Citation: Tian-xiao Chang, Hang-tian Zhang, Cong-jie Lu, Yi-xian Wu. In situ Synthesis and Characterization of Chitosan-g-polytetrahydrofuran Graft Copolymer/Ag Nanocomposite via Living Cationic Polymerization[J]. Acta Polymerica Sinica, ;2018, 0(6): 700-711. doi: 10.11777/j.issn1000-3304.2017.17290 shu

In situ Synthesis and Characterization of Chitosan-g-polytetrahydrofuran Graft Copolymer/Ag Nanocomposite via Living Cationic Polymerization

State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing Laboratory of Biomedical Materials, Beijing 100029

Corresponding author: Yi-xian Wu, wuyx@mail.buct.edu.cn
Received Date: 18 October 2017
Revised Date: 22 November 2017
Available Online: 25 April 2018

A novel nanocomposite material of chitosan-g-polytetrahydrofuran (PTHF) graft copolymers with silver (Ag) nanoparticles, CS-g-PTHF/Ag, was successfully in situ prepared via combination of living cationic opening polymerization of tetrahydrofuran (THF) with controlled termination of living PTHF chains " grafting onto” chitosan macromolecular backbone. Chemical structure of CS-g-PTHF/Ag was confirmed by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (¹H-NMR), and X-ray photoelectron spectroscopy (XPS). The total content of Ag, drug releasing rate and micromorphology of CS-g-PTHF/Ag composites were characterized by ultraviolet spectroscopy (UV), polarizing microscopy (POM), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high-resolution TEM (HR-TEM), respectively. The results show that the acylation degree of average functional groups in single glucosamine was 20%. The number-average molecular weight (M_n) and average grafting number could be designed by changing the dosage of allylBr/AgClO₄ initiating system and the molar ratio of living PTHF chains to the ―NH₂ functional groups in chitosan backbone. The M_n,PTHF ranged from 1400 to 2600 and average grafting number increased from 4 to 21 on the basis of every 1000 glucosamine units along the macromolecular backbone. The PTHF branches influenced the crystallinity of the acylated chitosan backbone. The microphase separation of CS-g-PTHF/Ag nanocomposite was observed, and the micromorphology was related to grafting density in the CS-g-PTHF graft copolymers. The crystallization activity of the backbone was limited with an increase in the grafting number of PTHF branches. Meanwhile, the CS-g-PTHF graft copolymer was found to behave pH-sensitive drug delivery. The size of the drug-loaded microspheres decreased with the increasing average grafting number in CS-g-PTHF graft copolymers. Drug-loading percentage of different CS-g-PTHF drug deliveries varied from 53% to 80%. Taking CS-g₆-PTHF_1.4k as an example, its drug-releasing rate (DRR) was accelerated in weak acid of phosphate buffered solution (pH = 6.0). The drug-releasing process included three stages: in the first stage (4 h), CS-g₆-PTHF_1.4k drug delivery released fast with a DRR of 63%. In the second stage from 4 h to 8 h, DRR was slightly changed. In the third stage, drug delivery accelerated and DRR reached 100%. Drug was inhibited to release in the simulated intestinal fluid (pH = 1.2), simulated gastrointestinal fluid (pH = 7.4), simulated blood (pH = 7.4). In simulated intestinal fluid (pH = 1.2), drug release was fast in the first 4 h, and the accumulated drug release was 29%, and accumulated DRR was 35% within 25 h. In simulated gastrointestinal fluid (pH = 7.4) and simulated blood (pH = 7.4), the drug-release rate reached a maximum in the first 2 h, and DDR was 51% in 25 h. The total mass content of Ag in CS-g-PTHF/Ag nanocomposite varied from 2.2% to 5.7%, which led to antibacterial performance in CS-g-PTHF/Ag nanocomposite. For CS-g₇-PTHF_2.6k/Ag-5.7, diameter of inhibition zone of Escherichhia coli was 13.0 mm, and of Aspergillus niger was 10.5 mm. This novel CS-g-PTHF/Ag nanocomposite, with the biocompatibility of rigid chitosan, the humidity resistance of soft polytetrahydrofuran, and the antibacterial activity of nano-silver all combined, would have a prospect in biomedical application.
- Chitosan,
- Polytetrahydrofuran,
- Graft copolymer,
- Cationic polymerization,
- Nanocomposite
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