Citation: Meng-juan Wei, Qi Zhang, Hang-tian Zhang, Yi-xian Wu. In situ Preparation and Properties of Poly(γ-benzyl-L-glutamate)-g-(polytetrahydrofuran-b-polyisobutylene)/Ag Nanocomposites via Cationic Polymerization[J]. Acta Polymerica Sinica, ;2018, (4): 464-474. doi: 10.11777/j.issn1000-3304.2017.17130 shu

In situ Preparation and Properties of Poly(γ-benzyl-L-glutamate)-g-(polytetrahydrofuran-b-polyisobutylene)/Ag Nanocomposites via Cationic Polymerization

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

Corresponding author: Yi-xian Wu, wuyx@mail.buct.edu.cn
Received Date: 12 May 2017
Revised Date: 22 May 2017

The living cationic ring opening polymerization of tetrahydrofuran (THF) was carried out using polyisobulylene with functional terminal group (PIB-AllylBr) as a macroinitiator in the presence of AgClO₄ to synthesize PIB-b-PTHF living polymer chains. And then, the novel PBLG-g-(PTHF-b-PIB) block graft copolymer/silver (Ag) nanocomposites were in situ prepared via grafting the living polymer chains onto poly(γ-benzyl-L-glutamate) (PBLG) backbone. Several PBLG-g-(PTHF-b-PIB)/Ag nanocomposites with different grafting densities and average branch lengths have been achieved. The effect of grafting density on the surface morphology and self-assembly behavior of PBLG-g-(PTHF-b-PIB)/Ag nanocomposites was studied by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The effects of grafting density and average branch length on the drug loading and release behavior were studied using ibuprofen (IBU) as a mimetic drug. The content, distribution, crystal form and morphology of nano-silver in nanocomposites were investigated by thermogravimetric analysis (TGA), UV-Vis spectroscopy (XPS), X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). The content of nano-silver in the above nanocomposites was ranged from 0.25% to 3.9%, which coincided with the theoretical content of nano-silver. The crystal form of nano-silver was face-centered cubic structure as observed by XRD test. The size of the nano-silver particles was ranged from 5 nm to 10 nm, estimated by HRTEM, and the obvious diffraction fringes were observed. The water contact angle of the above nanocomposite films increased from 96° to 118° with an increase in grafting density from 15% to 45%, and with that in nano-silver content from 0.45% to 1.48%. PBLG-g-(PTHF-b-PIB)/Ag/IBU microspheres were found to be well drug-loaded with ibuprofen as mimetic drug, attributed to the α-helical secondary structure in PBLG backbone in the middle, the amide bond in PBLG backbone and the ether bond in PTHF segments. Both drug loading and cumulative release rate increased with increasing grafting density or length of PTHF segment. The release rate at 37℃ was around 3 times of that at 25℃ for the same copolymer. No cytotoxicity of the nanocomposite was found by MTT assay since the cell viability was 97.7% after one week with the content of nano-silver of 1.48%. Antimicrobial experiments were performed on PBLG-g-(PTHF-b-PIB)/Ag nanocomposites by antibacterial ring method and the results showed that these nanocomposites demonstrated excellent antibacterial activity.
- Cationic polymerization,
- PBLG-g-(PTHF-b-PIB),
- Block graft copolymer,
- Composite,
- Antibacterial
1. [1]
  Aoi K, Okada M. Prog Polym Sci, 1996, 21:151-208 doi: 10.1016/0079-6700(95)00020-8
2. [2]
  Lee S C, Chang Y, Yoon J S, Kim C, Kwon I C, Kim Y H, Jeong S Y. Macromolecules, 1999, 32(6):1847-1852 doi: 10.1021/ma981664k
3. [3]
  Weberskirch R, Hettich R, Nuyken O, Schmaljohann D, Voit B. Macromol Chem Phys, 1999, 200(4):863-873 doi: 10.1002/(ISSN)1521-3935
4. [4]
  Langer R. Acc Chem Res, 2000, 33(2):94-101 doi: 10.1021/ar9800993
5. [5]
  Gombotz W R, Pettit D K. Bioconjugate Chem, 1995, 6(4):332-351 doi: 10.1021/bc00034a002
6. [6]
  Thambi T, Deepagan V G, Chang K Y. Polymer, 2011, 52(21):4753-4759 doi: 10.1016/j.polymer.2011.08.024
7. [7]
  Zhang Suning, Chen Tao, Lin Jiaping, Dong Xiubin, Lin Shaoliang. Acta Polymerica Sinica, 2005, (6):929-932
8. [8]
  Tang D M, Lin J P, Lin S L, Zhang S N, Chen T, Tian X H. Macromol Rapid Commun, 2004, 25:1241-1246 doi: 10.1002/(ISSN)1521-3927
9. [9]
  Mu C G, Fan X D, Tian W, Bai Y, Yang Z, Fan W W, Chen H. Polym Chem, 2012, 3:3330-3339 doi: 10.1039/c2py20586f
10. [10]
  Matyjaszewski K. New York: Marcel Dekker, 1996. 521-523
11. [11]
  Guo A R, Yang F, Yu R, Wu Y X. Chinese J Polym Sci, 2015, 33(1):23-35 doi: 10.1007/s10118-015-1571-9
12. [12]
  Cheradame H, Sassatelli M, Pomel C, Sanh A, Gau-Racine J, Bacri L, Auvray L, Guegan P. Macromol Symp, 2008, 261:167-181 doi: 10.1002/(ISSN)1521-3900
13. [13]
  Rueda L L, D'Arlas B F, Eur Polym J, 2009, 45(7):2096-2109 doi: 10.1016/j.eurpolymj.2009.03.013
14. [14]
  Goethals E J, Dubreuil M F, Tanghe L. Macromol Symp, 2000, 161:135-140 doi: 10.1002/(ISSN)1521-3900
15. [15]
  Guo A R, Yang W X, Yang F, Yu R, Wu Y X. Macromolecules, 2014, 47:5450-5461 doi: 10.1021/ma501060y
16. [16]
  Kennedy J P. J Polym Sci, Part A:Polym Chem, 2005, 43(14):2951-2963 doi: 10.1002/(ISSN)1099-0518
17. [17]
  Wei Mengjuan, Guo Anru, Wu Yixian. Acta Polymerica Sinica, 2017, (3):506-515
18. [18]
  Vukomanović M, Repnik U, Zavašnikbergant T. ACS Biomater Sci Eng, 2015, 1(10):935-946 doi: 10.1021/acsbiomaterials.5b00170
19. [19]
  Tobaldi D M, Piccirillo C, Pullar R C. J Phys Chem C, 2014, 118(9):137-146
20. [20]
  Kahveci M U, Yagci Y. Macromolecules, 2011, 44(14):5569-5572 doi: 10.1021/ma200783x
21. [21]
  Kasapoglu F, Yagci Y. Macromol Rapid Commun, 2002, 23(9):567-570 doi: 10.1002/1521-3927(20020601)23:9<567::AID-MARC567>3.0.CO;2-8
22. [22]
  Nehlig E, Schneider R, Vidal L, Balan L. Langmuir, 2012, 28(51):17795-17802 doi: 10.1021/la303923p
23. [23]
  Tehfe M A, Jamois R, Cousin P, Elkoun S, Robert M. Langmuir, 2015, 31(14):4305-4313 doi: 10.1021/la504518c
24. [24]
  Li Y D, He Y P. Chinese J Chem Phys, 1999, (4):465-468
25. [25]
  Mbhele Z H, Salemane M G, van Sittert C, Nedeljkovic J M, Djokovic V, Luyt A S. Chem Mater, 2003, 15:5019-5024 doi: 10.1021/cm034505a
26. [26]
  Compton J, Thompson, D, Kranbuehl D, Ohl S, Gain O, David L, Espuche E. Polymer, 2006, 47:5303-5313 doi: 10.1016/j.polymer.2006.05.048
27. [27]
  Eksik O, Tasdelen M A, Erciyes A T, Yagci Y. Compos Interfaces, 2010, 17:357-369 doi: 10.1163/092764410X495289
28. [28]
  Balan L, Malval J P, Schneider R, Le Nouen D, Lougnot D J. Polymer, 2010, 51:1363-1369 doi: 10.1016/j.polymer.2009.05.003
29. [29]
  Destaye A G, Lin C K, Lee C K. ACS Applied Mater Interfaces, 2013, 5(11):4745-4752 doi: 10.1021/am401730x
30. [30]
  Wei Q B, Fu F, Zhang Y Q. Adv Polym Technol, 2013, 32:624-632 doi: 10.1002/adv.v32.1s
31. [31]
32. [32]
  Yan P F, Guo A R, Liu Q, Wu Y X. J Polym Sci, Part A:Polym Chem, 2012, 50(16):3383-3392 doi: 10.1002/pola.v50.16
33. [33]
  Wu Yixian, Zhou Qi, Du Jie, Wang Nan. Acta Polymerica Sinica, 2017, (3):1047-1057
34. [34]
  Ojha U, Rajkhowa R, Agnihotra S R, Faust R. Macromolecules, 2008, 41(11):3832-3841 doi: 10.1021/ma7027209
35. [35]
  Tan Dexin, Wang Yanli, Xu Guocai. Chinese J Inorg Chem, 2006, 22(10):1921-1922 doi: 10.3321/j.issn:1001-4861.2006.10.037
36. [36]
  Aleksandra N. Krklješ, Milena T. Marinović-Cincović, Zorica M. Kacarevic-Popovic. Eur Polym J, 2007, 43(6):2171-2176 doi: 10.1016/j.eurpolymj.2007.03.023
1. [1]
  Xiaotong LU , Pan ZHANG , Zijie ZHAO , Lei HUANG , Hongwei ZUO , Lili LIANG . Antitumor and antibacterial activities of pyridyl Schiff base indium and dysprosium complexes. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1523-1532. doi: 10.11862/CJIC.20250073
2. [2]
  Weijie Yang , Mansheng Chen , Chen Xu , Fujian Xu . Hydroxyl-Rich Polycations: Innovative Materials Empowering Life and Health. University Chemistry, 2025, 40(9): 332-343. doi: 10.12461/PKU.DXHX202410072
3. [3]
  Yihan Xue , Xue Han , Jie Zhang , Xiaoru Wen . NCQDs修饰FeOOH基复合材料的制备及其电容脱盐性能. Acta Physico-Chimica Sinica, 2025, 41(7): 100072-0. doi: 10.1016/j.actphy.2025.100072
4. [4]
  Shipeng WANG , Shangyu XIE , Luxian LIANG , Xuehong WANG , Jie WEI , Deqiang WANG . Piezoelectric effect of Mn, Bi co-doped sodium niobate for promoting cell proliferation and bacteriostasis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1919-1931. doi: 10.11862/CJIC.20240094
5. [5]
  Yijing GU , Huan PANG , Rongmei ZHU . Applications of nickel-based metal-organic framework compounds in supercapacitors. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 2029-2038. doi: 10.11862/CJIC.20250186
6. [6]
  Shiyang He , Dandan Chu , Zhixin Pang , Yuhang Du , Jiayi Wang , Yuhong Chen , Yumeng Su , Jianhua Qin , Xiangrong Pan , Zhan Zhou , Jingguo Li , Lufang Ma , Chaoliang Tan . Pt Single-Atom-Functionalized 2D Al-TCPP MOF Nanosheets for Enhanced Photodynamic Antimicrobial Therapy. Acta Physico-Chimica Sinica, 2025, 41(5): 100046-0. doi: 10.1016/j.actphy.2025.100046
7. [7]
  Xiangyu CAO , Jiaying ZHANG , Yun FENG , Linkun SHEN , Xiuling ZHANG , Juanzhi YAN . Synthesis and electrochemical properties of bimetallic-doped porous carbon cathode material. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 509-520. doi: 10.11862/CJIC.20240270
8. [8]
  Yang Li , Jiachen Li , Daidi Fan . 二硫化钼纳米片的制备及其纳米酶性能探究——介绍一个大学化学综合实验. University Chemistry, 2025, 40(8): 233-240. doi: 10.12461/PKU.DXHX202410016
9. [9]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
10. [10]
  Zhihuan XU , Qing KANG , Yuzhen LONG , Qian YUAN , Cidong LIU , Xin LI , Genghuai TANG , Yuqing LIAO . Effect of graphene oxide concentration on the electrochemical properties of reduced graphene oxide/ZnS. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1329-1336. doi: 10.11862/CJIC.20230447
11. [11]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
12. [12]
  Jiatong Hu , Qiyi Wang , Ruiwen Tang , Jiajing Feng . Photocatalytic Journey of Perylene Diimides in a Competitive Arena. University Chemistry, 2025, 40(5): 328-333. doi: 10.12461/PKU.DXHX202407015
13. [13]
  Hongling Yuan , Jialin Xie , Jiawei Wang , Jixiang Zhao , Jiayan Liu , Qing Feng , Wei Qi , Min Liu . Cyclic Olefin Copolymer (COC): The Agile Vanguard in the Realm of Materials. University Chemistry, 2024, 39(7): 294-298. doi: 10.12461/PKU.DXHX202311041
14. [14]
  Changqing MIAO , Fengjiao CHEN , Wenyu LI , Shujie WEI , Yuqing YAO , Keyi WANG , Ni WANG , Xiaoyan XIN , Ming FANG . Crystal structures, DNA action, and antibacterial activities of three tetranuclear lanthanide-based complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2455-2465. doi: 10.11862/CJIC.20240192
15. [15]
  Wei Sun , Yongjing Wang , Kun Xiang , Saishuai Bai , Haitao Wang , Jing Zou , Arramel , Jizhou Jiang . CoP Decorated on Ti₃C₂T_x MXene Nanocomposites as Robust Electrocatalyst for Hydrogen Evolution Reaction. Acta Physico-Chimica Sinica, 2024, 40(8): 2308015-0. doi: 10.3866/PKU.WHXB202308015
16. [16]
  Yaping ZHANG , Tongchen WU , Yun ZHENG , Bizhou LIN . Z-scheme heterojunction β-Bi₂O₃ pillared CoAl layered double hydroxide nanohybrid: Fabrication and photocatalytic degradation property. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 531-539. doi: 10.11862/CJIC.20240256
17. [17]
  Zhangyong LIU , Lihui XU , Yue YANG , Liming WANG , Hong PAN , Xinzhe HUANG , Xueqiang FU , Yingxiu ZHANG , Meiran DOU , Meng WANG , Yi TENG . Preparation and photocatalytic performance of Cs_xWO₃/TiO₂ based on full spectral response. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1445-1464. doi: 10.11862/CJIC.20240345
18. [18]
  Jiahong ZHENG , Jiajun SHEN , Xin BAI . Preparation and electrochemical properties of nickel foam loaded NiMoO₄/NiMoS₄ composites. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 581-590. doi: 10.11862/CJIC.20230253
19. [19]
  Fangfang WANG , Jiaqi CHEN , Weiyin SUN . CuBi@Cu-MOF composite catalysts for electrocatalytic CO₂ reduction to HCOOH. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 97-104. doi: 10.11862/CJIC.20240350
20. [20]
  Guanghui SUI , Yanyan CHENG . Application of rice husk-based activated carbon-loaded MgO composite for symmetric supercapacitors. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 521-530. doi: 10.11862/CJIC.20240221

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(248)
HTML views(13)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142