Citation: CHENG Xiaomeng, JIAO Dongxia, LIANG Zhihao, WEI Jinjin, LI Hongping, YANG Junjiao. Self-Assembly Behavior of Amphiphilic Diblock Copolymer PS-b-P4VP in CO₂-Expanded Liquids[J]. Acta Physico-Chimica Sinica, ;2018, 34(8): 945-951. doi: 10.3866/PKU.WHXB201801292 shu

Self-Assembly Behavior of Amphiphilic Diblock Copolymer PS-b-P4VP in CO₂-Expanded Liquids

1.
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R. China
2.
Beijing Key Laboratory of Environmentally Harmful Chemical Analysis, Beijing University of Chemical Technology, Beijing 100029, P. R. China

Corresponding author: LI Hongping, lihongping@zzu.edu.cn YANG Junjiao, yangjj@mail.buct.edu.cn
Received Date: 3 January 2018
Revised Date: 20 January 2018
Accepted Date: 25 January 2018
Available Online: 29 August 2018
Fund Project: This work was supported by the National Natural Science Foundation of China J1210060the Innovative Research Grant for Undergraduate Students of National/Zhengzhou University 201710459008This work was supported by the National Natural Science Foundation of China 21773215This work was supported by the National Natural Science Foundation of China (21773215, J1210060) and the Innovative Research Grant for Undergraduate Students of National/Zhengzhou University (201710459008)

The self-assembly behavior of block copolymers and their assembled micellar morphologies have attracted considerable attention because of their potential applications in biomedicine, drug delivery, and catalysis. Herein we report that CO₂-expanded liquids (CXLs) facilitate the morphology control of the self-assembled aggregates (SAAs) of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) formed in CO₂-expanded toluene. It is found that the anti-solvent effect of CXLs can successfully regulate the self-assembly behavior of the copolymer PS-b-P4VP. The difference in amphiphilicity between PS and P4VP block is reduced with increasing pressure of CO₂-expanded toluene owing to the anti-solvent effect of CO₂. In addition, this diminished difference may influence the interfacial tension at the P4VP core-PS corona interface, which triggers a morphological change of the aggregate. The SAA structures are dependent on both CXL pressure and copolymer composition under the experimental conditions implemented in this work. The morphological evolution of the SAAs in CXLs exhibits remarkable pressure dependence. As the pressure increases, the SAA structure of PS₁₆₈-b-P4VP₄₂₀ transits from primarily spheres (0.1 MPa) to mostly interconnected rods (6.35 MPa), the SAA of PS₇₉₀-b-P4VP₂₆₃ evolves from small vesicles (0.1 MPa) to large compound vesicles (LCVs, 6.35 MPa), whereas the PS₁₅₃-b-P4VP₁₅₃₀ counterpart switches from large compound micelles (LCMs, 0.1 MPa) to mainly large compound vesicles (LCVs, 6.35 MPa). Moreover, transmission electron microscopy (TEM) data on constant copolymer composition implies that the packing parameter p of the SAAs increases with the CXLs pressure. Especially, under the experimental conditions employed in this work, we find that the major factor controlling the SAA shape in conventional toluene is the copolymer composition, while in CO₂-expanded toluene, the dominant factor controlling the SAA morphology might be the varying contact area between shell-forming segment PS and the CXLs with increasing pressure. This work proves that the CXL method facilitates the modulation of morphology of the SAAs, and opens a green route for the development of new nano-functional materials.
- CO₂-expanded liquids,
- Colloidal aggregates,
- Morphology control,
- PS-b-P4VP,
- Self-assembly
1. [1]
  Mai, Y.; Eisenberg, A. Chem. Soc. Rev.2012, 41, 5969. doi: 10.1039/c2cs35115c doi: 10.1039/c2cs35115c
2. [2]
  Chen, S. C.; Kuo, S. W.; Chang, F. C. Langmuir2011, 27, 10197. doi: 10.1021/la201506y doi: 10.1021/la201506y
3. [3]
  Zhang, L.; Eisenberg, A. J. Am. Chem. Soc. 1996, 118, 3168. doi: 10.1021/ja953709s doi: 10.1021/ja953709s
4. [4]
  Mizuno, H.; Buriak, J. M. J. Am. Chem. Soc. 2008, 130, 17656. doi: 10.1021/ja807708r doi: 10.1021/ja807708r
5. [5]
  Hanson, J. A.; Chang, C. B.; Graves, S. M.; Li, Z. B.; Mason, T. G.; Deming, T. J. Nature 2008, 455, 85. doi: 10.1038/nature07197 doi: 10.1038/nature07197
6. [6]
  Mai, Y.; Eisenberg, A. J. Am. Chem. Soc.2010, 132, 10078. doi: 10.1021/ja1024063 doi: 10.1021/ja1024063
7. [7]
  Wu, J.; Eisenberg, A. J. Am. Chem. Soc.2006, 128, 2880. doi: 10.1021/ja056064x doi: 10.1021/ja056064x
8. [8]
  Sidorenko, A.; Tokarev, I.; Minko, S.; Stamm, M. J. Am. Chem. Soc. 2003, 125, 12211. doi: 10.1021/ja036085w doi: 10.1021/ja036085w
9. [9]
  Yao, X.; Chen, D.; Jiang, M. Macromolecules2004, 37, 4211. doi: 10.1021/ma0497308 doi: 10.1021/ma0497308
10. [10]
  Peng, H.; Chen, D.; Jiang, M. Langmuir 2003, 19, 10989. doi: 10.1021/la0348721 doi: 10.1021/la0348721
11. [11]
  Ali, N.; Park, S. Y. Langmuir2009, 25, 13426. doi: 10.1021/la902346u doi: 10.1021/la902346u
12. [12]
  Clodt, J. I.; Rangou, S.; Schroder, A.; Buhr, K.; Hahn, J.; Jung, A.; Filiz, V.; Abetz, V. Macromol. Rapid Commun. 2013, 34, 190. doi: 10.1002/marc.201200680 doi: 10.1002/marc.201200680
13. [13]
  Hameed, N.; Salim, N. V.; Parameswaranpillai, J.; Fox, B. L. Mater. Lett. 2015, 147, 92. doi: 10.1016/j.matlet.2015.02.036 doi: 10.1016/j.matlet.2015.02.036
14. [14]
  Liu, H.; Gao, C. Q.; Ding, Z. L.; Zhang, W. Q. Macromol. Chem. Phys.2016, 217, 467. doi: 10.1002/macp.201500273 doi: 10.1002/macp.201500273
15. [15]
  Liu, F.; Eisenberg, A. J. Am. Chem. Soc.2003, 125, 15059. doi: 10.1021/ja038142r doi: 10.1021/ja038142r
16. [16]
  Geng, Z.; Cheng, Z. K.; Zhu, Y. T.; Jiang, W. J. Phys. Chem. B 2016, 120, 5527. doi: 10.1021/acs.jpcb.6b00273 doi: 10.1021/acs.jpcb.6b00273
17. [17]
  Yi, Z.; Zhang, P. B.; Liu, C. J.; Zhu, L. P. Macromolecules 2016, 49, 3343. doi: 10.1021/acs.macromol.6b00166 doi: 10.1021/acs.macromol.6b00166
18. [18]
  Zhang, L.; Shen, H.; Eisenberg, A. Macromolecules 1997, 30, 1001. doi: 10.1021/ma961413g doi: 10.1021/ma961413g
19. [19]
  Harada, A.; Kataoka, K. Macromolecules1995, 28, 5294. doi: 10.1021/ma946318r doi: 10.1021/ma946318r
20. [20]
  Duan, H.; Chen, D.; Jiang, M.; Gan, W.; Li, S.; Wang, M.; Gong, J. J. Am. Chem. Soc. 2001, 123, 12097. doi: 10.1021/ja011502v doi: 10.1021/ja011502v
21. [21]
  Zhu, J.; Yu, H.; Jiang, W. Macromolecules 2005, 38, 7492. doi: 10.1021/ma0510744 doi: 10.1021/ma0510744
22. [22]
  Anand, M., You, S.; Hurst K. M.; Saunders, S. R.; Kitchens, C. L.; Ashurst, W. R.; Roberts, C. B. Ind. Eng. Chem. Res. 2008, 47, 553. doi: 10.1021/ie070981p doi: 10.1021/ie070981p
23. [23]
  Dehghani, F.; Foster, N. R. Cur. Opin. Solid State Mater. Sci. 2003, 7, 363. doi: 10.1016/j.cossms.2003.11.001 doi: 10.1016/j.cossms.2003.11.001
24. [24]
  Cheng, X.; Huang, S.; Li, H.; An, N.; Wang, Q.; Li, Y. RSC Adv. 2016, 6, 4545. doi: 10.1039/c5ra25725e doi: 10.1039/c5ra25725e
25. [25]
  Liu, Y.; Wei, Y.; Qin, R.; Zhang, L.; Yang, L.; Li, H.; Li, X. eXPRESS Polym. Lett. 2011, 5, 60. doi: 10.3144/expresspolymlett.2011.7 doi: 10.3144/expresspolymlett.2011.7
26. [26]
  Su, M.; Wei, Y.; Qi, L.; Pang, Y.; Guo, Y.; Li, P.; Li, J.; Li, H. eXPRESS Polym. Lett. 2011, 5, 1102. doi: 10.3144/expresspolymlett.2011.107 doi: 10.3144/expresspolymlett.2011.107
27. [27]
  Xue, W.; Qi, L.; Li, X.; Huang, S.; Li, H.; Guan, X.; Bai, G.; Liu, L. E. Chem. Eng. J. 2012, 209, 118. doi: 10.1016/j.cej.2012.08.022 doi: 10.1016/j.cej.2012.08.022
28. [28]
  Cheng, X.; Zheng, X.; Zhang, Y.; Li, Y.; Li, H.; Cao, R.; Li, Q. RSC Adv. 2016, 6, 77796. doi: 10.1039/c6ra15855b doi: 10.1039/c6ra15855b
29. [29]
  Chiefari, J.; Chong, Y. K.; Ercole, F.; Krstina, J.; Jeffery, J.; Le, T. P. T.; Mayadunne, R. T. A.; Meijs, G. F.; Moad, C. L.; Moad, G.; et al. Macromolecules 1998, 31, 5559. doi: 10.1021/ma9804951 doi: 10.1021/ma9804951
30. [30]
  Antonietti, M.; Foster, S. Adv. Mater. 2003, 15, 1323. doi: 10.1002/adma.200300010 doi: 10.1002/adma.200300010
31. [31]
  Izzo, D.; Marques, C. M.Macromolecules 1997, 30, 6544. doi: 10.1021/ma970264e doi: 10.1021/ma970264e
1. [1]
  Yuanpeng Ye , Longfei Yao , Guofeng Liu . Engineering circularly polarized luminescence through symmetry manipulation in achiral tetraphenylpyrazine structures. Chinese Journal of Structural Chemistry, 2025, 44(2): 100460-100460. doi: 10.1016/j.cjsc.2024.100460
2. [2]
  Sifan Du , Yuan Wang , Fulin Wang , Tianyu Wang , Li Zhang , Minghua Liu . Evolution of hollow nanosphere to microtube in the self-assembly of chiral dansyl derivatives and inversed circularly polarized luminescence. Chinese Chemical Letters, 2024, 35(7): 109256-. doi: 10.1016/j.cclet.2023.109256
3. [3]
  Yuwen Zhu , Xiang Deng , Yan Wu , Baode Shen , Lingyu Hang , Yuye Xue , Hailong Yuan . Formation mechanism of herpetrione self-assembled nanoparticles based on pH-driven method. Chinese Chemical Letters, 2025, 36(1): 109733-. doi: 10.1016/j.cclet.2024.109733
4. [4]
  Jiayi Guo , Liangxiong Ling , Qinwei Lu , Yi Zhou , Xubiao Luo , Yanbo Zhou . Degradation of chloroxylenol by CoS_x activated peroxomonosulfate: Role of cobalt-sulfur ratio. Chinese Chemical Letters, 2025, 36(4): 110380-. doi: 10.1016/j.cclet.2024.110380
5. [5]
  Jingqi Xin , Shupeng Han , Meichen Zheng , Chenfeng Xu , Zhongxi Huang , Bin Wang , Changmin Yu , Feifei An , Yu Ren . A nitroreductase-responsive nanoprobe with homogeneous composition and high loading for preoperative non-invasive tumor imaging and intraoperative guidance. Chinese Chemical Letters, 2024, 35(7): 109165-. doi: 10.1016/j.cclet.2023.109165
6. [6]
  Keyang Li , Yanan Wang , Yatao Xu , Guohua Shi , Sixian Wei , Xue Zhang , Baomei Zhang , Qiang Jia , Huanhua Xu , Liangmin Yu , Jun Wu , Zhiyu He . Flash nanocomplexation (FNC): A new microvolume mixing method for nanomedicine formulation. Chinese Chemical Letters, 2024, 35(10): 109511-. doi: 10.1016/j.cclet.2024.109511
7. [7]
  Xuanyu Wang , Zhao Gao , Wei Tian . Supramolecular confinement effect enabling light-harvesting system for photocatalytic α-oxyamination reaction. Chinese Chemical Letters, 2024, 35(11): 109757-. doi: 10.1016/j.cclet.2024.109757
8. [8]
  Xian Yan , Huawei Xie , Gao Wu , Fang-Xing Xiao . Boosted solar water oxidation steered by atomically precise alloy nanocluster. Chinese Chemical Letters, 2025, 36(1): 110279-. doi: 10.1016/j.cclet.2024.110279
9. [9]
  Feng Cao , Chunxiang Xian , Tianqi Yang , Yue Zhang , Haifeng Chen , Xinping He , Xukun Qian , Shenghui Shen , Yang Xia , Wenkui Zhang , Xinhui Xia . Gelation-pyrolysis strategy for fabrication of advanced carbon/sulfur cathodes for lithium-sulfur batteries. Chinese Chemical Letters, 2025, 36(3): 110575-. doi: 10.1016/j.cclet.2024.110575
10. [10]
  Fengying Ye , Ming Hu , Jun Luo , Wei Yu , Zhirong Xu , Jinjin Fu , Yansong Zheng . Significantly boosting circularly polarized luminescence by synergy of helical and planar chirality. Chinese Chemical Letters, 2025, 36(5): 110724-. doi: 10.1016/j.cclet.2024.110724
11. [11]
  Yi Zhou , Wei Zhang , Rong Fu , Jiaxin Dong , Yuxuan Liu , Zihang Song , Han Han , Kang Cai . Self-assembly of two pairs of homochiral M₂L₄ coordination capsules with varied confined space using Tröger's base ligands. Chinese Chemical Letters, 2025, 36(2): 109865-. doi: 10.1016/j.cclet.2024.109865
12. [12]
  Bing Niu , Honggao Huang , Liwei Luo , Li Zhang , Jianbo Tan . Coating colloidal particles with a well-defined polymer layer by surface-initiated photoinduced polymerization-induced self-assembly and the subsequent seeded polymerization. Chinese Chemical Letters, 2025, 36(2): 110431-. doi: 10.1016/j.cclet.2024.110431
13. [13]
  Xiaofei NIU , Ke WANG , Fengyan SONG , Shuyan YU . Self-assembly of [Pd₆(L)₄]⁸⁺-type macrocyclic complexes for fluorescent sensing of HSO₃^-. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1233-1242. doi: 10.11862/CJIC.20240057
14. [14]
  Zhongjie Li , Xiangyue Kong , Yuhao Liu , Huayu Qiu , Lingling Zhan , Shouchun Yin . Progress of additives for morphology control in organic photovoltaics. Chinese Chemical Letters, 2024, 35(6): 109378-. doi: 10.1016/j.cclet.2023.109378
15. [15]
  Zhenzhu Wang , Chenglong Liu , Yunpeng Ge , Wencan Li , Chenyang Zhang , Bing Yang , Shizhong Mao , Zeyuan Dong . Differentiated self-assembly through orthogonal noncovalent interactions towards the synthesis of two-dimensional woven supramolecular polymers. Chinese Chemical Letters, 2024, 35(5): 109127-. doi: 10.1016/j.cclet.2023.109127
16. [16]
  Cheng-Yan Wu , Yi-Nan Gao , Zi-Han Zhang , Rui Liu , Quan Tang , Zhong-Lin Lu . Enhancing self-assembly efficiency of macrocyclic compound into nanotubes by introducing double peptide linkages. Chinese Chemical Letters, 2024, 35(11): 109649-. doi: 10.1016/j.cclet.2024.109649
17. [17]
  Changlin Su , Wensheng Cai , Xueguang Shao . Water as a probe for the temperature-induced self-assembly transition of an amphiphilic copolymer. Chinese Chemical Letters, 2025, 36(4): 110095-. doi: 10.1016/j.cclet.2024.110095
18. [18]
  Zengchao Guo , Weiwei Liu , Tengfei Liu , Jinpeng Wang , Hui Jiang , Xiaohui Liu , Yossi Weizmann , Xuemei Wang . Engineered exosome hybrid copper nanoscale antibiotics facilitate simultaneous self-assembly imaging and elimination of intracellular multidrug-resistant superbugs. Chinese Chemical Letters, 2024, 35(7): 109060-. doi: 10.1016/j.cclet.2023.109060
19. [19]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
20. [20]
  Ruoxi Sun , Yiqian Xu , Shaoru Rong , Chunmiao Han , Hui Xu . The Enchanting Collision of Light and Time Magic: Exploring the Footprints of Long Afterglow Lifetime. University Chemistry, 2024, 39(5): 90-97. doi: 10.3866/PKU.DXHX202310001

Get Citation

PDF

XML

Metrics

PDF Downloads(6)
Abstract views(256)
HTML views(14)

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

Self-Assembly Behavior of Amphiphilic Diblock Copolymer PS-b-P4VP in CO2-Expanded Liquids

Metrics

通讯作者: 陈斌, bchen63@163.com

Self-Assembly Behavior of Amphiphilic Diblock Copolymer PS-b-P4VP in CO₂-Expanded Liquids