Abstract
A series of copolymers and their corresponding hydrogels were prepared essentially from N-isopropyl acrylamide (NIPAAm) and acrylamidoazobenzene (AAAB) at different molar ratios. The AAAB was synthesized in advance and verified by elemental analysis, 1H-, and 13C NMR techniques. The effect of AAAB contents on the thermal and ultraviolet response of the copolymer and their corresponding hydrogels was investigated. The results showed that a changed quantity of AAAB in the copolymers and hydrogels would only slightly affect their LCSTs and CGTTs. In addition, the copolymers and their hydrogels show good thermo- and photo-response due to NIPAAm structure and the cis-trans isomerization of azobenzene group upon UV irradiation. Furthermore, effects of AAAB contents on the physical properties and drug release behavior of the copolymeric hydrogels were also examined.
Similar content being viewed by others
References
Heskins M, Guillet JE, James EJ (1968) Solution properties of poly(N-isopropyl acrylamide. J Macromol Sci Chem 2(8):1441–1455
Hirotsu S (1987) Phase transition of a polymer gel in pure and mixed solvent media. J Phys Soc Jpn 56:233–242
Bae YH, Okano T, Kim SW (1990) Temperature dependence of swelling of crosslinked poly(N, N-alkyl substituted acrylamides) in water. J Polym Sci Polym Phys 28:923–936
Zhang XZ, Zhuo RX (2000) Novel synthesis of temperature-sensitive poly(N-isopropyl acrylamide) hydrogel with fast deswelling rate. Eur Polym J 36:643–645
Chu LY, Park SH, Yamaguchi T, Nakao SI (2001) Preparation of thermo-responsive core-shell microcapsules with a porous membrane and poly(N-isopropylacrylamide) gates. J Membr Sci 192:27–39
Wang M, Fang Y, Hu D (2001) Preparation and properties of chitosan-poly(N-isopropylacrylamide) full-IPN hydrogels. React Funct Polym 48:215–221
Peppas NA (1991) Physiologically responsive hydrogels. J Bioact Compat Polym 6:241–246
Kang MS, Gupta VK (2002) Photochromic cross-links in thermoresponsive hydrogels of poly(N-isopropylacrylamide): enthalpic and entropic consequences on swelling behavior. J Phys Chem B 106:4127–4132
Harmon ME, Kuckling D, Frank CW (2003) Photo-cross-linkable PNIPAAm copolymers. 2. Effects of constraint on temperature and ph-responsive hydrogel layers. Macromolecules 36:162–172
Harmon ME, Kuckling D, Frank CW (2003) Photo-cross-linkable PNIPAAm copolymers. 5. Mechanical properties of hydrogel layers. Langmuir 19:10660–10665
Kuckling D, Hoffmann J, Plötner M, Ferse D, Kretschmer K, Adler HP, Arndt KF, Reichelt R (2003) Photocross-linkable poly(N-isopropyl acrylamide) copolymers III: micro-fabricated temperature responsive hydrogels. Polymer 44:4455–4462
Irwan GS, Aoyama Y, Kuroda SI, Kubota H, Kondo T (2005) Photografting of N-isopropyl acrylamide and glycidyl methacrylate binary monomers on polyethylene film: effect of mixed solvent consisting of water and organic solvent. J Appl Polym Sci 97:2469–2475
Sumaru K, Ohi K, Takagi T, Kanamori T, Shinbo T (2006) Photoresponsive properties of poly(N-isopropyl acrylamide) hydrogel partly modified with spirobenzopyran. Langmuir 22:4353–4356
Moniruzzaman M, Fernando GF, Talbot JDR (2004) Synthesis and characterization of an azobenzene- and acrylamide-based photoresponsive copolymer and gel. J Polym Sci A Polym Chem 42:2886–2896
Yager KG, Barrett CJ (2006) Novel switching using azobenzene functional materials. J Photochem Photobiol A182:250–261
Barrett CJ, Mamiya JI, Yager KG, Ikeda T (2007) Photo-mechanical effects in azobenzene-containing soft materials. Soft Matter 3:1249–1261
Kucharski S, Janik R, Hodge P, Westc D, Khand K (2002) Photochemical transformations of chromophoric methacrylates under the influence of light and laser radiation. J Mater Chem 12:449–454
Pouliquen G, Tribe C (2006) Light-triggered association of bovine serum albumin and azobenzene-modified poly(acrylic acid) in dilute and semidilute solutions. Macromolecules 39:373–383
Luca AR, Rocha L, Resmerita AM, Macovei A, Hamel M, Macsim A-M, Nichita N, Hurduc N (2011) Rigid and flexible azopolymers modified with donor/acceptor groups synthesis and photochromic behavior. Express Polym Lett 5(11):959–969
Merino E, Ribagorda M (2012) Control over molecular motion using the cis–trans photoisomerization of the azo group. Beilstein J Org Chem 8:1071–1090
Tomatsu I, Peng K, Kros A (2011) Photoresponsive hydrogel for biomedical application. Adv Drug Deliv Rev 63:1257–1266
Chen L, Li SG, Zhao YP, Wang YC, Wang QW (2005) Photoresponses and pH responses of hydrogels composed of acrylamido azobenzene and acrylic acid. J Appl Polym Sci 96:2163–2167
Treloar LRG (1975) The physics of rubber elasticity. Clarendon Press, Oxford
Peppas NA, Barr-Howell BD (1986) Characterization of the crosslinked structure of hydrogels. In: Peppas NA (ed) Hydrogels in medicine and pharmacy. Fundamentals, vol 1. CRC Press, Boca Raton, pp 27–56
Lee WF, Liu TM (2006) Effect of fluorinated hydrophobic monomer on the drug release behavior for the thermosensitive hydrogels. J Appl Polym Sci 100(6):4661–4667
Lee WF, Yeh YC (2006) Effect of porosigen and hydrophobic monomer on the fast swelling–deswelling behaviors for the porous thermoreversible copolymeric hydrogels. J Appl Polym Sci 100(4):3152–3160
Rachkov A, Minoura N, Shimizu T (2002) Photoisomerization study of p-phenylazoacrylanilide and its homo- and copolymers. Opt Mater 21:307
Acknowledgments
The authors would like to thank Dr. Ta-Hsien Lin in the Veterans General Hospital at Taipei for the technical support of NMR facility. The authors would also thank the Tatung University for their financial support under Grant B 100-C01-017.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Lin, YS., Lin, CH. & Lee, WF. Investigation of the synthesis and properties of the copolymeric hydrogels based on N-isopropyl acrylamide and acrylamidoazobenzene. J Polym Res 21, 364 (2014). https://doi.org/10.1007/s10965-014-0364-0
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s10965-014-0364-0