Abstract
The novel quaternized hydroxypropyl cellulose-g-poly(THF-co-epichlorohydrin) graft copolymers, HPC-g-QCP(THF-co-ECH), have been successfully synthesized to combine the properties from hydrophilic hard HPC biomacromolecular backbone and hydrophobic flexible polyether branches. Firstly, the P(THF-co-ECH) living chains were synthesized by cationic ring-opening copolymerization of THF with ECH. Secondly, P(THF-co-ECH) living chains were grafted onto HPC backbone by reaction with —OH groups along HPC to produce HPC-g-P(THF-co-ECH) graft copolymers. Thirdly, the mentioned graft copolymers were quaternized by reaction with ternary amine to generate functionalized HPC-g-QCP(THF-co-ECH). The HPC-g-QCP(THF-co-ECH) graft copolymers exhibited good antibacterial ability against S. aureus or E. coli bacteria. The ibuprofen (IBU)-loaded microparticles of HPC-g-(QC)P(THF-co-ECH) graft copolymers were prepared by electrospraying. The in vitro pH-responsive drug-release behavior of IBU reached up to 75% of drug-loaded at pH = 7.4. This quaternized graft copolymer was beneficial to solving the problems of a burst effect and fast release of HPC as drug carriers.
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
Herzberger, J.; Niederer, K.; Pohlit, H.; Seiwert, J.; Worm, M.; Wurm, F. R.; Frey, H. Polymerization of ethylene oxide, propylene oxide, and other alkylene oxides: synthesis, novel polymer architectures, and bioconjugation. Chem. Rev.2016, 116, 2170–2243.
Kobayashi, S.; Danda, H.; Saegusa, T. Superacids and their derivatives IV. Kinetic studies on the ring-opening polymerization of tetrahydrofuran initiated with ethyl trifluoromethanesulfonate by means of 19F and 1H nuclear magnetic resonance spectroscopy. evidence for the oxonium-ester equilibrium of the propagating species. Macromolecules1974, 7, 415–420.
Doran, S.; Yilmaz, G.; Yagci, Y. Tandem photoinduced cationic polymerization and CuAAC for macromolecular synthesis. Macromoleccles2015, 48, 7446–7452.
You, L.; Ling, J. Janus polymerization. Macromoecules2014, 47, 2219–2225.
Lai, Y.; Kuang, X.; Zhu, P.; Huang, M.; Dong, X.; Wang, D. Colorless, transparent, robust, and fast scratch-self-healing elastomers via a phase-locked dynamic bonds design. Adv. Mater.2018, 30, 1802556.
Mi, H. Y.; Jing, X.; Napiwocki, B. N.; Hagerty, B. S.; Chen, G.; Turng, L. S. Biocompatible, degradable thermoplastic polyurethane based on polycaprolactone-block-polytetrahydrofuran-block-polycaprolactone copolymers for soft tissue engineering. J. Mater. Chem. B2017, 5, 4137–4151.
Kim, D.; Lee, D. G.; Kim, J. C.; Lim, C. S.; Kong, N. S.; Kim, J. H.; Jung, H. W.; Noh, S. M.; Park, Y. I. Effect of molecular weight of polyurethane toughening agent on adhesive strength and rheological characteristics of automotive structural adhesives. Int. J. Adhes. Adhes.2017, 74, 21–27.
Zhao, J. C.; Du, F. P.; Zhou, X. P.; Cui, W.; Wang, X. M.; Zhu, H.; Xie, X. L.; Mai, Y. W. Thermal conductive and electrical properties of polyurethane/hyperbranched poly(urea-urethane)-grafted multi-walled carbon nanotube composites. Compos. Part B2011, 42, 2111–2116.
Mu, C G.; Fan, X. D.; Tian, W.; Bai, Y.; Yang, Z.; Fan, W. W.; Chen, H. Synthesis and stimulus-responsive micellization of a well-defined H-shaped terpolymer. Polym. Chem.2012, 3, 3330–3339.
Bazban-Shotorbani, S.; Hasani-Sadrabadi, M. M.; Karkhaneh, A.; Serpooshan, V.; Jacob, K. I.; Moshaverinia, A.; Mahmoudi, M. Revisiting structure-property relationship of pH-responsive polymers for drug delivery applications. J. Control. Release2017, 253, 46–63.
Matricardi, P.; Meo, C. D.; Coviello, T.; Hennink, W. E.; Alhaique, F. Interpenetrating polymer networks polysaccharide hydrogels for drug delivery and tissue engineering. Adv. Drcg Deliver. Rev.2013, 65, 1172–1187.
B.; Thomas, Raj, M. C.; B, A. K.; H, R. M.; Joy, J.; Moores, A.; Drisko, G. L.; Sanchez, C. Nanocellulose, a versatile green platform: from biosources to materials and their applications. Chem. Rev.2018, 118, 11575–11625.
Xu, F. J.; Zhu, Y.; Liu, F. S.; Nie, J.; Ma, J.; Yang, W. T. Comb-shaped conjugates comprising hydroxypropyl cellulose backbones and low-molecular-weight poly(N-isopropylacryamide) side chains for smart hydrogels: synthesis, characterization, and biomedical applications. Bioconjcgate Chem.2010, 21, 456–464.
Chang, C.; Zhang, L. Cellulose-based hydrogels: present status and application prospects. Carbohydr. Polym.2011, 84, 40–53.
Xu, F. J.; Ping, Y.; Ma, J.; Tang, G. P.; Yang, W. T.; Li, J.; Kang, E. T.; Neoh, K. G. Comb-shaped copolymers composed of hydroxypropyl cellulose backbones and cationic poly((2-dimethyl amino) ethyl methacrylate) side chains for gene delivery. Bioconjcgate Chem.2009, 20, 1449–1458.
Stamatialis, D. F.; Rolevink, H. H. M.; Gironès, M.; Nymeijer, D. C.; Koops, G. H. In vitro evaluation of a hydroxypropyl cellulose gel system for transdermal delivery of timolol. Curr. Drug Deliver.2004, 1, 313–319.
Joubert, F.; Musa, O. M.; Hodgson, D. R. W.; Cameron, N. R. The preparation of graft copolymers of cellulose and cellulose derivatives using ATRP under homogeneous reaction conditions. Chem. Soc. Rev.2014, 43, 7217–7235.
Tizzotti, M.; Charlot, A.; Fleury, E.; Stenzel, M.; Bernard, J. Modification of polysaccharides through controlled/living radical polymerization grafting-towards the generation of high performance hybrids. Macromol. Rapid Commun.2010, 31, 1751–1772.
Kang, H.; Liu, R.; Huang, Y. Graft modification of cellulose: methods, properties and applications. Polymer2015, 70, A1–A16.
Hansson, S.; Trouillet, V.; Tischer, T.; Goldmann, A. S.; Carlmark, A.; Barner-Kowollik, C.; Malmström, E. Grafting efficiency of synthetic polymers onto biomaterials: a comparative study of grafting-from versus grafting-to. Biomacromoleccles2013, 14, 64–74.
Yoo, Y.; Youngblood, J. P. Green one-pot synthesis of surface hydrophobized cellulose nanocrystals in aqueous medium. ACS Scstain. Chem. Eng.2016, 4, 3927–3938.
Yang, X.; Liu, G.; Peng, L.; Guo, J.; Tao, L.; Yuan, J.; Chang, C.; Wei, Y.; Zhang, L. Highly efficient self-healable and dual responsive cellulose-based hydrogels for controlled release and 3D cell culture. Adv. Funct. Mater.2017, 27, 1703174.
Liu, Z.; Chen, M.; Guo, Y.; Wang, X.; Zhang, L.; Zhou, J.; Li, H.; Shi, Q. Self-assembly of cationic amphiphilic cellulose-g-poly(p-dioxanone) copolymers. Carbohydr. Polym.2019, 204, 214–222.
Cheng, M.; He, H.; Zhu, H.; Guo, W.; Chen, W.; Xue, F.; Zhou, S.; Chen, X.; Wang, S. Preparation and properties of pH-responsive reversible-wettability biomass cellulose-based material for controllable oil/water separation. Carbohydr. Polym.2019, 203, 246–255.
Li, B.; Zhang, Y.; Wu, C.; Guo, B.; Luo, Z. Fabrication of mechanically tough and self-recoverable nanocomposite hydrogels from polyacrylamide grafted cellulose nanocrystal and poly(acrylic acid). Carbohydr. Polym.2018, 198, 1–8.
Bai, C.; Huang, X.; Xie, F.; Xiong, X. Microcrystalline cellulose surface-modified with acrylamide for reinforcement of hydrogels. ACS Scstain. Chem. Eng.2018, 6, 12320–12327.
Esmaeili, A.; Haseli, M. Optimization, synthesis, and characterization of coaxial electrospun sodium carboxymethyl cellulose-graft-methyl acrylate/poly(ethylene oxide) nanofibers for potential drug-delivery applications. Carbohydr. Polym.2017, 173, 645–653.
Rajesh, S.; Crandall, C.; Schneiderman, S.; Menkhaus, T. J. Cellulose-graft-polyethyleneamidoamine anion-exchange nanofiber membranes for simultaneous protein adsorption and virus filtration. ACS Appl. Nano Mater.2018, 1, 3321–3330.
Demircan, D.; Zhang, B. Facile synthesis of novel soluble cellulose-grafted hyperbranchedpolymers as potential natural antimicrobial materials. Carbohydr. Polym.2017, 157, 1913–1921.
Zhao, J.; Li, Q.; Zhang, X.; Xiao, M.; Zhang, W.; Lu, C. Grafting of polyethylenimine onto cellulose nanofibers for interfacial enhancement in their epoxy nanocomposites. Carbohydr. Polym.2017, 157, 1419–1425.
Li, M.; Gong, Y.; Wang, W.; Xu, G.; Liu, Y.; Guo, J. In-situ reduced silver nanoparticles on populus fiber and the catalytic application. Appl. Surf. Sci.2017, 394, 351–357.
Ma, P.; Shen, T.; Lin, L.; Dong, W.; Chen, M. Cellulose-g-poly(D-lactide) nanohybrids induced significant low melt viscosity and fast crystallization of fully bio-based nanocomposites. Carbohydr. Polym.2017, 155, 498–506.
Ci, J.; Kang, H.; Liu, C.; He, A.; Liu, R. Thermal sensitivity and protein anti-adsorption of hydroxypropyl cellulose-g-poly(2-(methacryloyloxy) ethyl phosphorylcholine). Carbohydr. Polym.2017, 157, 757–765.
Ott, M. W.; Herbert, H.; Graf, M.; Biesalski, M. Cellulose-grat-polystyrene bottle-brush copolymers by homogeneous RAFT polymerization of soluble cellulose macro-CTAs and “CTA-shuttled” R-group approach. Polymer2016, 98, 505–515.
Yuan, H.; Chi, H.; Yuan, W. Ethyl cellulose amphiphilic graft copolymers with lcst-ucst transition: opposite self-assembly behavior, hydrophilic-hydrophobic surface and tunable crystalline morphologies. Carbohydr. Polym.2016, 147, 261–271.
Kalaoglu, Ö. İ.; Ünlü, C. H.; Galioğlu Atıcı, O. Synthesis, characterization and electrospinning of corn cob cellulose-graft-polyacrylonitrile and their clay nanocomposites. Carbohydr. Polym.2016, 147, 37–44.
Guo, A.; Yang, F.; Yu, R.; Wu, Y. Real-time monitoring of living cationic ring-opening polymerization of THF and direct prediction of equilibrium molecular weight of polyTHF. Chinese J. Polym. Sci.2015, 33, 23–35.
Guo, A.; Yang, W.; Yang, F.; Yu, R.; Wu, Y. Well-defined poly(γ-benzyl-L-glutamate)-g-polytetrahydrofuran: synthesis, characterization, and properties. Macromelcules2014, 47, 5450–5461.
Wei, M.; Guo, A.; Wu, Y. Microstructure and micromorphology of poly(γ-benzyl-L-glutamate)-g-(polytetrahydrofuran-b-polyisobutylene) copolymer. Acta Polymerica Sinica (in Chinese) 2017, 506–515.
Chang, T.; Zhang, H.; Lu, C.; Wu, Y. In situ synthesis and characterization of chitosan-g-polytetrahydrofuran graft copolymer/Ag nanocomposite via living cationic polymerization. Acta Polymerica Sinica (in Chinese) 2018, 700–711.
Yao, C.; Li, X.; Neoh, K. G.; Shi, Z.; Kang, E. T. Surface modification and antibacterial activity of electrospun polyurethane fibrous membranes with quaternary ammonium moieties. J. Membr. Sci.2008, 320, 259–267.
Zhu, Y.; Xu, C.; Zhang, N.; Ding, X.; Yu, B.; Xu, F. J. Polycationic synergistic antibacterial agents with multiple functional components for efficient anti-infective therapy. Adv. Funct. Mater.2018, 28, 1706709.
Hadgraft, J.; Valenta, C. pH, pKa and dermal delivery. Int. J. Pharm.2000, 200, 243–247.
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (Nos. 21574007 and 51521062).
Author information
Authors and Affiliations
Corresponding author
Electronic Supplementary Information
10118_2020_2372_MOESM1_ESM.pdf
Antibacterial and pH-responsive Quaternized Hydroxypropyl Cellulose-g-Poly(THF-co-epichlorohydrin) Graft Copolymer: Synthesis, Characterization and Properties
Rights and permissions
About this article
Cite this article
Deng, JR., Zhao, CL. & Wu, YX. Antibacterial and pH-responsive Quaternized Hydroxypropyl Cellulose-g-Poly(THF-co-epichlorohydrin) Graft Copolymer: Synthesis, Characterization and Properties. Chin J Polym Sci 38, 704–714 (2020). https://doi.org/10.1007/s10118-020-2372-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10118-020-2372-3