Citation: Chu Wang, Li Wang, Jin-hao Huo, Jian Zhou. Computer Simulation on the pH-Responsive Block Copolymer Membrane[J]. Acta Polymerica Sinica, ;2018, (4): 515-523. doi: 10.11777/j.issn1000-3304.2017.17137 shu

Computer Simulation on the pH-Responsive Block Copolymer Membrane

Guangdong Provincial Key Laboratory for Green Chemical Product technology, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640

Corresponding author: Jian Zhou, jianzhou@scut.edu.cn
Received Date: 22 May 2017
Revised Date: 12 July 2017

Dissipative particle dynamics (DPD) was employed to investigate the self-assembly of tri-block copolymer PS-PAA-PEO into channel membrane by non-solvent induced phase separation method. The micro-phase separation process was simulated by solvent exchange method, which mimics the practical membrane preparation process. The polymer concentration has a significant effect on the micro-phase separation process:a too high polymer concentration would limit the micro-phase separation, while a too low concentration would result in lamellar structure. For the PS-PAA-PEO system, it was found that the channel membrane could be obtained in the concentration range of 30%-45%. The morphology evolution clearly showed the micro-phase separation process. The polymer chains of PS formed the matrix part of the channel membrane and the chains of PAA acted as the "open/close" switch, while the chains of PEO were distributed in the innermost. Because PAA possesses weak acidic groups that can gain or lose protons in response to pH, the sizes of the channel pores at different pH are calculated. At pH lower than the pK_a of PAA, the carboxyl groups of PAA are protonated, therefore the membrane pore is in the "open" state because of the reduced electrostatic repulsion between PAA on the inner pore surface. In contrast, at neutral pH, the carboxyl groups of PAA are dissociated and negatively charged; the membrane pore is in the "closed" state because the repulsion between negative groups makes PAA chains extensively swelled. With pH values changing from 1 to 6.25, the membrane pore size decreased from 19.3 nm to 2.9 nm. After the porous membrane was solidified, small-sized nanoparticles could pass through the middle of the channel. The filtration of different sized nanoparticles was studied to justify the accuracy of the pore sizes under different dissociation degrees. The permeation results confirmed that the channel membrane, which was in the "close" state due to the swollen conformation of PAA, had the size-based filtration function.
- Dissipative particle dynamics,
- Polymer membrane,
- Non-solvent induced phase separation,
- pH-Responsive,
- Molecular switch
1. [1]
  Ang W L, Mohammad A W, Hilal N, Leo C P. Desalination, 2015, 363:2-18 doi: 10.1016/j.desal.2014.03.008
2. [2]
  Patching S G. Biochimica et Biophysica Acta (BBA)-Biomembranes 2014, 1838(1):43-55
3. [3]
  Ning Dan, Hu Zhaoxia, Chen Rong, Chen Hanwen, Yang Hui, Chen Shouwen. Acta Polymerica Sinica, 2017, (5):842-850
4. [4]
  Shenvi S S, Isloor A M, Ismail A. Desalination, 2015, 368(15):10-26
5. [5]
  Chan W F, Marand E, Martin S M. J Membr Sci, 2016, 509:125-137 doi: 10.1016/j.memsci.2016.02.014
6. [6]
  Chen X, Luo J, Qi B, Cao W, Wan Y. Water Process Eng, 2015, 7:1-10 doi: 10.1016/j.jwpe.2015.04.009
7. [7]
  Liu Z, Wang W, Xie R, Ju X J, Chu L Y. Chem Soc Rev, 2016, 45(3):460-475 doi: 10.1039/C5CS00692A
8. [8]
  Guo H, Qiu X, Zhou J. J Chem Phys, 2013, 139(8):084907 doi: 10.1063/1.4817003
9. [9]
  Min W, Zhao D, Quan X, Sun D, Li L, Zhou J. Colloids Surf B, 2017, 152(1):260-268
10. [10]
  Hu Yadong, Xu Pei, Luo Xiao, Zuo Xingang, Chen Fang, Ding Yunsheng. Acta Polymerica Sinica, 2017, (5):776-784
11. [11]
  Thévenot J, Oliveira H, Sandre O, Lecommandoux S. Chem Soc Rev, 2013, 42(17):7099-7116 doi: 10.1039/c3cs60058k
12. [12]
  Ma Xiang, Tian He. Acta Polymerica Sinica, 2017, (1):27-36
13. [13]
  Yu H, Qiu X, Behzad A, Musteata V, Smilgies D-M, Nunes S, Peinemann K V. Chem Commun, 2016, 2016, 52(81):12064-12067
14. [14]
  Tripathi B P, Dubey N C, Choudhury S, Simon F, Stamm M. J Mater Chem B, 2013, 1(27):3397-3409 doi: 10.1039/c3tb20386g
15. [15]
  Tang Y H, Lin H H, Liu T Y, Matsuyama H. J Membr Sci, 2016, 515(1):258-267
16. [16]
  Nunes S P. Macromolecules, 2016, 49(8):2905-2916 doi: 10.1021/acs.macromol.5b02579
17. [17]
  Baldi A, Narayan T C, Koh A L, Dionne J A. Nat Mater, 2014, 13(12):1143-1148 doi: 10.1038/nmat4086
18. [18]
  Liu Y, Li Y, He J, Duelge K J, Lu Z, Nie Z. J Am Chem Soc, 2014, 136(6):2602-2610 doi: 10.1021/ja412172f
19. [19]
  Huang Zihan, Dong Bojun, Chen Pengyu, Yang Ye, Zhu Guolong, Yan Litang. Acta Polymerica Sinica, 2016, (8):979-991 doi: 10.11777/j.issn1000-3304.2016.16055
20. [20]
  Lin H H, Tang Y H, Liu T Y, Matsuyama H, Wang X L. J Membr Sci, 2016, 507:143-153 doi: 10.1016/j.memsci.2016.01.049
21. [21]
  Zhou J, Zhu X, Hu J, Liu H, Hu Y, Jiang J. Phys Chem Chem Phys, 2014, 16(13):6075-6083 doi: 10.1039/c3cp55498h
22. [22]
  Konatham D, Yu J, Ho T A, Striolo A. Langmuir, 2013, 29(38):11884-11897 doi: 10.1021/la4018695
23. [23]
  Meyer J C, Kisielowski C, Erni R, Rossell M D, Crommie M, Zettl A. Nano Lett, 2008, 8(11):3582-3586 doi: 10.1021/nl801386m
24. [24]
  He Z, Zhou J, Lu X, Corry B. ACS Nano, 2013, 7(11):10148-10157 doi: 10.1021/nn4043628
25. [25]
  Gao W, Liang H, Ma J, Han M, Chen Z L, Han Z S, Li G B. Desalination, 2011, 272(1):1-8
26. [26]
  Wang C, Ma S, Hu Y, Wang R. Langmuir, 2017, 33(14):3427-3433 doi: 10.1021/acs.langmuir.6b04509
27. [27]
  Shin J M, Kim Y, Yun H, Yi G R, Kim B J. ACS Nano, 2017, 11(2):2133-2142 doi: 10.1021/acsnano.6b08342
28. [28]
  Sepehr F, Liu H, Luo X, Bae C, Tuckerman M E, Hickner M A, Paddison S J. Macromolecules, 2017, 50(11):4397-4405 doi: 10.1021/acs.macromol.7b00082
29. [29]
  Wang Jian, Lu Yuyuan, Xu Yuci, Ruan Yongjin, Li Liangyi, An Lijia. Acta Polymerica Sinica, 2015, (3):271-287
30. [30]
  Qian Junhu, Jiao Guisheng, Li Yanchun, Lv Zhongyuan. Acta Polymerica Sinica, 2016, (8):1011-1020 doi: 10.11777/j.issn1000-3304.2016.16067
31. [31]
  Liu Hongyan, Guo Hongyu, Zhou Jian. Acta Chim Sin, 2012, 70(23):2445-2450
32. [32]
  Sun Delin, Zhou Jian. Acta Physico-Chimica Sinica, 2012, 28(4):909-916
33. [33]
  Groot R D, Warren P B. J Chem Phys, 1997, 107(11):4423-4435 doi: 10.1063/1.474784
34. [34]
  Groot R D. J Chem Phys, 2003, 118(24):11265-11277 doi: 10.1063/1.1574800
35. [35]
  González-Melchor M, Mayoral E, Velázquez M E, Alejandre J. J Chem Phys, 2006, 125(22):224107 doi: 10.1063/1.2400223
36. [36]
  Karunakaran M, Nunes S P, Qiu X, Yu H, Peinemann K V. J Membr Sci, 2014, 453471-477 doi: 10.1016/j.memsci.2013.11.015
37. [37]
  Kacar G, de With G. Phys Chem Chem Phys, 2016, 18(14):9554-9560 doi: 10.1039/C6CP00729E
38. [38]
  Cheng F, Guan X, Cao H, Su T, Cao J, Chen Y, Cai M, He B, Gu Z, Luo X. Int J Pharm, 2015, 492(1-2):152-160 doi: 10.1016/j.ijpharm.2015.07.031
39. [39]
  Bautista-Reyes R, Soto-Figueroa C, Vicente L. Model Simul Mater Sci Eng, 2016, 24(4):045004 doi: 10.1088/0965-0393/24/4/045004
40. [40]
  Kacar G, Peters E. EPL (Europhysics Letters), 2013, 102(4):40009 doi: 10.1209/0295-5075/102/40009
41. [41]
  Brandrup J, Immergut E H, Grulke E A, Abe A, Bloch D R. Polymer Handbook. New York:Wiley, 1989
42. [42]
  Groot R D, Madden T J. J Chem Phys, 1998, 108(20):8713-8724 doi: 10.1063/1.476300
43. [43]
  Groot R D, Rabone K L. Biophys J, 2001, 81(2):725-736 doi: 10.1016/S0006-3495(01)75737-2
44. [44]
  Clark S J, Segall M D, Pickard C J, Hasnip P J, Probert M I, Refson K, Payne M C. Zeitschrift für Kristallographie-Crystalline Materials, 2005, 220(5/6):567
45. [45]
  Shuichi N. Prog Theor Phys Suppl, 1991, 103:1-46 doi: 10.1143/PTPS.103.1
46. [46]
  Andersen H C. J Chem Phys, 1980, 72(4):2384-2393 doi: 10.1063/1.439486
47. [47]
  Sun H, Jin Z, Yang C, Akkermans R L, Robertson S H, Spenley N A, Miller S, Todd S M. J Mol Model, 2016, 22(2):47 doi: 10.1007/s00894-016-2909-0
48. [48]
  Zhang Naiwen, Chen Jiabin, Yu Zhijia. Chemical Engineering Thermodynamics. Dalian:Dalian University of Technology Press. 2006. 109-117
49. [49]
  Yu H, Qiu X, Behzad A, Musteata V, Smilgies D M, Nunes S P, Peinemann K V. Chem Commun, 2016, 52(81):12064-12067 doi: 10.1039/C6CC06402G
50. [50]
  Hess S C, Kohll A X, Raso R A, Schumacher C M, Grass R N, Stark W J. ACS Appl Mater Interfaces, 2015, 7(1):611-617 doi: 10.1021/am506737n
51. [51]
  Seaton M A, Anderson R L, Metz S, Smith W. Mol Simul, 2013, 39(10):796-821 doi: 10.1080/08927022.2013.772297
52. [52]
  Mai J, Sun D, Li L, Zhou J. J Chem Eng Data, 2016, 61(12):3998-4005 doi: 10.1021/acs.jced.6b00522
53. [53]
  May Junlin, Sun Delin, Quan Xuebo, Li Libo, Zhou Jian. Acta Physico-Chimica Sinica, 2016, 32(7):1649-1657 doi: 10.3866/PKU.WHXB2016032804
54. [54]
  Wielema T A, Engberts J B. Eur Polym J, 1990, 26(4):415-421 doi: 10.1016/0014-3057(90)90043-4
55. [55]
  Nie S Y, Sun Y, Lin W J, Wu W S, Guo X D, Qian Y, Zhang L J. J Phys Chem B, 2013, 117(43):13688-13697 doi: 10.1021/jp407529u
56. [56]
  Xu X, Chen S, Zhuang L, Zheng C, Wu Y. J Mater Sci, 2014, 49(7):2853-2863 doi: 10.1007/s10853-013-7991-4
57. [57]
  Berezkin A V, Papadakis C M, Potemkin I I. Macromolecules, 2015, 49(1):415-424
58. [58]
  Yong X, Qin S, Singler T J. Extre Mech Lett, 2016, 790-103
59. [59]
  Boles M A, Engel M, Talapin D V. Chem Rev, 2016, 116(18):11220-11289 doi: 10.1021/acs.chemrev.6b00196
60. [60]
  Wang Z, Guo L, Wang Y. J Membr Sci, 2015, 476:449-456 doi: 10.1016/j.memsci.2014.12.009
61. [61]
  Sarkisov L, Harrison A. Mol Simul, 2011, 37(15):1248-1257 doi: 10.1080/08927022.2011.592832
62. [62]
  Nunes S P. Macromolecules, 2016, 49(8):2905-2916 doi: 10.1021/acs.macromol.5b02579
63. [63]
  Yu H, Qiu X, Moreno N, Ma Z, Calo V M, Nunes S P, Peinemann K V. Angew Chem Int Ed, 2015, 54(47):13937-13941 doi: 10.1002/anie.201505663
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