Citation: Li Rongye, Mehul Khiman, Sheng Li, Sun Jing. pH/Solvent Tunable Hierarchical Nanostructures Assembled from an Amphiphilic Polypeptide-containing Triblock Copolymer[J]. Acta Chimica Sinica, ;2020, 78(11): 1235-1239. doi: 10.6023/A20080339 shu

pH/Solvent Tunable Hierarchical Nanostructures Assembled from an Amphiphilic Polypeptide-containing Triblock Copolymer

Li Rongye ^† ,
Mehul Khiman ^† ,
Sheng Li ,
Sun Jing ^,

College of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

Corresponding author: Sun Jing, jingsun@qust.edu.cn
Received Date: 1 August 2020
Available Online: 4 September 2020
Fund Project: the National Natural Science Foundation of China 21674054Project supported by the National Natural Science Foundation of China (Nos. 51722302 and 21674054) and the Natural Science Foundation of Shandong Province (No. ZR2019JQ17)the National Natural Science Foundation of China 51722302the Natural Science Foundation of Shandong Province ZR2019JQ17

Figures(6)

Similar to natural proteins, polypeptides can form secondary structures depending on their physical properties. Many efforts have been made towards the self-assembly of triblock copolymer containing polypeptide as an important component to construct hierarchical structures by utilizing the pH-responsive conformation transformation. In this work, a pH-responsive poly(ethylene glycol)-b-poly(L-lysine)-b-poly(styrene) (PEG-b-PLL-b-PS) triblock copolymer was prepared via a combination of controlled ring opening polymerization (ROP) and atom transfer radical polymerization (ATRP). In the triblock copolymer, PLL is water-soluble in acidic solution with random coil conformation, but becomes insoluble helix in alkaline solution. PEG has excellent water solubility that can exhibit protein-resistant property. PS serves as hydrophobic part. Self-assembly of the polymer was examined by transmission electron microscopy (TEM), atomic force microscopy (AFM) and attenuated total reflection-infrared spectrometer (ATR-IR). The triblock copolymer forms spherical micelles in 1:1 volume ratio of tetrahydrofuran-water mixed solvent, in which the hydrophobic PS segment forms a core and the two hydrophilic segments PLL and PEG serve as shell and corona, respectively. The spheres as the subunits further transform into hierarchical 1D fiber-like structure in the presence of THF after 7 d of aging, confirmed by both TEM and AFM techniques. Upon removing THF, the spherical shape was re-obtained with slightly smaller diameter, so called "frozen micelles". Further, the diameter of the spheres increases with pH increasing. A sphere-to-vesicle transition was observed at pH 13 as the secondary conformation of PLL transforms from coil to α-helix. The dialysis of these solutions can convert the vesicles back into spherical morphology with slightly smaller diameter.
- triblock copolymer,
- ring-opening polymerization,
- atom transfer radical polymerization,
- self-assembly,
- pH responsive,
- nanostructure
1. [1]
  Mai, Y.; Eisenberg, A. Chem. Soc. Rev. 2012, 41, 5969. doi: 10.1039/c2cs35115c
2. [2]
  Qiu, H.; Gao, Y.; Boott, C. E.; Gould, O. E. C.; Harniman, R. L.; Miles, M. J.; Webb, S. E. D.; Winnik, M. A.; Manners, I. Science 2016, 352, 697. doi: 10.1126/science.aad9521
3. [3]
  Qiu, H.; Hudson, Z. M.; Winnik, M. A.; Manners, I. Science 2015, 347, 1329. doi: 10.1126/science.1261816
4. [4]
  Gröschel, A. H.; Walther, A.; Löbling, T. I.; Schacher, F. H.; Schmalz, H.; Müller, A. H. Nature 2013, 503, 247. doi: 10.1038/nature12610
5. [5]
  Xu, X.; Wu, G.; Zhang, J.; Wang, Y.; Fan, Y.; Ma, J. Acta Chim. Sinica 2008, 66, 1102(in Chinese).
6. [6]
  Cademartiri, L.; Bishop, K. J. M. Nat. Mater. 2015, 14, 2. doi: 10.1038/nmat4184
7. [7]
  Walther, A.; Müller, A. H. Chem. Rev. 2013, 113, 5194. doi: 10.1021/cr300089t
8. [8]
  Movassaghian, S.; Merkel, O. M.; Torchilin, V. P. Wiley Interdiplinary Reviews Nanomedicine & Nanobiotechnology 2015, 7, 691.
9. [9]
  Jiang, J.; Shen, N.; Ci, T.; Tang, Z.; Gu, Z.; Li, G.; Chen, X. Adv. Mater. 2019, 31, 1.
10. [10]
  Li, Z.; Kesselman, E.; Talmon, Y.; Hillmyer, M. A.; Lodge, T. P. Science 2004, 306, 98. doi: 10.1126/science.1103350
11. [11]
  Kubowicz, S.; Baussard, J. F.; Lutz, J. F.; Thünemann, A. F.; Berlepsch, H. V.; Laschewsky, A. Angew. Chem. Int. Ed. 2005, 44, 5262. doi: 10.1002/anie.200500584
12. [12]
  Gröschel, A. H.; Schacher, F. H.; Schmalz, H.; Borisov, O. V.; Zhulina, E. B.; Walther, A.; Müller, A. H. Nat. Commun. 2012, 3, 710. doi: 10.1038/ncomms1707
13. [13]
  Zhuang, Z.; Jiang, T.; Lin, J.; Gao, L.; Yang, C.; Wang, L.; Cai, C. Angew. Chem. Int. Ed. 2016, 55, 12522. doi: 10.1002/anie.201607059
14. [14]
  Zhang, L.; Eisenberg, A. Science 1995, 268, 1728. doi: 10.1126/science.268.5218.1728
15. [15]
  Hadjichristidis, N.; Hirao, A.; Tezuka, Y.; Prez, F. D. Wiley InterScience, John Wiley & Sons Inc., New York, 2011, p. 823.
16. [16]
  Zhang, J.; Chen, X.; Wei, H.; Wan, X. Chem. Soc. Rev. 2013, 42, 9127. doi: 10.1039/c3cs60192g
17. [17]
  Chen, P.; Qiu, M.; Deng, C.; Meng, F.; Zhang, J.; Cheng, R.; Zhong, Z. Biomacromolecules 2015, 16, 1322. doi: 10.1021/acs.biomac.5b00113
18. [18]
  Ran, M.; Shi, D.; Dong, H.; Chen, M.; Zhao, Z. Acta Chim. Sinica 2015, 73, 1047(in Chinese).
19. [19]
  Sheng, L.; Chen, H.; Fu, W.; Li, Z. Acta Polym. Sinica 2015, 8, 982(in Chinese).
20. [20]
  Sheng, L.; Chen, H.; Fu, W.; Li, Z. Langmuir 2015, 31, 11964. doi: 10.1021/acs.langmuir.5b02417
21. [21]
  Boott, C. E.; Gwyther, J.; Harniman, R. L.; Hayward, D. W.; Manners, I. Nat. Chem. 2017, 9, 785. doi: 10.1038/nchem.2721
22. [22]
  Yu, K.; Eisenberg, A. Macromolecules 1996, 29, 6359. doi: 10.1021/ma960381u
23. [23]
  Betthausen, E.; Hanske, C.; Müller, M.; Fery, A.; Schacher, F. H.; Müller, A. H. E.; Pochan, D. J. Macromolecules 2014, 47, 1672. doi: 10.1021/ma402555c
24. [24]
  Zhang, S.; Li, Q.; Lin, J.; Cai, C.; Wang, L. Acta Polym. Sinica 2017, 2, 294(in Chinese).
25. [25]
  Bhargava, P.; Tu, Y.; Zheng, J.; Xiong, H.; Quirk, R. P.; Cheng, S. Z. D. J. Am. Chem. Soc. 2007, 129, 1113. doi: 10.1021/ja0653019
26. [26]
  Özdemir, C.; Güner, A. Eur. Polym. J. 2007, 43, 3068. doi: 10.1016/j.eurpolymj.2007.02.022
27. [27]
  Rozenberg, M.; Shoham, G. Biophys. Chem. 2007, 125, 166. doi: 10.1016/j.bpc.2006.07.008
28. [28]
  Prestrelski, S. J.; Tedeschi, N.; Arakawa, T.; Carpenter, J. F. Biophys. J. 1993, 65, 661. doi: 10.1016/S0006-3495(93)81120-2
29. [29]
  Mauerer, A.; Lee, G. Eur. J. Pharm. Sci. 2006, 62, 131.
30. [30]
  Jain, S.; Bates, F. S. Macromolecules 2004, 37, 1511. doi: 10.1021/ma035467j
31. [31]
  Rager, T.; Meyer, W. H.; Wegner, G. Macromol. Chem. Phys. 1999, 200, 1672. doi: 10.1002/(SICI)1521-3935(19990701)200:7<1672::AID-MACP1672>3.0.CO;2-V
32. [32]
  Stam, J. V.; Creutz, S.; Schryver, F. C. D.; Jérôme, R. Macromolecules 2000, 33, 6388. doi: 10.1021/ma992174a
33. [33]
  Zhang, L.; Barlow, R. J.; Eisenberg, A. Macromolecules 1995, 28, 6055. doi: 10.1021/ma00122a010
34. [34]
  Tuzar, Z.; Kratochvil, P. Surf. Colloid Sci. 1993, 15, 1.
35. [35]
  Munk, P. Solvents and Self-Organization of Polymers, Springer, Netherlands, New York, 1996, p. 19.
36. [36]
  Zhang, Y.; Jiang, M.; Zhao, J.; Wang, Z.; Dou, H.; Chen, D. Langmuir 2005, 21, 1531. doi: 10.1021/la047912p
37. [37]
  Lei, L.; Gohy, J.; Willet, N.; Zhang, J.; Varshney, S.; Jérôme, R. Macromolecules 2004, 37, 1089. doi: 10.1021/ma034255j
38. [38]
  Jada, A.; Hurtrez, G.; Siffert, B.; Riess, G. Macromol. Chem. Phys 1996, 197, 3697. doi: 10.1002/macp.1996.021971117
39. [39]
  Zhang, L.; Yu, K.; Eisenberg, A. Science 1996, 272, 1777. doi: 10.1126/science.272.5269.1777
40. [40]
  Ray, J. G.; Naik, S. S.; Hoff, E. A.; Johnson, A. J.; Ly, J. T.; Easterling, C. P.; Patton, D. L.; Savin, D. A. Macromol. Chem. Phys. 2012, 33, 819.
41. [41]
  Naik, S. S.; Ray, J. G.; Savin, D. A. Langmuir 2011, 27, 7231. doi: 10.1021/la200882f
42. [42]
  Zhang, W.; He, J.; Liu, Z.; Ni, P.; Zhu, X. J. Polym. Sci. Part A:Polym. Chem. 2010, 48, 1079. doi: 10.1002/pola.23863
43. [43]
  Jackson, M.; Mantsch, H. H. Crit. Rev. Biochem. Mol. 1995, 30, 95. doi: 10.3109/10409239509085140
44. [44]
  Dzwolak, W.; Smirnovas, V. Biophys. Chem. 2005, 115, 49. doi: 10.1016/j.bpc.2005.01.003
45. [45]
  Mirtič, A.; Grdadolnik, J. Biophys. Chem. 2013, 175-176, 47. doi: 10.1016/j.bpc.2013.02.004
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