes Pigments 89:324–329CrossRefGoogle Scholar
  37. 37.
    Shiraishi Y, Matsunaga Y, Hirai T (2012) Selective colorimetric sensing of co(II) in aqueous media with a spiropyran-amide-dipicolylamine linkage under UV irradiation. Chem Commun 48:5485–5487CrossRefGoogle Scholar
  38. 38.
    Sahoo PR, Kumar S (2016) Synthesis of an optically switchable salicylaldimine substituted naphthopyran for selective and reversible Cu2+ recognition in aqueous solution. RSC Adv 6:20145–20154CrossRefGoogle Scholar
  39. 39.
    Heng S, McDevitt CA, Stubing DB, Whittall JJ, Thompson JG, Engler TK, Abell AD, Monro TM (2013) Microstructured optical fibers and live cells: a water-soluble, photochromic zinc sensor. Biomacromolecules 14:3376–3379CrossRefGoogle Scholar
  40. 40.
    Banerjee A, Sahana A, Guha S, Lohar S, Hauli I, Mukhopadhyay SK, Matalobos JS, Das D (2012) Nickel(II)-induced excimer formation of a naphthalene-based fluorescent probe for living cell imaging. Inorg Chem 51:5699–5704CrossRefGoogle Scholar
  41. 41.
    Han SL, Chen Y (2011) Mercury ion induced activation of the C-O bond in a photo-responsive spiropyran. Dyes Pigments 88:235–239CrossRefGoogle Scholar
  42. 42.
    Bing QJ, Wang L, Li DL, Wang G (2018) A new high selective and sensitive turn-on fluorescent and ratiometric absorption chemosensor for Cu2+ based on benzimidazole in aqueous solution and its application in live cell. Spectrochim Acta A 202:305–313CrossRefGoogle Scholar
  43. 43.
    Qi Y, Zhao J, Weng GJ, Li JJ, Zhu J, Zhao JW (2018) Modification-free colorimetric and visual detection of Hg2+ based on the etching from core-shell structural au-ag nanorods to nanorices. Sensor Actuat B-Chem 267:181–190CrossRefGoogle Scholar
  44. 44.
    Choodum A, Sriprom W, Wongniramaikul W (2019) Portable and selective colorimetric film and digital image colorimetry for detection of iron. Spectrochim Acta A 208:40–47CrossRefGoogle Scholar
  45. 45.
    Najarzadekan H, Sereshti H (2018) Transparent polycaprolactam electrospun nanofibers doped with 1,10-phenanthroline optical sensor for colorimetric determination of iron (II) and vitamin C. Fiber Polym 19:2149–2156CrossRefGoogle Scholar

Copyright information

© The Polymer Society, Taipei 2019

Authors and Affiliations

  1. 1.College of Chemistry and Chemical EngineeringCentral South UniversityChangshaPeople’s Republic of China
  2. 2.Hunan Provincial Key Laboratory of Efficient and Clean Utilization of Manganese ResourcesCentral South UniversityChangshaPeople’s Republic of China

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