Abstract
Despite the fact that some progress has been made in the self-assembly of H-shaped polymers, the corresponding self-assemblies that respond to external stimulus and are further utilized to adjust the release of drugs are still deficient. The stimuli-responsive segments with amphiphilic H-shaped structure are generally expected to enhance the controllability of self-assembly process. The synthesis and self-assembly behavior of thermo-responsive amphiphilic H-shaped polymers with poly(ethylene glycol) (PEG), polytetrahydrofuran (PTHF) and poly(N-isopropyl acrylamide) (PNIPAM) as building blocks are reported in this paper. The inner architecture structure and size of complex micelles formed by H-shaped self-assemblies were effectively adjusted when the solution temperature was increased above the lower critical solution temperature of PNIPAM segments. Furthermore, it was found that the architecture of self-assemblies underwent a transition from the complex micelles based on primary micelles with hybrid PEG/PNIPAM shells to large complex micelles based on primary micelles with hybrid PTHF/PNIPAM cores and PEG shells during the thermal-induced self-assembly process. The adjustable release rate of doxorubicin (DOX) from the DOX-loaded complex micelles and basic cell experiments further proved the feasibility of these self-assemblies as the thermal-responsive drug delivery system.
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References
Liu, Y. Y.; Zhong, Y. B.; Nan, J. K.; Tian, W. Star polymers with both temperature sensitivity and inclusion functionalities. Macromolecules 2010, 43(24), 10221–10230.
Liu, H.; Li, C. H.; Liu, H. W.; Liu, S. Y. pH-Responsive supramolecular self-assembly of well-defined zwitterionic ABC miktoarm star terpolymers. Langmuir 2009, 25(8), 4724–4734.
Pang, X. C.; Zhao, L.; Akinc, M.; Kim, J. K.; Lin, Z. Q. Novel amphiphilic multi-arm, star-like block copolymers as unimolecular micelles. Macromolecules 2011, 44, 3746–3752.
Huang, X. Y.; Wang, D. L.; Dong, R. J.; Tu, C. L.; Zhu, B. S.; Yan, D. Y.; Zhu, X. Y. Supramolecular ABC miktoarm star terpolymer based on host-guest inclusion complexation. Macromolecules 2012, 45, 5941–5947.
Mu, C. G.; Fan, X. D.; Tian, W.; Bai, Y.; Zhou, X. Miktoarm star polymers with poly(N-isopropylacryamide) or poly(oligo(ethylene glycol) methacrylate) as building blocks: synthesis and comparison of thermally-responsive behaviors. Polym. Chem. 2012, 3(5), 1137–1149.
Li, Y. G.; Shi, P. J.; Pan, C. Y. Synthesis, characterization, and thermal behavior of H-shaped copolymers prepared by atom transfer radical polymerization. Macromolecules 2004, 37, 5190–5195.
Yu, X. F.; Shi, T. F.; Zhang, G.; An, L. J. Synthesis of asymmetric H-shaped block copolymer by the combination of atom transfer radical polymerization and living anionic polymerization. Polymer 2006, 47, 1538–1546.
Liu, H. H.; Li, S. X.; Zhang, M. J.; Shao, W.; Zhao, Y. L. Facile synthesis of ABCDE-type H-shaped quintopolymers by combination of ATRP, ROP, and click chemistry and their potential applications as drug carriers. J. Polym. Sci., Part A: Polym. Chem. 2012, 50, 4705–4716.
Zhang, Z. X.; Liu, X.; Xu, F. J.; Loh, X. J.; Kang, E. T.; Neoh, K. G.; Li, J. Pseudo-block copolymer based on star-shaped poly(N-isopropylacylamide) with a β-Cyclodextrin core and guest-bearing PEG: controlling thermoresponsive through supramolecular self-assembly. Macromolecules 2008, 41, 5967–5970.
Bai, Y.; Fan, X. D.; Tian, W.; Yao, H.; Zhuo, L. H.; Zhang, H. T.; Fan, W. W.; Yang, Z.; Zhang, W. B. Synthesis and thermally-triggered self-assembly behaviors of a dumbbellshaped polymer carring β-cyclodextrin at branch points. Polymer 2013, 54, 3566–3573.
Cao, Z. L.; Chen, M. J.; Hu, Y. Y.; Dong, S. L.; Cui, J. W.; Hao, J. C. Tunable assembly and disassembly of responsive supramolecular polymer brushes. Polym. Chem. 2017, 8, 2764–2772.
Wu, J. Y.; Cao, C. Sliding supramolecular polymer brushes with tunable amphiphilicity: one-step parallel click synthesis and self-assembly. Macromolecules 2010, 43, 7139–7146.
Feng, A. C.; Yan, Q.; Zhang, H. J.; Peng, L.; Yuan, J. J. Electrochemical redox responsive polymeric micelles formed from amphiphilic supramolecular brushes. Chem. Commun. 2014, 50, 4740–4742.
Roling, O.; Mardyukov, A.; Krings, J. A.; Studer, A.; Ravoo, B. J. Polymer brushes exhibiting versatile supramolecular interactions grown by nitroxide-mediated polymerization and structured via microcontact chemistry. Macromolecules 2014, 47, 2411–2419.
Xu, Y. Y.; Bolisetty, S.; Ballauff, M.; Müller, A. H. E. Switching the morphologies of cylindrical polycation brushes by ionic and supramolecular inclusion complexes. J. Am. Chem. Soc. 2009, 131, 1640–1641.
Yang, B.; Huang, Q. T.; Liu, H. H.; Zhao, Y. L.; Du, J. Z. Hairy cyclinders based on a coil-comb-coil copolymer. RSC Adv. 2016, 6, 104911–104918.
Jiang, X.; Zhang, M. J.; Li, S. X.; Shao, W.; Zhao, Y. L. Facile synthesis and versatile topological transformation of mono-cleavable symmetric starlike terpolymers. Chem. Commun. 2012, 48, 9906–9908.
Gao, C.; Yan, D. Y. Hyperbranched polymers: from synthesis to applications. Prog. Polym. Sci. 2004, 29, 183–275.
Dong, R. J.; Liu, Y.; Zhou, Y. F.; Yan, D. Y.; Zhu, X. Y. Photo-reversible supramolecular hyperbranched polymer based on host-guest interactions. Polym. Chem. 2011, 2, 2771–2774.
Ge, Z. S.; Liu, H.; Zhang, Y. F.; Liu, S. Y. Supramolecular thermoresponsive hyperbranched polymers constructed from poly(N-isopropylacrylamide) containing one adamantyl and two β-Cyclodextrin terminal moieties. Macromol. Rapid Commun. 2012, 32, 68–73.
Bai, Y.; Fan, X. D.; Tian, W.; Liu, T. T.; Yao, H.; Yang, Z.; Zhang, H. T.; Zhang, W. B. Morphology transitions of supramolecular hyperbranched polymers induced by double supramolecular driving forces. Polym. Chem. 2015, 6, 752–757.
Voit, B. I.; Lederer, A. Hyperbranched and highly branched polymer architectures-synthetic strategies and major characterization aspects. Chem. Rev. 2009, 109, 5924–5973.
Chen, P. Y.; Li, Z. The design of second-order nonlinear optical dendrimers: from "branch only" to "root containing" Chinese J. Polym. Sci. 2017, 35(7), 793–798.
Dong, R. J.; Zhou, Y. F.; Zhu, X. Y. Supramolecular dendritic polymers: from synthesis to application. Accounts Chem. Res. 2014, 47, 2006–2016.
Munteanu, M.; Kolb, U.; Ritter, H. Supramolecular nanocycles comprising β-cyclodextrin-click-ferrocene units: rings of rings of rings. Macromol. Rapid Commun. 2010, 31, 616–618.
Ge, Z. S.; Zhou, Y. M.; Xu, J.; Liu, H. W.; Chen, D. Y.; Liu, S. Y. High-efficiency preparation of macrocyclic diblock copolymers via selective click reaction in micellar media. J. Am. Chem. Soc. 2009, 131, 1628–1629.
Huang, Z. H.; Zhou, Y. Y.; Wang, Z. M.; Li, Y.; Zhang, W.; Zhou, N. C.; Zhang, Z. B.; Zhu, X. L. Recent advances of CuAAC click reaction in building cyclic polymer. Chinese J. Polym. Sci. 2017, 35(3), 317–341.
Sonke, S.; Tomalia, D. A. Dendrimers in biomedical applications-reflections on the field. Adv. Drug Deliver. Rev. 2005, 57, 2106–2129.
Lapienis, G. Star-shaped polymers having PEO arms. Prog. Polym. Sci. 2009, 34, 852–892.
Konkolewicz, D.; Monteiro, J. M.; Perrier, S. Dendritic and hyperbranched polymers from macromolecular units: elegant approaches to the synthesis of functional polymers. Macromolecules 2011, 44, 7076–7087.
Boas, U.; Heegaard, P. M. H. Dentrimers in drug research. Chem. Soc. Rev. 2004, 33, 43–63.
He, X. H.; Wu, X. M.; Cai, X.; Lin, S. L.; Xie, M. R.; Zhu, X. Y.; Yan, D. Y. Functionalization of magnetic nanoparticles with dentritic-linear-brush-like triblock copolymers and their drug release properties. Langmuir 2012, 28, 11938–11947.
Cong, Y.; Li, B. Y.; Han, Y. C.; Li, Y. G.; Pan, C. Y. Self-assembly of H-shaped block copolymers. Macromolecules 2005, 38, 9836–9846.
Bai, Y.; Fan, X. D.; Tian, W.; Mu, C. G.; Yang, Z.; Fan, W. W.; Zhang, H. T.; Zhang, W. B. Large complex micelles formed from amphiphilic H-shaped terpolymers with adjustable block ratio by ultrasonic vibration. Polymer 2013, 54, 1734–1738.
Wang, G. T.; Wang, C.; Wang, Z. Q.; Zhang, X. H-shaped supra-amphiphiles based on dynamic covalent bond. Langmuir 2012, 28, 14567–14572.
Wei, Y. H.; Huang, W. H.; Li, B. Y.; Han, Y. C.; Pan, C. Y. Square lamellar structure having phase-separated microdomain in H-shaped block copolymer thin film. Macromol. Rapid Commun. 2008, 29, 1378–1384.
Yoshida, A.; Honda, S.; Goto, H.; Sugimoto, H. Synthesis of H-shaped carbon-dioxide-derived poly(propylene carbonate) for topology-based reduction of the glass transition temperature. Polym. Chem. 2014, 5, 1883–1890.
Altintas, O.; Schulze-Suenninghausen, D.; Luy, B.; Barner-Kowollik, C. Facile preparation of supramolecular H-shaped (ter)polymers via multiple hydrogen bonding. ACS Macro Lett. 2013, 2, 211–216.
Yuan, W. Z.; Zhang, J. C.; Zou, H.; Ren, J. Synthesis, crystalline morphologies, self-Assembly, and properties of H-shaped amphiphilic dually responsive terpolymers. J. Polym. Sci., Part A: Polym. Chem. 2012, 50, 2541–2552.
Zou, P.; Pan, C. Y. Multiple vesicle morphologies formed from reactive H-shaped block copolymers. Macromol. Rapid Commun. 2008, 29, 763–771.
Huang, Q. T.; Yang, B.; Liu, H. H.; Zhao, Y. L.; Du, J. Z. Silkworm cocoons by cylinders self-assembled from H-shaped alternating polymer brushes. Polym. Chem. 2015, 6, 886–890.
Schmidt. B. V. K. J.; Barner-Kowollik, C. Supramolecular Xand H- shaped star block copolymers via cyclodextrin-driven supramolecular self-assembly. Polym. Chem. 2014, 5, 2461–2472.
Ji, R.; Chen, J.; Yang, T.; Song, C. C.; Li, L.; Du, F. S.; Li, Z. C. Shell-sheddable, pH-sensitive supramolecular nanoparticles based on ortho ester-modified cyclodextrin and adamantly PEG. Biomacromolecules 2014, 15, 3531–3539.
Tian, Z.; Wang, M.; Zhang, A. Y., Feng, Z. G. Preparation and evaluation of novel amphiphilic glycopeptide block copolymers as carriers for controlled drug release. Polymer 2008, 49, 446–454.
Yao, C. G.; Wang, X. R.; Liu, G. H.; Hu, J. M.; Liu, S. Y. Distinct morphological transitions of photoreactive and thermoresponsive vesicles for controlled release and nanoreactors. Macromolecules 2016, 49, 8282–8295.
Gheorghe, A.; Matsuno, A.; Reiser, O. Expedient immobilization of TEMPO by copper-catalyzed azide-alkyne [3+2] cycloaddition onto polystyrene resin. Adv. Synth. Catal. 2006, 348, 1016–1020.
Schild, H. G. Poly(N-isopropylacrylamide): experiment, theory and application. Prog. Polym. Sci. 1992, 17,163–249.
Lutz, J. F.; Akdemir, Ö.; Hoth. A. Point by point comparison of two thermosensitive polymers exhibiting a similar LCST: is the age of poly(NIPAM) over? J. Am. Chem. Soc. 2006, 128, 13046–13047.
Ohashi, H.; Hiraoka, Y.; Yamaguchi, T. An autonomous phase transition-complexation/decomplexation polymer system with a molecular recognition property. Macromolecules 2006, 39, 2614–2620.
Sun, S. T.; Wu, P. Y.; Zhang, W. D.; Zhang, W.; Zhu, X. L. Effect of structural constraint on dynamic self-assembly behavior of PNIPAM-based nonlinear multihydrophilic block copolymers. Soft Matter 2013, 9, 1807–1816.
Murugesan, M.; Scibioh, M. A.; Jayakumar, R. Structural transition of nonionic peptide aggregates in aqueous medium. Langmuir 1999, 15, 5467–5473.
Liu, T. T.; Tian, W.; Song, Y. L.; Bai, Y.; Wei, P. L.; Yao, H.; Yan, H. X. Reversible self-assembly of backbonethermoresponsive long chain hyperbranched poly(N-isopropyl acrylamide). Polymers 2016, 8, 33–47.
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This work was financially supported by the National Natural Science Foundation of China (No. 21674086) and Scientific Research Program Funded by Shaanxi Provincial Education Department (No. 17JK0103).
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Bai, Y., Xie, FY. & Tian, W. Controlled Self-assembly of Thermo-responsive Amphiphilic H-shaped Polymer for Adjustable Drug Release. Chin J Polym Sci 36, 406–416 (2018). https://doi.org/10.1007/s10118-018-2086-y
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DOI: https://doi.org/10.1007/s10118-018-2086-y