Self-assembly and pH-Responsive Properties of Poly(L-glutamic acid-r-Lleucine) and Poly(L-glutamic acid-r-L-leucine)-b-Polysarcosine

Citation: Ce Tian, Jun Ling, You-qing Shen. Self-assembly and pH-Responsive Properties of Poly(L-glutamic acid-r-Lleucine) and Poly(L-glutamic acid-r-L-leucine)-b-Polysarcosine[J]. Chinese Journal of Polymer Science, 2015, 33(8): 1186-1195. doi: 10.1007/s10118-015-1669-0 shu

Self-assembly and pH-Responsive Properties of Poly(L-glutamic acid-r-Lleucine) and Poly(L-glutamic acid-r-L-leucine)-b-Polysarcosine

Ce Tian ^1, ,
Jun Ling ^{1,
,} ,
You-qing Shen ^2,

1.
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
2.
Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China

通讯作者: Jun Ling,

基金项目:
This work was financially supported by the National Natural Science Foundation of China (Nos. 21174122 and 51390481).

摘要: Polypeptides and polypeptoids were widely used as biomedical materials because of their good biocompatibility. In this work we reported a series of pH-responsive copolypeptides and polypeptide-polypeptoid block copolymers, i.e. random copolymers of L-glutamic acid (Glu) with L-leucine (Leu) [poly(Glu-r-Leu)s], as well as their block copolymers with polysarcosine (polySar). Well-defined poly(Glu-r-Leu)s with predictable compositions and molecular weights were synthesized by ring opening polymerization of corresponding N-carboxyanhydride monomers. We investigated the relationship between hydrophilicity-hydrophobicity transition and copolymer composition. With increasing Leu fraction, both the pH value of cloud point and the micellar size increased. Poly(Glu-r-Leu) with 60% Leu exhibited a cloud point at the pH of 5.0 to 6.0 the same as that in endosome and lysosome. Poly(Glu-r-Leu)-b-polySars assembled in phosphate buffer and performed pH-responsive morphology change from orbicular micelles at high pH to worm-like micelles at low pH. They were potential pH-responsive carriers for drug and gene delivery to enhance cargo release in cellules.

关键词:

-Amino acid NCA
/ Random/block copolypeptide
/ pH-Responsive
/ Hydrophilicity-hydrophobicity transition

English

Self-assembly and pH-Responsive Properties of Poly(L-glutamic acid-r-Lleucine) and Poly(L-glutamic acid-r-L-leucine)-b-Polysarcosine

Ce Tian ^1, ,
Jun Ling ^{1,
,} ,
You-qing Shen ^2,

1.
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
2.
Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China

Corresponding author: Jun Ling,

Received Date: 05 January 2015
Revised Date: 06 February 2015
Available Online: 05 August 2015
Fund Project:
This work was financially supported by the National Natural Science Foundation of China (Nos. 21174122 and 51390481).

Abstract: Polypeptides and polypeptoids were widely used as biomedical materials because of their good biocompatibility. In this work we reported a series of pH-responsive copolypeptides and polypeptide-polypeptoid block copolymers, i.e. random copolymers of L-glutamic acid (Glu) with L-leucine (Leu) [poly(Glu-r-Leu)s], as well as their block copolymers with polysarcosine (polySar). Well-defined poly(Glu-r-Leu)s with predictable compositions and molecular weights were synthesized by ring opening polymerization of corresponding N-carboxyanhydride monomers. We investigated the relationship between hydrophilicity-hydrophobicity transition and copolymer composition. With increasing Leu fraction, both the pH value of cloud point and the micellar size increased. Poly(Glu-r-Leu) with 60% Leu exhibited a cloud point at the pH of 5.0 to 6.0 the same as that in endosome and lysosome. Poly(Glu-r-Leu)-b-polySars assembled in phosphate buffer and performed pH-responsive morphology change from orbicular micelles at high pH to worm-like micelles at low pH. They were potential pH-responsive carriers for drug and gene delivery to enhance cargo release in cellules.

Key words:

-Amino acid NCA
/ Random/block copolypeptide
/ pH-Responsive
/ Hydrophilicity-hydrophobicity transition

1. [1]
  Deming, T.J., Adv. Mater., 1997, 9(4): 299
2. [2]
  Huang, J. and Heise, A., Chem. Soc. Rev., 2013, 42(17): 7373
3. [3]
  Wong, S., Shim, M.S. and Kwon, Y.J., J. Mater. Chem. B, 2014, 2(6): 595
4. [4]
  Lu, H., Wang, J., Song, Z.Y., Yin, L.C., Zhang, Y.F., Tang, H.Y., Tu, C.L., Lin, Y. and Cheng, J.J., Chem. Commun., 2014, 50(2): 139
5. [5]
  Deming, T.J., Prog. Polym. Sci., 2007, 32(8-9): 858
6. [6]
  Shi, N.Q., Qi, X.R., Xiang, B. and Zhang, Y., J. Control. Release, 2014, 194: 53
7. [7]
  Wang, F.H., Wang, Y., Zhang, X., Zhang, W.J., Guo, S.G. and Jin, F., J. Control. Release, 2014, 174: 126
8. [8]
  Deming, T.J., Nature, 1997, 390(6658): 386
9. [9]
  Peng, H., Chen, W.L., Kong, J., Shen, Z.Q. and Ling, J., Chinese J. Polym. Sci., 2014, 32(6): 743
10. [10]
  Mavrogiorgis, D., Bilalis, P., Karatzas, A., Skoulas, D., Fotinogiannopoulou, G. and Iatrou, H., Polym. Chem., 2014, 5(21): 6256
11. [11]
  He, C.L., Zhuang, X.L., Tang, Z.H., Tian, H.Y. and Chen, X.S., Adv. Healthc. Mater., 2012, 1(1): 48
12. [12]
  Huang, Y., Tang, Z.H., Zhang, X.F., Yu, H.Y., Sun, H., Pang, X. and Chen, X.S., Biomacromolecules, 2013, 14(6): 2023
13. [13]
  Wang, J., Lu, H., Kamat, R., Pingali, S.V., Urban, V.S., Cheng, J.J. and Lin, Y., J. Am. Chem. Soc., 2011, 133(33): 12906
14. [14]
  Rodriguez-Hernandez, J. and Lecommandoux, S., J. Am. Chem. Soc., 2005, 127(7): 2026
15. [15]
  Xia, J.L., Chen, J., Tian, H.Y. and Chen, X.S., Scientia Sinica Chimica, 2010, 40(3): 255
16. [16]
  Holowka, E.P., Pochan, D.J. and Deming, T.J., J. Am. Chem. Soc., 2005, 127(35): 12423
17. [17]
  Fasman, G.D., Lindblow, C. and Bodenheimer, E., Biochemistry, 1964, 3(2): 155
18. [18]
  Bychkova, V.E., Gudkov, A.T., Miller, W.G., Mitin, Y.V., Ptitsyn, O.B. and Shpungin, I.L., Biopolymers, 1975, 14(8): 1739
19. [19]
  Beverung, C.J., Radke, C.J. and Blanch, H.W., Biophys. Chem., 1998, 70(2): 121
20. [20]
  Soderquist, M.E., Gershman, H., Anderson, J.M. and Walton, A.G., J. Biomed. Mater. Res., 1979, 13(6): 865
21. [21]
  Helmus, M.N., Gibbons, D.F. and Jones, R.D., J. Biomed. Mater. Res., 1984, 18(2): 165
22. [22]
  Jayakumar, R., Murali, J., Koteeswari, D. and Gomathi, K., J. Biochem., 2004, 136(4): 457
23. [23]
  Tao, X.F., Deng, Y.W., Shen, Z.Q. and Ling, J., Macromolecules, 2014, 47(18): 6173
24. [24]
  Fetsch, C., Grossmann, A., Holz, L., Nawroth, J.F. and Luxenhofer, R., Macromolecules, 2011, 44(17): 6746
25. [25]
  Birke, A., Huesmann, D., Kelsch, A., Weilbaecher, M., Xie, J., Bros, M., Bopp, T., Becker, C., Landfester, K. and Barz, M., Biomacromolecules, 2014, 15(2): 548
26. [26]
  Tao, X.F., Deng, C. and Ling, J., Macromol. Rapid Commun., 2014, 35(9): 875
27. [27]
  Luxenhofer, R., Fetsch, C. and Grossmann, A., J. Polym. Sci., Part A: Polym. Chem., 2013, 51(13): 2731
28. [28]
  Ulbricht, J., Jordan, R. and Luxenhofer, R., Biomaterials, 2014, 35(17): 4848
29. [29]
  Ostuni, E., Chapman, R.G., Holmlin, R.E., Takayama, S. and Whitesides, G.M., Langmuir, 2001, 17(18): 5605
30. [30]
  Zhou, M., Liu, H.W., Venkiteshwaran, A., Kilduff, J., Anderson, D.G., Langer, R. and Belfort, G., J. Mater. Chem., 2011, 21(3): 693
31. [31]
  Heller, P., Birke, A., Huesmann, D., Weber, B., Fischer, K., Reske-Kunz, A., Bros, M. and Barz, M., Macromol. Biosci., 2014, 14(10): 1380
32. [32]
  Daly, W.H. and Poche, D., Tetrahedron Lett., 1988, 29(46): 5859
33. [33]
  Peng, H., Ling, J. and Shen, Z.Q., J. Polym. Sci., Part A: Polym. Chem., 2012, 50(6): 1076
34. [34]
  Peng, H., Ling, J., Zhu, Y.H., You, L.X. and Shen, Z.Q., J. Polym. Sci., Part A: Polym. Chem., 2012, 50(15): 3016
35. [35]
  Kricheldorf, H.R., von Lossow, C. and Schwarz, G., Macromol. Chem. Phys., 2004, 205(7): 918
36. [36]
  Guo, L. and Zhang, D., J. Am. Chem. Soc., 2009, 131(50): 18072
37. [37]
  Lahasky, S.H., Hu, X.K. and Zhang, D.H., ACS Macro Lett., 2012, 1(5): 580
38. [38]
  Huesmann, D., Birke, A., Klinker, K., Tuerk, S., Raeder, H.J. and Barz, M., Macromolecules, 2014, 47(3): 928
39. [39]
  Maruyama, K., Yuda, T., Okamoto, A., Kojima, S., Suginaka, A. and Iwatsuru, M., Biochim. Biophys. Acta., 1992, 1128(1): 44
40. [40]
  Blanazs, A., Armes, S.P. and Ryan, A.J., Macromol. Rapid Commun., 2009, 30(4-5): 267

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Self-assembly and pH-Responsive Properties of Poly(L-glutamic acid-r-Lleucine) and Poly(L-glutamic acid-r-L-leucine)-b-Polysarcosine

通讯作者: Jun Ling,

English

Self-assembly and pH-Responsive Properties of Poly(L-glutamic acid-r-Lleucine) and Poly(L-glutamic acid-r-L-leucine)-b-Polysarcosine

Corresponding author: Jun Ling,

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Self-assembly and pH-Responsive Properties of Poly(L-glutamic acid-r-Lleucine) and Poly(L-glutamic acid-r-L-leucine)-b-Polysarcosine

通讯作者: Jun Ling,

English

Self-assembly and pH-Responsive Properties of Poly(L-glutamic acid-r-Lleucine) and Poly(L-glutamic acid-r-L-leucine)-b-Polysarcosine

Corresponding author: Jun Ling,

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