Abstract
Thermo-responsive poly(N-isopropylacrylamide) with terminal azobenzene group (PNIPAM-Azo) can show distinct property changes in response to temperature and light. In this paper, azobenzene-terminated trithiocarbonate (DDMAT-Azo) was synthesized as chain transfer agent, with which PNIPAM-Azo was prepared by reversible addition-fragmentation transfer (RAFT) polymerization of NIPAM in 1, 4-dioxane at 80 °C under N2 atmosphere, azodiisobutyronitrile as initiator. The structure of DDMAT-Azo was characterized by nuclear magnetic resonance (NMR) and fourier transform infrared spectra, and PNIPAM-Azo was characterized by NMR spectra and Gel Permeation Chromatography (GPC). The result from GPC showed the numerical average molecular weight of PNIPAM-Azo was 3870 and its molecular weight distribution index was 1.31. Furthermore, thermo- and light-responsive hydrogel was obtained by introducing PNIPAM-Azo. Both PNIPAM-Azo and the hydrogel showed good light sensitivity and thermo sensitivity. Such double-stimuli sensitive hydrogel will be applied in biomaterials such as sensor, drug controlled release, information storage etc.
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The authors confirm that the data supporting the findings of this study are available within the article. Otherwise, the data that support the findings of this study can be obtained from the corresponding author, [Li], upon reasonable request.
References
Gil ES, Hudson SM (2004) Stimuli-reponsive polymers and their bioconjugates. Prog Polym Sci 29:1173–1222
Liu F, Urban MW (2010) Recent advances and challenges in designing stimuli-responsive polymers. Prog Polym Sci 35:3–23
Roy D, Cambre JN, Sumerlin BS (2010) Future perspectives and recent advances in stimuli-responsive materials. Prog Polym Sci 35:278–301
Schild HG (1992) Poly(N-isopropylacrylamide): experiment, theory and application. Prog Polym Sci 17:163–249
Halperin A, Kröger M, Winnik FM (2015) Poly(N-isopropylacrylamide) phase diagrams: fifty years of research. Angew Chem Int Edit 54:15342–15367
Li C, Xue Q, Ji Z, Li Y, Zhang H, Li D (2020) Construction of photonic crystals with thermally adjustable pseudo-gaps. Soft Matter 16:3063–3068
Tagliazucchi M, Blaber MG, Schatz GC, Weiss EA, Szleifer I (2012) Optical properties of responsive hybrid Au@polymer nanoparticles. ACS Nano 6:8397–8406
Li D, Liu N, Gao Y, Lin W, Li C (2017) Thermosensitive polymer stabilized core-shell AuNR@Ag nanostructures as “smart” recyclable catalyst. J Nanopart Res 19:377
Li D, Li C, Yang Y, He Q, Li J (2011) Interfacial dispersion of poly(N-isopropylacrylamide)/gold nanocomposites. J Nanosci Nanotechnol 11:2052–2056
Xu X, Bizmark N, Christie KSS, Datta SS, Ren ZJ, Priestley RD (2022) Thermoresponsive polymers for water treatment and collection. Macromolecules 55:1894–1909
Jochum FD, Theato P (2013) Temperature- and light-responsive smart polymer materials. Chem Soc Rev 42:7468–7483
Jochum FD, Zur Borg L, Roth PJ, Theato P (2009) Thermo- and light-responsive polymers containing photoswitchable azobenzene end groups. Macromolecules 42:7854–7862
Jochum FD, Theato P (2010) Thermo- and light responsive micellation of azobenzene containing block copolymers. Chem Commun 46:6717–6719
Ren H, Qiu X-P, Shi Y, Yang P, Winnik FM (2019) Light, temperature, and pH control of aqueous azopyridine-terminated poly(N-isopropylacrylamide) solutions. Polym Chem 10:5080–5086
Kumar GS, Neckers DC (1989) Photochemistry of azobenzene-containing polymers. Chem Rev 89:1915–1925
Zhang QM, Li X, Islam MR, Wei M, Serpe MJ (2014) Light switchable optical materials from azobenzene crosslinked poly(N-isopropylacrylamide)-based microgels. J Mater Chem C 2:6961–6965
Colaco R, Appiah C, Staubitz A (2023) Controlling the LCST-phase transition in azobenzene-functionalized poly (n-isopropylacrlyamide) hydrogels by light. Gels 9:75
Kungwatchakun D, Irie M (1988) Photoresponsive polymers. Photocontrol of the phase separation temperature of aqueous solutions of poly-[N-isopropylacrylamide-co-N-(4-phenylazophenyl)acrylamide]. Makromol Chemie Rapid Commun 9:243–246
Kröger R, Menzel H, Hallensleben ML (1994) Light controlled solubility change of polymers: Copolymers of N, N-dimethylacrylamide and 4-phenylazophenyl acrylate. Macromol Chem Phys 195:2291–2298
Akiyama H, Tamaoki N (2004) Polymers derived from N-isopropylacrylamide and azobenzene-containing acrylamides: Photoresponsive affinity to water. J Polym Sci Pol Chem 42:5200–5214
Desponds A, Freitag R (2003) Synthesis and characterization of photoresponsive n-isopropylacrylamide cotelomers. Langmuir 19:6261–6270
Chiefari J, Chong YK, Ercole F, Krstina J, Jeffery J, Le TPT, Mayadunne RTA, Meijs GF, Moad CL, Moad G, Rizzardo E, Thang SH (1998) Living free-radical polymerization by reversible addition−fragmentation chain transfer: the RAFT process. Macromolecules 31:5559–5562
Ma Y-M, Wei D-X, Yao H, Wu L-P, Chen G-Q (2016) Synthesis, characterization and application of thermoresponsive polyhydroxyalkanoate-graft-poly(n-isopropylacrylamide). Biomacromolecules 17:2680–2690
Li C, Wang C, Ji Z, Jiang N, Lin W, Li D (2019) Synthesis of thiol-terminated thermoresponsive polymers and their enhancement effect on optical limiting property of gold nanoparticles. Eur Polym J 113:404–410
Díaz-Silvestre SE, St Thomas C, Maldonado-Textle H, Rivera-Vallejo C, de León-Gómez RED, Jiménez-Regalado EJ (2018) Effect of N-isopropylacrylamide thermoresponsive blocks on the rheological properties of water-soluble thermoassociative copolymers synthesized via RAFT polymerization. Colloid Polym Sci 296:1699–1710
Ishii N, Obeid R, Qiu X-P, Mamiya J-I, Ikeda T, Winnik FM (2010) Synthesis and association behavior of telechelic poly(N-isopropylacrylamides) with azobenzene end groups. Mol Cryst Liq Cryst 529:60–70
Qiu X, Koga T, Tanaka F, Winnik FM (2013) New insights into the effects of molecular weight and end group on the temperature-induced phase transition of poly(N-isopropylacrylamide) in water. Sci China Chem 56:56–64
Lai JT, Filla D, Shea R (2002) Functional polymers from novel carboxyl-terminated trithiocarbonates as highly efficient RAFT agents. Macromolecules 35:6754–6756
Mayadunne RTA, Rizzardo E, Chiefari J, Krstina J, Moad G, Postma A, Thang SH (2000) Living polymers by the use of trithiocarbonates as reversible addition−fragmentation chain transfer (RAFT) agents: ABA triblock copolymers by radical polymerization in two steps. Macromolecules 33:243–245
Maldonado-Textle H, Jiménez-Regalado EJ, St Thomas C (2022) Thickening behavior of thermo-associative water soluble multiblock copolymers under redox RAFT polymerization. Polym Eng Sci 62:2932–2946
Peppas NA, Hilt JZ, Khademhosseini A, Langer R (2006) Hydrogels in biology and medicine: from molecular principles to bionanotechnology. Adv Mater 18:1345–1360
Guan Y, Zhao H-B, Yu L-X, Chen S-C, Wang Y-Z (2014) Multi-stimuli sensitive supramolecular hydrogel formed by host–guest interaction between PNIPAM-Azo and cyclodextrin dimers. RSC Adv 4:4955–4959
Xu X, Liu Y, Fu W, Yao M, Ding Z, Xuan J, Li D, Wang S, Xia Y, Cao M (2020) Poly(N-isopropylacrylamide)-based thermoresponsive composite hydrogels for biomedical applications. Polymers 12:580
Li Y, Xue Q, Zhang H, Ji Z, Li D, Li C (2020) Synthesis of optothermal responsive polymers by thiol-ene click reaction and their aggregation behavior. J Polym Res 27:172
Acknowledgments
This work was financially supported by National Natural Science foundation of China (21975139) and Department of Chemistry, Qingdao University of Science and Technology (No. QUSTHX201812).
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Li, D., Qian, X., Huang, R. et al. Preparation of PNIPAM-Azo by RAFT polymerization and their application in thermo- and light-responsive hydrogel. J Polym Res 30, 155 (2023). https://doi.org/10.1007/s10965-023-03541-9
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DOI: https://doi.org/10.1007/s10965-023-03541-9