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High tri-stimulus response photochromic cotton fabrics based on spiropyran dye by thiol-ene click chemistry

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Abstract

In this paper, we proposed to prepare a spiropyran (SP)-based photochromic cotton fabric with high tri-stimulus response by thiol-ene click chemistry, which has excellent photochromic properties, good durability, and can quickly return to its original state under three different stimulations. The SP target monomer with ene group in the side chain was synthesized, and the cotton fabric was subjected to thiol modification by using 3-mercaptopropyltriethoxysilane. The SP molecule was grafted to the modified cotton fabric by covalent bonding, therefore effectively enhanced its durability in practical daily use. The results of FTIR, NMR, Raman and UV spectra confirmed the chemical composition. SEM images and energy-dispersive X-ray spectroscopy mapping spectra verified the grafting between this SP-based dye and modified cotton fabrics. The test data of color characteristic values indicated that the fabric undergoes significant color changes with fast photochromic response, high fatigue resistance, and maintains impressive reusability after experiencing 20 reversible cycles. The photochromic mechanism of cotton fabrics was attributed to the cleavage of C–O bond in the molecular structure of SP under ultraviolet (UV) irradiation. In addition, the properties related to practical applications including washing fastness and UV resistance have also been studied, proving its great potential in wearable and flexible textile-based sensors.

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References

  1. Aldib M, Christie RM (2011) Textile applications of photochromic dyes. Part 4: application of commercial photochromic dyes as disperse dyes to polyester by exhaust dyeing. Color Technol 127:282–287. https://doi.org/10.1111/j.1478-4408.2011.00308.x

  2. Arkhipova AN, Panchenko PA, Fedorov YV, Fedorova OA (2017) Relationship between the photochromic and fluorescent properties of 4-styryl derivatives of N-butyl-1,8-naphthalimide. Mendeleev Commun 27:53–55. https://doi.org/10.1016/j.mencom.2017.01.016

  3. Athanassiou A et al (2006) Photocontrolled variations in the wetting capability of photochromic polymers enhanced by surface nanostructuring. Langmuir 22:2329–2333. https://doi.org/10.1021/la052122g

  4. Ayazi-Yazdi S, Karimi L, Mirjalili M, Karimnejad M (2017) Fabrication of photochromic, hydrophobic, antibacterial, and ultraviolet-blocking cotton fabric using silica nanoparticles functionalized with a photochromic dye. J Text Inst 108:856–863. https://doi.org/10.1080/00405000.2016.1195088

  5. Billah SMR, Christie RM, Shamey R (2008) Direct coloration of textiles with photochromic dyes. Part 1: application of spiroindolinonaphthoxazines as disperse dyes to polyester, nylon and acrylic fabrics. Color Technol 124:223–228. https://doi.org/10.1111/j.1478-4408.2008.00145.x

  6. Bretel G, Le Grognec E, Jacquemin D, Hirose T, Matsuda K, Felpin F-X (2019) Fabrication of robust spatially resolved photochromic patterns on cellulose papers by covalent printing for anticounterfeiting applications. ACS Appl Polym Mater 1:1240–1250. https://doi.org/10.1021/acsapm.9b00266

  7. Buback J, Kullmann M, Langhojer F, Nuernberger P, Schmidt R, Wuerthner F, Brixner T (2010) Ultrafast bidirectional photoswitching of a spiropyran. J Am Chem Soc 132:16510–16519. https://doi.org/10.1021/ja1062746

  8. Cheng T, Lin T, Fang J, Brady R (2007) Photochromic wool fabrics from a hybrid silica coating. Text Res J 77:923–928. https://doi.org/10.1177/0040517507083523

  9. Cheng T, Lin T, Brady R, Wang X (2008a) Fast response photochromic textiles from hybrid silica surface coating. Fibers Polym 9:301–306. https://doi.org/10.1007/s12221-008-0048-7

  10. Cheng T, Lin T, Brady R, Wang X (2008b) Photochromic fabrics with improved durability and photochromic performance. Fibers Polym 9:521–526. https://doi.org/10.1007/s12221-008-0083-4

  11. Chowdhury MA, Joshi M, Butola BS (2014) Photochromic and thermochromic colorants in textile applications. J Eng Fibers Fabr 9:107–123. https://doi.org/10.1177/155892501400900113

  12. Crespy D, Rossi RN (2007) Temperature-responsive polymers with LCST in the physiological range and their applications in textiles. Polym Int 56:1461–1468. https://doi.org/10.1002/pi.2277

  13. Fan F, Wu Y (2017) Photochromic properties of color-matching, double-shelled microcapsules covalently bonded onto cotton fabric and applications to outdoor clothing. J Appl Polym Sci 134:44698. https://doi.org/10.1002/app.44698

  14. Fan F, Zhang W, Wang C (2015) Covalent bonding and photochromic properties of double-shell polyurethane-chitosan microcapsules crosslinked onto cotton fabric. Cellulose 22:1427–1438. https://doi.org/10.1007/s10570-015-0567-5

  15. Fan J, Wang W, Yu D (2018) Preparation of photochromic wool fabrics based on thiol-halogen click chemistry. Dyes Pigm 151:348–355. https://doi.org/10.1016/j.dyepig.2018.01.019

  16. Feczko T, Kovacs M, Voncina B (2012) Improvement of fatigue resistance of spirooxazine in ethyl cellulose and poly(methyl methacrylate) nanoparticles using a hindered amine light stabilizer. J Photochem Photobiol, A 247:1–7. https://doi.org/10.1016/j.jphotochem.2012.08.001

  17. Fleming CL, Li S, Grotli M, Andreasson J (2018) Shining new light on the spiropyran photoswitch: a photocage decides between cis-trans or spiro-merocyanine isomerization. J Am Chem Soc 140:14069–14072. https://doi.org/10.1021/jacs.8b09523

  18. Gerkman MA, Yuan S, Duan P, Taufan J, Schmidt-Rohr K, Han GGD (2019) Phase transition of spiropyrans: impact of isomerization dynamics at high temperatures. Chem Commun 55:5813–5816. https://doi.org/10.1039/c9cc02141h

  19. Ghosh KK, Ha H-H, Kang N-Y, Chandran Y, Chang Y-T (2011) Solid phase combinatorial synthesis of a xanthone library using click chemistry and its application to an embryonic stem cell probe. Chem Commun 47:7488–7490. https://doi.org/10.1039/c1cc11962a

  20. Ghosh S, Remanan S, Mondal S, Ganguly S, Das P, Singha N, Das NC (2018) An approach to prepare mechanically robust full IPN strengthened conductive cotton fabric for high strain tolerant electromagnetic interference shielding. Chem Eng J 344:138–154. https://doi.org/10.1016/j.cej.2018.03.039

  21. Haitao S et al (2013) Spirooxazine-based multifunctional molecular switches with tunable photochromism and nonlinear optical. J Mater Chem C 1:5779–5790. https://doi.org/10.1039/c3tc31131g

  22. Hansen RV, Zhong L, Khor KA, Zheng L, Yang J (2016) Tuneable electrochromism in weavable carbon nanotube/polydiacetylene yarns. Carbon 106:110–117. https://doi.org/10.1016/j.carbon.2016.05.029

  23. Hu J, Meng H, Li G, Ibekwe SI (2012) A review of stimuli-responsive polymers for smart textile applications. Smart Mater Struct 21:053001. https://doi.org/10.1088/0964-1726/21/5/053001

  24. Hu Y, Wang W, Yu D (2016) Functional modification of wool fabric by thiol-epoxy click chemistry. Fibers Polym 17:30–35. https://doi.org/10.1007/s12221-016-5770-y

  25. Jochum FD, Theato P (2013) Temperature- and light-responsive smart polymer materials. Chem Soc Rev 42:7468–7483. https://doi.org/10.1039/c2cs35191a

  26. Julia-Lopez A, Ruiz-Molina D, Hernando J, Roscini C (2019) Solid materials with tunable reverse photochromism. ACS Appl Mater Interfaces 11:11884–11892. https://doi.org/10.1021/acsami.8b22335

  27. Khattab TA, Rehan M, Hamdy Y, Shaheen TI (2018a) Facile development of photoluminescent textile fabric via spray coating of Eu(II)-doped strontium aluminate. Ind Eng Chem Res 57:11483–11492. https://doi.org/10.1021/acs.iecr.8b01594

  28. Khattab TA, Rehan M, Hamouda T (2018b) Smart textile framework: photochromic and fluorescent cellulosic fabric printed by strontium aluminate pigment. Carbohydr Polym 195:143–152. https://doi.org/10.1016/j.carbpol.2018.04.084

  29. Khattab TA et al (2019) Co-encapsulation of enzyme and tricyanofuran hydrazone into alginate microcapsules incorporated onto cotton fabric as a biosensor for colorimetric recognition of urea. React Funct Polym 142:199–206. https://doi.org/10.1016/j.reactfunctpolym.2019.06.016

  30. Kinashi K, Nakamura S, Imamura M, Ishida K, Ueda Y (2012) The mechanism for negative photochromism of spiropyran in silica. J Phys Org Chem 25:462–466. https://doi.org/10.1002/poc.1926

  31. Kinashi K, Suzuki T, Yasunaga H, Tsuchida H, Sakai W, Tsutsumi N, Yamane H (2017) Carrier-assisted dyeing of poly(L-lactic acid) fibers with dispersed photochromic spiropyran dyes. Dyes Pigm 145:444–450. https://doi.org/10.1016/j.dyepig.2017.06.040

  32. Klajn R (2014) Spiropyran-based dynamic materials. Chem Soc Rev 43:148–184. https://doi.org/10.1039/c3cs60181a

  33. Kortekaas L, Browne WR (2019) The evolution of spiropyran: fundamentals and progress of an extraordinarily versatile photochrome. Chem Soc Rev 48:3406–3424. https://doi.org/10.1039/c9cs00203k

  34. Kunigunde C, Christoph Z, Thomas K, Niko M, Gerhard TS (2010) Woven electronic fibers with sensing and display functions for smart textiles. Adv Mater 22:5071–5071. https://doi.org/10.1002/adma.201090145

  35. Lee J et al (2015) Conductive fiber-based ultrasensitive textile pressure sensor for wearable electronics. Adv Mater 27:2433–2439. https://doi.org/10.1002/adma.201500009

  36. Mao H, Lin L, Ma Z, Wang C (2018) Dual-responsive cellulose fabric based on reversible acidichromic and photoisomeric polymeric dye containing pendant azobenzene. Sens Actuators, B 266:195–203. https://doi.org/10.1016/j.snb.2018.02.131

  37. McCoy CP, Donnelly L, Jones DS, Gorman SP (2007) Synthesis and characterisation of polymerisable photochromic spiropyrans: towards photomechanical biomaterials. Tetrahedron Lett 48:657–661. https://doi.org/10.1016/j.tetlet.2006.11.110

  38. Moses JE, Moorhouse AD (2007) The growing applications of click chemistry. Chem Soc Rev 36:1249–1262. https://doi.org/10.1039/b613014n

  39. Palacin T et al (2009) Efficient functionalization of carbon nanotubes with porphyrin dendrons via click chemistry. J Am Chem Soc 131:15394–15402. https://doi.org/10.1021/ja906020e

  40. Pardo R, Zayat M, Levy D (2009) Reaching bistability in a photochromic spirooxazine embedded sol-gel hybrid coatings. J Mater Chem 19:6756–6760. https://doi.org/10.1039/b909198j

  41. Pardo R, Zayat M, Levy D (2011) Photochromic organic-inorganic hybrid materials. Chem Soc Rev 40:672–687. https://doi.org/10.1039/c0cs00065e

  42. Parhizkar M, Zhao Y, Wang X, Lin T (2014) Photostability and durability properties of photochromic organosilica coating on fabric. J Eng Fibers Fabr 9:65–73. https://doi.org/10.1177/155892501400900308

  43. Partington SM, Towns AD (2014) Photochromism in spiroindolinonaphthoxazine dyes: effects of alkyl and ester substituents on photochromic properties. Dyes Pigm 104:123–130. https://doi.org/10.1016/j.dyepig.2014.01.005

  44. Peng L, Guo R, Jiang S, Lan J, He Y, Huang X (2015) Ultrasound-aided dyeing of cotton fabric with spirooxazines and photochromic properties. Fibers Polym 16:1312–1318. https://doi.org/10.1007/s12221-015-1312-2

  45. Pinto TV et al (2016a) Naphthopyran-based silica nanoparticles as new high-performance photoresponsive materials. ACS Appl Mater Interfaces 8:7221–7231. https://doi.org/10.1021/acsami.5b11983

  46. Pinto TV et al (2016b) Screen-printed photochromic textiles through new inks based on SiO2@naphthopyran nanoparticles. ACS Appl Mater Interfaces 8:28935–28945. https://doi.org/10.1021/acsami.6b06686

  47. Rong L et al (2018) Facile fabrication of thiol-modified cellulose sponges for adsorption of Hg2+ from aqueous solutions. Cellulose 25:3025–3035. https://doi.org/10.1007/s10570-018-1758-7

  48. Rosace G, Guido E, Colleoni C, Brucale M, Piperopoulos E, Milone C, Plutino MR (2017) Halochromic resorufin-GPTMS hybrid sol-gel: chemical-physical properties and use as pH sensor fabric coating. Sens Actuators, B 241:85–95. https://doi.org/10.1016/j.snb.2016.10.038

  49. Son Y-A, Park Y-M, Park S-Y, Shin C-J, Kim S-H (2007) Exhaustion studies of spiroxazine dye having reactive anchor on polyamide fibers and its photochromic properties. Dyes Pigm 73:76–80. https://doi.org/10.1016/j.dyepig.2005.10.012

  50. Sun B, He Z, Hou Q, Liu Z, Cha R, Ni Y (2013) Interaction of a spirooxazine dye with latex and its photochromic efficiency on cellulosic paper. Carbohydr Polym 95:598–605. https://doi.org/10.1016/j.carbpol.2013.03.032

  51. Sun D, Wang W, Yu D (2017) Highly hydrophobic cotton fabrics prepared with fluorine-free functionalized silsesquioxanes. Cellulose 24:4519–4531. https://doi.org/10.1007/s10570-017-1388-5

  52. Tsuru Y, Kohri M, Taniguchi T, Kishikawa K, Karatsu T, Hayashi M (2019) Preparation of photochromic liquid core nanocapsules based on theoretical design. J Colloid Interface Sci 547:318–329. https://doi.org/10.1016/j.jcis.2019.04.008

  53. Wang L, Li Q (2018) Photochromism into nanosystems: towards lighting up the future nanoworld. Chem Soc Rev 47:1044–1097. https://doi.org/10.1039/c7cs00630f

  54. Wang Q et al (2018) Dynamic photoswitching of electron energy levels at hybrid ZnO/Organic photochromic molecule junctions. Adv Funct Mater 28:1800716. https://doi.org/10.1002/adfm.201800716

  55. Wang Y, Wang W, Xu R, Zhu M, Yu D (2019) Flexible, durable and thermal conducting thiol-modified rGO-WPU/cotton fabric for robust electromagnetic interference shielding. Chem Eng J 360:817–828. https://doi.org/10.1016/j.cej.2018.12.045

  56. Xu L, Wang W, Yu D (2017) Durable flame retardant finishing of cotton fabrics with halogen-free organophosphonate by UV photoinitiated thiol-ene click chemistry. Carbohydr Polym 172:275–283. https://doi.org/10.1016/j.carbpol.2017.05.054

  57. Yang R, Aubrecht KB, Ma H, Wang R, Grubbs RB, Hsiao BS, Chu B (2014) Thiol-modified cellulose nanofibrous composite membranes for chromium (VI) and lead (II) adsorption. Polymer 55:1167–1176. https://doi.org/10.1016/j.polymer.2014.01.043

  58. Zhang S et al (2018) New insights into synergistic antimicrobial and antifouling cotton fabrics via dually finished with quaternary ammonium salt and zwitterionic sulfobetaine. Chem Eng J 336:123–132. https://doi.org/10.1016/j.cej.2017.10.168

  59. Zhao K, Wang Y, Wang W, Yu D (2018) Moisture absorption, perspiration and thermal conductive polyester fabric prepared by thiol-ene click chemistry with reduced graphene oxide finishing agent. J Mater Sci 53:14262–14273. https://doi.org/10.1007/s10853-018-2671-z

  60. Zheng T, Xu Z, Zhao Y, Li H, Jian R, Lu C (2018) Multiresponsive polysiloxane bearing photochromic spirobenzopyran for sensing pH changes and Fe3+ ions and sequential sensing of Ag+ and Hg2+ ions. Sens Actuators, B 255:3305–3315. https://doi.org/10.1016/j.snb.2017.09.158

  61. Zuo B, Wang M, Lin B-P, Yang H (2018) Photomodulated tricolor-changing artificial flowers. Chem Mater 30:8079–8088. https://doi.org/10.1021/acs.chemmater.8b04204

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Acknowledgments

This work was supported by National Nature Science Foundation of China (No. 51403032).

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Correspondence to Dan Yu.

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Fan, J., Bao, B., Wang, Z. et al. High tri-stimulus response photochromic cotton fabrics based on spiropyran dye by thiol-ene click chemistry. Cellulose 27, 493–510 (2020). https://doi.org/10.1007/s10570-019-02786-2

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Keywords

  • Photochromic
  • Spiropyran
  • Thiol-ene click chemistry
  • Tri-stimulus response
  • Cotton fabric