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

Tian-xiao Chang; Hang-tian Zhang; Cong-jie Lu; Yi-xian Wu

doi:10.11777/j.issn1000-3304.2017.17290

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

Research Article | 更新时间：2021-01-26

- In situ Synthesis and Characterization of Chitosan-g-polytetrahydrofuran Graft Copolymer/Ag Nanocomposite via Living Cationic Polymerization
- Acta Polymerica Sinica Vol. 0, Issue 6, Pages: 700-711(2018)
- 作者机构：
  
  北京化工大学化工资源有效利用国家重点实验室生物医用材料北京实验室　北京 100029
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2017.17290
  CLC：
- Published：2018-6，
  
  Received：18 October 2017，
  
  Revised：22 November 2017，
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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 0(6):700-711(2018)
DOI：

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 0(6):700-711(2018) DOI： 10.11777/j.issn1000-3304.2017.17290.

摘要

采用活性正离子开环聚合方法合成聚四氢呋喃(PTHF)活性链，再通过“grafting onto”方式接枝到壳聚糖(CS)刚性主链上，原位制备壳聚糖-

-聚四氢呋喃接枝共聚物/银纳米复合材料. 采用FTIR、

H-NMR和XPS分别表征该接枝共聚物化学结构，采用AFM、TEM、HR-TEM、POM、SEM、TGA和UV研究复合材料的Ag含量、微观结构与形态，并研究该复合材料的载药/释药性和抗菌性能. 结果表明：通过上述方法可以原位制备出壳聚糖-

-聚四氢呋喃接枝共聚物/银(CS-

-PTHF/Ag)纳米复合材料，PTHF支链的平均分子量为1400 ~ 2600，以1000个氨基葡萄糖环为整体计算接枝链PTHF的平均支链数目为4 ~ 21，纳米Ag的质量含量为2.2% ~ 5.7%. 所制备的CS-

-PTHF接枝共聚物形成明显的微观相分离结构，主链CS的结晶性随着侧链PTHF接枝数目增大而受到限制，结晶形态发生变化；CS-

-PTHF接枝共聚物可作为药物载体，载药率在53% ~ 80%之间，载药微球的尺寸随侧链PTHF接枝数目增大而减小；CS-

-PTHF接枝共聚物载药微球具有一定的pH敏感性，CS-

-PTHF

1.4k

在pH = 6.0的弱酸性环境中释放速率快，25 h时药物释放完全. CS-

-PTHF

2.6k

/Ag-5.7纳米复合材料表现出良好的抗菌性，对于抗大肠杆菌，抑菌圈直径为13.0 mm，对于抗黑曲霉，抑菌圈直径为10.5 mm. 所制备的CS-

-PTHF/Ag纳米复合材料结合了壳聚糖良好的生物相容性、聚四氢呋喃优异的抗湿强度与柔韧性以及纳米银优良的抗菌性，在生物医学领域具有潜在应用前景.

Abstract

A novel nanocomposite material of chitosan-

-polytetrahydrofuran (PTHF) graft copolymers with silver (Ag) nanoparticles

CS-

-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-

-PTHF/Ag was confirmed by Fourier transform infrared spectroscopy (FTIR)

nuclear magnetic resonance (

H-NMR)

and X-ray photoelectron spectroscopy (XPS). The total content of Ag

drug releasing rate and micromorphology of CS-

-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 (

) and average grafting number could be designed by changing the dosage of allylBr/AgClO

initiating system and the molar ratio of living PTHF chains to the ―NH

functional groups in chitosan backbone. The

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-

-PTHF/Ag nanocomposite was observed

and the micromorphology was related to grafting density in the CS-

-PTHF graft copolymers. The crystallization activity of the backbone was limited with an increase in the grafting number of PTHF branches. Meanwhile

the CS-

-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-

-PTHF graft copolymers. Drug-loading percentage of different CS-

-PTHF drug deliveries varied from 53% to 80%. Taking CS-

-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-

-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-

-PTHF/Ag nanocomposite varied from 2.2% to 5.7%

which led to antibacterial performance in CS-

-PTHF/Ag nanocomposite. For CS-

-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-

-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.

关键词

壳聚糖聚四氢呋喃接枝共聚物正离子聚合纳米复合材料

Keywords

ChitosanPolytetrahydrofuranGraft copolymerCationic polymerizationNanocomposite

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

College of Food Science and Technology, Nanjing Agricultural University

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