Citation: Jin-Long Zhang, Jun-Yan Tan, Xin-Hua Wan, Jie Zhang. A Luminescent Thermometer Based on Linearly Thermo-responsive Copolymer and Polyoxometalates[J]. Chinese Journal of Polymer Science, ;2019, 37(11): 1113-1118. doi: 10.1007/s10118-019-2287-z shu

A Luminescent Thermometer Based on Linearly Thermo-responsive Copolymer and Polyoxometalates

Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, Center for Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Corresponding author: Xin-Hua Wan, xhwan@pku.edu.cn Jie Zhang, jz10@pku.edu.cn
Received Date: 8 March 2019
Revised Date: 1 January 2019
Available Online: 19 June 2019

A novel switchable luminescent thermometer based on thermo-responsive triblock copolymer poly(ethylene glycol)-b-poly(acrylamide-co-acrylonitrile-co-dimethylaminoethylmethacrylate) (PEO₁₁₃-b-P(AAm₂₆₄-co-AN₁₁₂-co-DMA₈)) and Eu-containing polyoxometalate (Eu-POM) was successfully constructed. The copolymer synthesized by RAFT exhibited a linear response to temperature variations in aqueous media, which was quite different from the uncharged copolymer P(AAm-co-AN) having a specific upper critical solution temperature (UCST). Eu-POM was surrounded around thermo-responsive blocks through electrostatic interactions, and its luminescence could be finely tuned due to the sensitivity of copolymer to the temperature variation. In cold water, POMs were trapped in highly hydrophobic cores, exhibiting an intense emission. With the upraising of temperature, the emission intensity presented a gradual decrease and showed a linear correlation with temperature. When the complex solution cooled down, the luminescence could also be perfectly restored. This temperature-luminescence correlation could be held for numerous trials, showing a potential application in thermometer.
- Luminescent thermometer,
- Block copolymer,
- Polyoxometalate,
- UCST
1. [1]
  Gibson, M. I.; O'Reilly, R. K. To aggregate, or not to aggregate? Considerations in the design and application of polymeric thermally-responsive nanoparticles. Chem. Soc. Rev. 2013, 42, 7204-7213. doi: 10.1039/C3CS60035A
2. [2]
  Roy, D.; Brooks, W. L.; Sumerlin, B. S. New directions in thermoresponsive polymers. Chem Soc Rev 2013, 42, 7214-43. doi: 10.1039/c3cs35499g
3. [3]
  Jochum, F. D.; Theato, P. Temperature- and light-responsive smart polymer materials. Chem. Soc. Rev. 2013, 42, 7468-7483. doi: 10.1039/C2CS35191A
4. [4]
  Grubbs, R. B.; Sun, Z. Shape-changing polymer assemblies. Chem. Soc. Rev. 2013, 42, 7436-45. doi: 10.1039/c3cs60079c
5. [5]
  Al-Ahmady, Z.; Kostarelos, K. Chemical components for the design of temperature-responsive vesicles as cancer therapeutics. Chem. Rev. 2016, 116, 3883-3918. doi: 10.1021/acs.chemrev.5b00578
6. [6]
  Seeboth, A.; Lötzsch, D.; Ruhmann, R.; Muehling, O. Thermochromic polymers—Function by design. Chem. Rev. 2014, 114, 3037-3068. doi: 10.1021/cr400462e
7. [7]
  Niskanen, J.; Tenhu, H. How to manipulate the upper critical solution temperature (UCST)? Polym. Chem. 2017, 8, 220-232. doi: 10.1039/C6PY01612J
8. [8]
  Yin, J.; Hu, J.; Zhang, G.; Liu, S. Schizophrenic core-shell microgels: Thermoregulated core and shell swelling/collapse by combining UCST and LCST phase transitions. Langmuir 2014, 30, 2551-2558. doi: 10.1021/la500133y
9. [9]
  Woodfield, P. A.; Zhu, Y.; Pei, Y.; Roth, P. J. Hydrophobically modified sulfobetaine copolymers with tunable aqueous UCST through postpolymerization modification of poly(pentafluorophenyl acrylate). Macromolecules 2014, 47, 750-762. doi: 10.1021/ma402391a
10. [10]
  Maji, T.; Banerjee, S.; Biswas, Y.; Mandal, T. K. Dual-stimuli-responsive L-serine-based zwitterionic UCST-type polymer with tunable thermosensitivity. Macromolecules 2015, 48, 4957-4966. doi: 10.1021/acs.macromol.5b01099
11. [11]
  Zhang, Q.; Hoogenboom, R. Polymers with upper critical solution temperature behavior in alcohol/water solvent mixtures. Prog. Polym. Sci. 2015, 48, 122-142. doi: 10.1016/j.progpolymsci.2015.02.003
12. [12]
  Seuring, J.; Bayer, F. M.; Huber, K.; Agarwal, S. Upper critical solution temperature of poly(N-acryloyl glycinamide) in water: A concealed property. Macromolecules 2012, 45, 374-384. doi: 10.1021/ma202059t
13. [13]
  Fu, W. X.; Zhao, B. Thermoreversible physically crosslinked hydrogels from UCST-type thermosensitive ABA linear triblock copolymers. Polym. Chem. 2016, 7, 6980-6991. doi: 10.1039/C6PY01517D
14. [14]
  Chen, L.; Honma, Y.; Mizutani, T.; Liaw, D. J.; Gong, J. P.; Osada, Y. Effects of polyelectrolyte complexation on the UCST of zwitterionic polymer. Polymer 2000, 41, 141-147. doi: 10.1016/S0032-3861(99)00161-5
15. [15]
  Seuring, J.; Agarwal, S. First example of a universal and cost-effective approach: Polymers with tunable upper critical solution temperature in water and electrolyte solution. Macromolecules 2012, 45, 3910-3918. doi: 10.1021/ma300355k
16. [16]
  Pineda-Contreras, B. A.; Schmalz, H.; Agarwal, S. pH dependent thermoresponsive behavior of acrylamide-acrylonitrile UCST-type copolymers in aqueous media. Polym. Chem. 2016, 7, 1979-1986. doi: 10.1039/C6PY00162A
17. [17]
  Zhang, H.; Tong, X.; Zhao, Y. Diverse thermoresponsive behaviors of uncharged UCST block copolymer micelles in physiological medium. Langmuir 2014, 30, 11433-11441. doi: 10.1021/la5026334
18. [18]
  Zhang, H.; Guo, S.; Fan, W.; Zhao, Y. Ultrasensitive pH-induced water solubility switch using UCST polymers. Macromolecules 2016, 49, 1424-1433. doi: 10.1021/acs.macromol.5b02522
19. [19]
  Käfer, F.; Liu, F.; Stahlschmidt, U.; Jérôme, V.; Freitag, R.; Karg, M.; Agarwal, S. LCST and UCST in one: Double thermoresponsive behavior of block copolymers of poly(ethylene glycol) and poly(acrylamide-co-acrylonitrile). Langmuir 2015, 31, 8940-8946. doi: 10.1021/acs.langmuir.5b02006
20. [20]
  Huang, G.; Li, H.; Feng, S.-T.; Li, X.; Tong, G.; Liu, J.; Quan, C.; Jiang, Q.; Zhang, C.; Li, Z. Self-assembled UCST-type micelles as potential drug carriers for cancer therapeutics. Macromol. Chem. Phys. 2015, 216, 1014-1023. doi: 10.1002/macp.v216.9
21. [21]
  Misdrahi, M. F.; Wang, M.; Pradeep, C. P.; Li, F.-Y.; Lydon, C.; Xu, L.; Cronin, L.; Liu, T. Amphiphilic properties of dumbbell-shaped inorganic-organic-inorganic molecular hybrid materials in solution and at an interface. Langmuir 2011, 27, 9193-9202. doi: 10.1021/la2013914
22. [22]
  Long, D.-L.; Tsunashima, R.; Cronin, L. Polyoxometalates: Building blocks for functional nanoscale systems. Angew. Chem. Int. Ed. 2010, 49, 1736-1758. doi: 10.1002/anie.v49:10
23. [23]
  Wang, S. S.; Yang, G. Y. Recent advances in polyoxometalate-catalyzed reactions. Chem. Rev. 2015, 115, 4893-4962. doi: 10.1021/cr500390v
24. [24]
  Wei, H. B.; Zhang, J. L.; Shi, N.; Liu, Y.; Zhang, B.; Zhang, J.; Wan, X. H. A recyclable polyoxometalate-based supramolecular chemosensor for efficient detection of carbon dioxide. Chem. Sci. 2015, 6, 7201-7205. doi: 10.1039/C5SC02020D
25. [25]
  Wei, H. B.; Shi, N.; Zhang, J. L.; Guan, Y.; Zhang, J.; Wan, X. H. pH-responsive inorganic-organic hybrid supramolecular hydrogels with jellyfish-like switchable chromic luminescence. Chem. Commun. 2014, 50, 9333-9335. doi: 10.1039/C4CC04000G
26. [26]
  Yang, Z.; Cao, J.; He, Y.; Yang, J. H.; Kim, T.; Peng, X.; Kim, J. S. Macro-/micro-environment-sensitive chemosensing and biological imaging. Chem. Soc. Rev. 2014, 43, 4563-4601. doi: 10.1039/C4CS00051J
27. [27]
  Okabe, K.; Inada, N.; Gota, C.; Harada, Y.; Funatsu, T.; Uchiyama, S. Intracellular temperature mapping with a fluorescent polymeric thermometer and fluorescence lifetime imaging microscopy. Nat. Commun. 2012, 3, 705. doi: 10.1038/ncomms1714
28. [28]
  Gota, C.; Okabe, K.; Funatsu, T.; Harada, Y.; Uchiyama, S. Hydrophilic fluorescent nanogel thermometer for intracellular thermometry. J. Am. Chem. Soc 2009, 131, 2766-2767. doi: 10.1021/ja807714j
29. [29]
  Seuring, J.; Agarwal, S. Polymers with upper critical solution temperature in aqueous solution. Macromol. Rapid. Commun 2012, 33, 1898-1920. doi: 10.1002/marc.v33.22
30. [30]
  Zhang, J.; Shi, N.; Zhang, J.; Guan, Y.; Qiao, W.; Wan, X. Light triggered co-assembly of photocleavable copolymers and polyoxometalates with enhanced photoluminescence. Macromol. Rapid. Commun 2017, 38, 1600550. doi: 10.1002/marc.v38.2
31. [31]
  Bu, W. F.; Li, H. L.; Li, W.; Wu, L. X.; Zhai, C. X.; Wu, Y. Q. Surfactant-encapsulated europium-substituted heteropolyoxotungstates: Structural characterizations and photophysical properties. J. Phys. Chem. B 2004, 108, 12776-12782. doi: 10.1021/jp0485237
32. [32]
  Zhang, T. R.; Spitz, C.; Antonietti, M.; Faul, C. F. J. Highly photoluminescent polyoxometaloeuropate-surfactant complexes by ionic self-assembly. Chem. Eur. J 2005, 11, 1001-1009 doi: 10.1002/(ISSN)1521-3765
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