Citation: Wen Tang, Kan Yue, Stephen Z. D. Cheng. Molecular Topology Effects in Self-assembly of Giant Surfactants[J]. Acta Polymerica Sinica, ;2018, 0(8): 959-972. doi: 10.11777/j.issn1000-3304.2018.18102 shu

Molecular Topology Effects in Self-assembly of Giant Surfactants

South China Advanced Institute for Soft Matter Science and Technology, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640

Corresponding author: Kan Yue, kanyue@scut.edu.cn Stephen Z. D. Cheng, scheng@scut.edu.cn
Received Date: 9 April 2018
Revised Date: 22 May 2018

Self-assembly of block copolymers, which are composed of covalently connected incompatible polymer chains, can result in various ordered structures at the nanometer scale. This phenomenon, widely known as the microphase separation of block copolymers, may provide a technological platform for the development of next-generation nanopatterning techniques based on the " top-down” strategy. During the past decade, a unique class of novel amphiphilic macromolecules termed as giant surfactants have been reported, which are constructed from selected building blocks of cluster-like molecules having three-dimensional rigid conformations and nanometer sizes. By combining different " click-type” reactions, a highly efficient and modular synthetic method has been developed to prepare covalent conjugates of these molecular clusters and polymer chains. The resulting giant surfactants can be viewed as structural analogues of common block copolymers, and similarly, they also display interesting self-assembly behaviors both in solutions and in bulk. Herein, recent advances on the study of self-assembly of giant surfactants are summarized, with a particular emphasis on the molecular topology effects that can significantly change their self-assembly behaviors. As revealed by small angle X-ray scattering and transmission electron microscopy techniques, giant surfactants were able to self-assemble in bulk to form a series of highly ordered nanostructures with feature sizes below 10 nm or even 5 nm, with clearly shifted phase boundaries. More importantly, through rational molecular design to tune the molecular topology of giant surfactants, formation of some unusual nanostructures driven by molecular topological variations was achieved. Typical examples include several unconventional spherical phases, such as the Frank-Kasper A15 phase, the Frank-Kasper σ phase, and a quasicrystalline spherical phase, which were observed in multitailed giant surfactants, and a highly asymmetric lamellar phase formed by self-assembly of multiheaded giant surfactants. It is believed that these studies provide not only insights towards understanding the molecular topological effects in macromolecular self-assembly, but also experimental foundation for the development of block copolymer lithography that can afford nanostructures with sub-10-nm feature sizes.
- Microphase separation,
- Giant surfactants,
- Block copolymers,
- Molecular topology,
- Self-assembly
1. [1]
  Cheng S Z D. J Polym Sci, Part B: Polym Phys, 2005, 43: 3361-3364 doi: 10.1002/(ISSN)1099-0488
2. [2]
  Bates C M, Maher M J, Janes D W, Ellison C J, Willson C G. Macromolecules, 2014, 47: 2-12 doi: 10.1021/ma401762n
3. [3]
  Bates F S, Fredrickson G H. Phys Today, 1999, 52: 32-38
4. [4]
  Bates F S, Fredrickson G H. Annu Rev Phys Chem, 1990, 41: 525-557 doi: 10.1146/annurev.pc.41.100190.002521
5. [5]
  Zhang L, Eisenberg A. Science, 1995, 268: 1728-1731 doi: 10.1126/science.268.5218.1728
6. [6]
  Sinturel C, Bates F S, Hillmyer M A. ACS Macro Lett, 2015, 4: 1044-1050 doi: 10.1021/acsmacrolett.5b00472
7. [7]
  Zhang W B, Yu X, Wang C L, Sun H J, Hsieh I F, Li Y, Dong X H, Yue K, Van Horn R, Cheng S Z D. Macromolecules, 2014, 47: 1221-1239 doi: 10.1021/ma401724p
8. [8]
  Yin G Z, Zhang W B, Cheng S Z D. Sci China Chem, 2017, 60: 338-352 doi: 10.1007/s11426-016-0436-x
9. [9]
10. [10]
  Yu X F, Zhong S, Li X P, Tu Y F, Yang S G, Van Horn R M, Ni C Y, Pochan D J, Quirk R P, Wesdemiotis C, Zhang W B, Cheng S Z D. J Am Chem Soc, 2010, 132: 16741-16744 doi: 10.1021/ja1078305
11. [11]
  Yu X, Zhang W B, Yue K, Li X, Liu H, Xin Y, Wang C L, Wesdemiotis C, Cheng S Z D. J Am Chem Soc, 2012, 134: 7780-7787 doi: 10.1021/ja3000529
12. [12]
  Yu X, Li Y, Dong X H, Yue K, Lin Z, Feng X, Huang M, Zhang W B, Cheng S Z D. J Polym Sci, Part B: Polym Phys, 2014, 52: 1309-1325 doi: 10.1002/polb.v52.20
13. [13]
  Yu X, Yue K, Hsieh I F, Li Y, Dong X H, Liu C, Xin Y, Wang H F, Shi A C, Newkome G R, Ho R M, Chen E Q, Zhang W B, Cheng S Z D. Proc Natl Acad Sci, 2013, 110: 10078-10083 doi: 10.1073/pnas.1302606110
14. [14]
  Yue K, Liu C, Huang M, Huang J, Zhou Z, Wu K, Liu H, Lin Z, Shi A C, Zhang W B, Cheng S Z D. Macromolecules, 2017, 50: 303-314 doi: 10.1021/acs.macromol.6b02446
15. [15]
  Yue K, He J, Liu C, Huang M, Dong X H, Guo K, Ni P, Wesdemiotis C, Quirk R, Cheng S D, Zhang W B. Chinese J Polym Sci, 2013, 31: 71-82 doi: 10.1007/s10118-013-1215-x
16. [16]
  Yue K, Liu C, Guo K, Wu K, Dong X H, Liu H, Huang M, Wesdemiotis C, Cheng S Z D, Zhang W B. Polym Chem, 2013, 4: 1056-1067 doi: 10.1039/C2PY20881D
17. [17]
  Yue K, Huang M, Marson R L, He J, Huang J, Zhou Z, Wang J, Liu C, Yan X, Wu K, Guo Z, Liu H, Zhang W, Ni P, Wesdemiotis C, Zhang W B, Glotzer S C, Cheng S Z D. Proc Natl Acad Sci, 2016, 113: 14195-14200 doi: 10.1073/pnas.1609422113
18. [18]
  Huang M, Yue K, Huang J, Liu C, Zhou Z, Wang J, Wu K, Shan W, Shi A C, Cheng S Z D. ACS Nano, 2018, 12: 1868-1877 doi: 10.1021/acsnano.7b08687
19. [19]
  Li Y, Dong X H, Guo K, Wang Z, Chen Z, Wesdemiotis C, Quirk R P, Zhang W B, Cheng S Z D. ACS Macro Lett, 2012, 1: 834-839 doi: 10.1021/mz300196x
20. [20]
  He J, Yue K, Liu Y, Yu X, Ni P, Cavicchi K A, Quirk R P, Chen E Q, Cheng S Z D, Zhang W B. Polym Chem, 2012, 3: 2112-2120 doi: 10.1039/c2py20101a
21. [21]
  Yue K, Liu C, Guo K, Yu X, Huang M, Li Y, Wesdemiotis C, Cheng S Z D, Zhang W B. Macromolecules, 2012, 45: 8126-8134 doi: 10.1021/ma3013256
22. [22]
  Li Y, Dong X H, Zou Y, Wang Z, Yue K, Huang M, Liu H, Feng X, Lin Z, Zhang W, Zhang W B, Cheng S Z D. Polymer, 2017, 125: 303-329 doi: 10.1016/j.polymer.2017.08.008
23. [23]
  Su H, Li Y, Yue K, Wang Z, Lu P, Feng X, Dong X H, Zhang S, Cheng S Z D, Zhang W B. Polym Chem, 2014, 5: 3697-3706 doi: 10.1039/c4py00107a
24. [24]
  Li Y, Su H, Feng X, Yue K, Wang Z, Lin Z, Zhu X, Fu Q, Zhang Z, Cheng S Z D, Zhang W B. Polym Chem, 2015, 6: 827-837 doi: 10.1039/C4PY01360C
25. [25]
  Su H, Zheng J, Wang Z, Lin F, Feng X, Dong X H, Becker M L, Cheng S Z D, Zhang W B, Li Y. ACS Macro Lett, 2013, 2: 645-650 doi: 10.1021/mz4002723
26. [26]
  Wang X M, Guo Q Y, Han S Y, Wang J Y, Han D, Fu Q, Zhang W B. Chem Eur J, 2015, 21: 15246-15255 doi: 10.1002/chem.v21.43
27. [27]
  Han S Y, Wang X M, Shao Y, Guo Q Y, Li Y, Zhang W B. Chem Eur J, 2016, 22: 6397-6403 doi: 10.1002/chem.v22.18
28. [28]
  Wang X M, Shao Y, Xu J, Jin X, Shen R H, Jin P F, Shen D W, Wang J, Li W, He J, Ni P, Zhang W B. Macromolecules, 2017, 50: 3943-3953 doi: 10.1021/acs.macromol.7b00503
29. [29]
  Wang X M, Shao Y, Jin P F, Jiang W, Hu W, Yang S, Li W, He J, Ni P, Zhang W B. Macromolecules, 2018, 51: 1110-1119 doi: 10.1021/acs.macromol.7b02383
30. [30]
  Zhang W B, Tu Y, Ranjan R, Van Horn R M, Leng S, Wang J, Polce M J, Wesdemiotis C, Quirk R P, Newkome G R, Cheng S Z D. Macromolecules, 2008, 41: 515-517 doi: 10.1021/ma702345r
31. [31]
  Lin Z, Lu P, Hsu C H, Sun J, Zhou Y, Huang M, Yue K, Ni B, Dong X H, Li X, Zhang W B, Yu X, Cheng S Z D. Macromolecules, 2015, 48: 5496-5503 doi: 10.1021/acs.macromol.5b00741
32. [32]
  Dong X H, Ni B, Huang M, Hsu C H, Chen Z, Lin Z, Zhang W B, Shi A C, Cheng S Z D. Macromolecules, 2015, 48: 7172-7179 doi: 10.1021/acs.macromol.5b01661
33. [33]
  Dong X H, Ni B, Huang M, Hsu C H, Bai R, Zhang W B, Shi A C, Cheng S Z D. Angew Chem Int Ed, 2016, 55: 2459-2463 doi: 10.1002/anie.201510524
34. [34]
  Huang M, Yue K, Wang J, Hsu C H, Wang L, Cheng S Z D. Sci China Chem, 2018, 61: 33-45
35. [35]
  Shao Y, Yin H, Wang X M, Han S Y, Yan X, Xu J, He J, Ni P, Zhang W B. Polym Chem, 2016, 7: 2381-2388 doi: 10.1039/C6PY00241B
36. [36]
  Huang M, Hsu C H, Wang J, Mei S, Dong X, Li Y, Li M, Liu H, Zhang W, Aida T, Zhang W B, Yue K, Cheng S Z D. Science, 2015, 348: 424-428 doi: 10.1126/science.aaa2421
37. [37]
  Lin Z, Yang X, Xu H, Sakurai T, Matsuda W, Seki S, Zhou Y, Sun J, Wu K Y, Yan X Y, Zhang R, Huang M, Mao J, Wesdemiotis C, Aida T, Zhang W, Cheng S Z D. J Am Chem Soc, 2017, 139: 18616-18622 doi: 10.1021/jacs.7b10193
38. [38]
  Feng X, Zhang R, Li Y, Hong Y L, Guo D, Lang K, Wu K Y, Huang M, Mao J, Wesdemiotis C, Nishiyama Y, Zhang W, Zhang W, Miyoshi T, Li T, Cheng S Z D. ACS Cent Sci, 2017, 3: 860-867 doi: 10.1021/acscentsci.7b00188
39. [39]
  Ren L J, Wu H, Hu M B, Wei Y H, Lin Y, Wang W. Chem Asian J, 2018, DOI: 10.1002/asia.201800005 doi: 10.1002/asia.201800005
40. [40]
  Ma C, Wu H, Huang Z H, Guo R H, Hu M B, Kübel C, Yan L T, Wang W. Angew Chem Int Ed, 2015, 54: 15699-15704 doi: 10.1002/anie.201507237
41. [41]
  Hou X S, Zhu G L, Ren L J, Huang Z H, Zhang R B, Ungar G, Yan L T, Wang W. J Am Chem Soc, 2018, 140: 1805-1811 doi: 10.1021/jacs.7b11324
42. [42]
  Liu H, Hsu C H, Lin Z, Shan W, Wang J, Jiang J, Huang M, Lotz B, Yu X, Zhang W B, Yue K, Cheng S Z D. J Am Chem Soc, 2014, 136: 10691-10699 doi: 10.1021/ja504497h
43. [43]
  Liu H, Luo J, Shan W, Guo D, Wang J, Hsu C H, Huang M, Zhang W, Lotz B, Zhang W B, Liu T, Yue K, Cheng S Z D. ACS Nano, 2016, 10: 6585-6596 doi: 10.1021/acsnano.6b01336
44. [44]
  Zhang W, Lu X, Mao J, Hsu C H, Mu G, Huang M, Guo Q, Liu H, Wesdemiotis C, Li T, Zhang W B, Li Y, Cheng S Z D. Angew Chem Int Ed, 2017, 56: 15014-15019 doi: 10.1002/anie.201709354
45. [45]
  Materials Genome Initiative for Global Competitiveness. Washington, D C: National Science and Technology Council, 2011 (https://www.mgi.gov/sites/default/files/documents/materials_genome_initiative-final.pdf, accessed on May 20^th, 2018).
1. [1]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
2. [2]
  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
3. [3]
  Kun JIANG , Yutong XUE , Kelin LIU , Miao WANG , Tongming SUN , Yanfeng TANG . CeVO₄ hollow microspheres: Fabrication and adsorption performance for dyes. Chinese Journal of Inorganic Chemistry, 2025, 41(11): 2229-2236. doi: 10.11862/CJIC.20250223
4. [4]
  Yukai Jiang , Yihan Wang , Yunkai Zhang , Yunping Wei , Ying Ma , Na Du . Characterization and Phase Diagram of Surfactant Lyotropic Liquid Crystal. University Chemistry, 2024, 39(4): 114-118. doi: 10.3866/PKU.DXHX202309033
5. [5]
  Congying Lu , Fei Zhong , Zhenyu Yuan , Shuaibing Li , Jiayao Li , Jiewen Liu , Xianyang Hu , Liqun Sun , Rui Li , Meijuan Hu . Experimental Improvement of Surfactant Interface Chemistry: An Integrated Design for the Fusion of Experiment and Simulation. University Chemistry, 2024, 39(3): 283-293. doi: 10.3866/PKU.DXHX202308097
6. [6]
  Renjie Xue , Chao Ma , Jing He , Xuechao Li , Yanning Tang , Lifeng Chi , Haiming Zhang . Catassembly in the Host-Guest Recognition of 2D Metastable Self-Assembled Networks. Acta Physico-Chimica Sinica, 2024, 40(9): 2309011-0. doi: 10.3866/PKU.WHXB202309011
7. [7]
  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
8. [8]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
9. [9]
  Wenjian Zhang , Mengxin Fan , Wenwen Fei , Wei Bai . Cultivation of Critical Thinking Ability: Based on RAFT Polymerization-Induced Self-Assembly. University Chemistry, 2025, 40(4): 108-112. doi: 10.12461/PKU.DXHX202406099
10. [10]
  Hongling Yuan , Jialin Xie , Jiawei Wang , Jixiang Zhao , Jiayan Liu , Qing Feng , Wei Qi , Min Liu . Cyclic Olefin Copolymer (COC): The Agile Vanguard in the Realm of Materials. University Chemistry, 2024, 39(7): 294-298. doi: 10.12461/PKU.DXHX202311041
11. [11]
  Lin LI , Jiaxue LI , Meixia YANG , Jiayu DING , Jiaqi JING , Ruiping ZHANG . Preparation of mitoxantrone self-assembled carrier-free nanodrugs regulated by sodium acetate for apoptosis induction of human breast carcinoma cells. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2536-2548. doi: 10.11862/CJIC.20250138
12. [12]
  Wen-Bing Hu . Systematic Introduction of Polymer Chain Structures. University Chemistry, 2025, 40(4): 15-19. doi: 10.3866/PKU.DXHX202401014
13. [13]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
14. [14]
  Changjun You , Chunchun Wang , Mingjie Cai , Yanping Liu , Baikang Zhu , Shijie Li . Improved Photo-Carrier Transfer by an Internal Electric Field in BiOBr/N-rich C₃N₅ 3D/2D S-Scheme Heterojunction for Efficiently Photocatalytic Micropollutant Removal. Acta Physico-Chimica Sinica, 2024, 40(11): 2407014-0. doi: 10.3866/PKU.WHXB202407014
15. [15]
  Wenyan Dan , Weijie Li , Xiaogang Wang . The Technical Analysis of Visual Software ShelXle for Refinement of Small Molecular Crystal Structure. University Chemistry, 2024, 39(3): 63-69. doi: 10.3866/PKU.DXHX202302060
16. [16]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 100034-0. doi: 10.3866/PKU.WHXB202406012
17. [17]
  Wen Tang , Luyu Sui , Qian Chen , Jun Shao , Xinwen Peng , Jianwen Jiang , Shuiliang Chen . Project-based Teaching of “the Condensed State of Polymers”: Unveiling the Lithium-Ion Battery Separator. University Chemistry, 2025, 40(11): 115-126. doi: 10.12461/PKU.DXHX202412108
18. [18]
  Yuan Chun , Yongmei Liu , Fuping Tian , Hong Yuan , Shu'e Song , Wanchun Zhu , Yunchao Li , Zhongyun Wu , Xiaokui Wang , Yunshan Bai , Li Wang , Jianrong Zhang , Shuyong Zhang . Suggestions on Operating Specifications of Physical Chemistry Experiment: Measurement of Colloidal and Surface Chemical Properties, Molecular Structure and Properties. University Chemistry, 2025, 40(5): 178-188. doi: 10.12461/PKU.DXHX202503053
19. [19]
  Yue Zhang , Bao Li , Lixin Wu . GO-Assisted Supramolecular Framework Membrane for High-Performance Separation of Nanosized Oil-in-Water Emulsions. Acta Physico-Chimica Sinica, 2024, 40(5): 2305038-0. doi: 10.3866/PKU.WHXB202305038
20. [20]
  Xue Wu , Yupeng Liu , Bingzhe Wang , Lingyun Li , Zhenjian Li , Qingcheng Wang , Quansheng Cheng , Guichuan Xing , Songnan Qu . Rationally assembling different surface functionalized carbon dots for enhanced near-infrared tumor photothermal therapy. Acta Physico-Chimica Sinica, 2025, 41(9): 100109-0. doi: 10.1016/j.actphy.2025.100109

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(190)
HTML views(7)

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