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
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