石墨烯诱导水凝胶成核的高强韧人造蛛丝

引用本文: 何文倩, 邸亚, 姜南, 刘遵峰, 陈永胜. 石墨烯诱导水凝胶成核的高强韧人造蛛丝[J]. 物理化学学报, 2022, 38(9): 220405. doi: 10.3866/PKU.WHXB202204059 shu

Citation: Wenqian He, Ya Di, Nan Jiang, Zunfeng Liu, Yongsheng Chen. Graphene-Oxide Seeds Nucleate Strong and Tough Hydrogel-Based Artificial Spider Silk[J]. Acta Physico-Chimica Sinica, 2022, 38(9): 220405. doi: 10.3866/PKU.WHXB202204059 shu

石墨烯诱导水凝胶成核的高强韧人造蛛丝

何文倩 ^1, ,
邸亚 ^2, ,
姜南 ^2, ,
刘遵峰 ^{1,
,} ,
陈永胜 ^{1,
,}

1.
南开大学药物化学生物学国家重点实验室, 高分子所, 化学学院, 天津 300071
2.
航宇救生装备有限公司武汉创新中心, 武汉 430000

通讯作者: 刘遵峰, liuzunfeng@nankai.edu.cn; 陈永胜, yschen99@nankai.edu.cn

基金项目:
国家自然科学基金 52090034

国家自然科学基金 51973093

国家自然科学基金 51773094

国家重点研发项目 2019YFE0119600

南开大学新有机质前沿科学中心 63181206

摘要: 天然蜘蛛丝是由β-sheet交联的蛛丝蛋白溶剂流入S-型导管后经牵引拉伸形成，它显示了高强度与高韧性的完美结合。其优异的力学性质主要源于它的多级结构：交联、线性排列的纳米组装体以及核壳结构。受此启发，我们合成了一种交联的水凝胶，通过牵引拉丝的方法，制备了交联的、含有取向排列的纳米组装体结构以及核壳结构的凝胶纤维，并通过少量引入二维纳米材料—氧化石墨烯(0.01%)，进一步调控纳米组装体的取向和尺寸，实现了蜘蛛丝般优异的力学性能(断裂强度560 MPa，断裂韧性200 MJ·m⁻³，缓冲能94%)。这种纤维可以用于高速下落物体的能量耗散和降低冲击力。

关键词:

English

Graphene-Oxide Seeds Nucleate Strong and Tough Hydrogel-Based Artificial Spider Silk

Wenqian He ^1, ,
Ya Di ^2, ,
Nan Jiang ^2, ,
Zunfeng Liu ^{1,
,} ,
Yongsheng Chen ^{1,
,}

1.
State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Functional Polymer Materials, College of Chemistry, Nankai University, Tianjin 300071, China
2.
Innovation Center of Hangyu Lifesaving Equipment, Wuhan 430000, China

Corresponding author: Email: liuzunfeng@nankai.edu.cn (Z.L.); yschen99@nankai.edu.cn (Y.C.)

Received Date: 30 April 2022
Accepted Date: 15 June 2022
Revised Date: 13 June 2022
Available Online: 15 September 2022
Fund Project:
the National Natural Science Foundation of China

the National Natural Science Foundation of China

the National Natural Science Foundation of China

the National Key Research and Development Program of China

Frontiers Science Center for New Organic Matter, Nankai University

Abstract: Natural spider silk is composed of spun spidroin protein containing beta-sheet crosslinking sites drawn from an S-shaped spinning duct. It exhibits an excellent combination of strength (1150 ± 200 MPa) and toughness (165 ± 30 MJ·m⁻³) that originates from its hierarchical structure, including crosslinking sites, highly aligned nano-aggregates, and a sheath-core structure. In this work, we prepared a hydrogel fiber that contains crosslinking sites, highly aligned nano-aggregates, and a sheath-core structure, by draw-spinning a bulk hydrogel composed of polyacrylic acid crosslinked with vinyl-functionalized silica nanoparticles (SNVs). The core-sheath structure was prepared by the water-evaporation-controlled self-assembly of the polyacrylic hydrogel, while nanometer-sized aggregates were formed by the self-assembly of polyacrylic acid chains. The addition of a tiny amount of graphene oxide (GO: 0.01%), a 2D nanomaterial, enhanced the mechanical properties of the fiber (breaking strength: 560 MPa; fracture toughness: 200 MJ·m⁻³; damping capacity: 94%). In addition, we investigated the factors responsible for the mechanical properties of the gel fibers, including fiber diameter, drying time in air, relative air humidity, and stretching speed. A higher breaking strength and a lower fracture strain was obtained by decreasing the fiber diameter, increasing the drying time, or increasing the stretching speed, while a lower fracture strain and higher breaking strength were obtained by increasing the relative air humidity. Polarized optical and SEM images revealed that the GO-seeded material is better aligned and contains smaller nano-aggregates, with GO seeding found to play a key role in the formation of nano-aggregates and polymer-chain alignment. The prepared fiber exhibited excellent mechanical properties compared to gel fibers prepared by other methods (e.g., electro-, wet, dry, and microfluidic spinning, as well as templating, and 3D printing, etc.). Repeated mechanical testing involving stretch-release cycles to 70% strain at 20% relative humidity revealed that the fibers have an energy-damping capacity of 93.6%, which exceeds that of natural spider silk and many types of artificial fiber. The relaxed stretched fiber recovered its initial length when exposed to 80% relative humidity, while the fiber recovered its initial mechanical properties when stored for 2 h at room temperature. A yarn composed of three hundred of the prepared gel fibers was shown to lift a 3 kg object without breaking; the prepared fiber was also shown to absorb dynamic energy and lower the impact force of a falling object.

Key words:

1. [1]
  Ling, S.; Qin, Z.; Li, C.; Huang, W.; Kaplan, D. L.; Buehler, M. J. Nat. Commun. 2017, 8, 1. doi: 10.1038/s41467-017-00613-5
2. [2]
  Omenetto, F. G.; Kaplan, D. L. Science 2010, 329, 528. doi: 10.1126/science.1188936
3. [3]
  Vollrath, F.; Knight, D. P. Nature 2001, 410, 541. doi: 10.1038/35069000
4. [4]
  Rising, A.; Johansson, J. Nat. Chem. Biol. 2015, 11, 309. doi: 10.1038/nchembio.1789
5. [5]
  Yarger, J. L.; Cherry, B. R.; Van Der Vaart, A. Nat. Rev. Mater. 2018, 3, 1. doi: 10.1038/natrevmats.2018.8
6. [6]
  Yoshioka, T.; Tsubota, T.; Tashiro, K.; Jouraku, A.; Kameda, T. Nat. Commun. 2019, 10, 1. doi: 10.1038/s41467-019-09350-3
7. [7]
  Du, N.; Yang, Z.; Liu, X. Y.; Li, Y.; Xu, H. Y. Adv. Funct. Mater. 2011, 21, 772. doi: 10.1002/adfm.201001397
8. [8]
  Eisoldt, L.; Smith, A.; Scheibel, T. Mater. Today 2011, 14, 80. doi: 10.1016/S1369-7021(11)70057-8
9. [9]
  Lefèvre, T.; Auger, M. Int. Mater. Rev. 2016, 61, 127. doi: 10.1080/09506608.2016.1148894
10. [10]
  Lin, T.-Y.; Masunaga, H.; Sato, R.; Malay, A. D.; Toyooka, K.; Hikima, T.; Numata, K. Biomacromolecules 2017, 18, 1350. doi: 10.1021/acs.biomac.7b00086
11. [11]
  Yazawa, K.; Malay, A. D.; Masunaga, H.; Numata, K. Macromol. Bioscience 2019, 19, 1800220. doi: 10.1002/mabi.201800220
12. [12]
  Gao, H.-L.; Zhao, R.; Cui, C.; Zhu, Y.-B.; Chen, S.-M.; Pan, Z.; Meng, Y.-F.; Wen, S.-M.; Liu, C.; Wu, H.-A. Natl. Sci. Rev. 2020, 7, 73. doi: 10.1093/nsr/nwz077
13. [13]
  Mittal, N.; Jansson, R.; Widhe, M.; Benselfelt, T.; Håkansson, K. M.; Lundell, F.; Hedhammar, M.; Söderberg, L. D. ACS Nano 2017, 11, 5148. doi: 10.1021/acsnano.7b02305
14. [14]
  Mohammadi, P.; Aranko, A. S.; Landowski, C. P.; Ikkala, O.; Jaudzems, K.; Wagermaier, W.; Linder, M. B. Sci. Adv. 2019, 5, eaaw2541. doi: 10.1126/sciadv.aaw2541
15. [15]
  Yu, Y.; He, Y.; Mu, Z.; Zhao, Y.; Kong, K.; Liu, Z.; Tang, R. Adv. Funct. Mater. 2020, 30, 1908556. doi: 10.1002/adfm.201908556
16. [16]
  Dou, Y.; Wang, Z.-P.; He, W.; Jia, T.; Liu, Z.; Sun, P.; Wen, K.; Gao, E.; Zhou, X.; Hu, X. Nat. Commun. 2019, 10, 1. doi: 10.1038/s41467-019-09234-6
17. [17]
  Wu, Y.; Shah, D. U.; Liu, C.; Yu, Z.; Liu, J.; Ren, X.; Rowland, M. J.; Abell, C.; Ramage, M. H.; Scherman, O. A. Proc. Nat. Acad. Sci. U. S. A. 2017, 114, 8163. doi: 10.1073/pnas.1705380114
18. [18]
  Deptula, A.; Wade, M.; Rogers, S. A.; Espinosa‐Marzal, R. M. Adv. Funct. Mater. 2022, 32, 2111414. doi: 10.1002/adfm.202111414
19. [19]
  Heidebrecht, A.; Eisoldt, L.; Diehl, J.; Schmidt, A.; Geffers, M.; Lang, G.; Scheibel, T. Adv. Mater. 2015, 27, 2189. doi: 10.1002/adma.201404234
20. [20]
  Li, J.; Zhu, Y.; Yu, H.; Dai, B.; Jun, Y.-S.; Zhang, F. ACS Nano 2021, 15, 11843. doi: 10.1021/acsnano.1c02944
21. [21]
  Li, Y.; Li, J.; Sun, J.; He, H.; Li, B.; Ma, C.; Liu, K.; Zhang, H. Angew. Chem. Int. Ed. 2020, 132, 8225. doi: 10.1002/anie.202102158
22. [22]
  Kabir, M. H.; Ahmed, K.; Gong, J.; Furukawa, H. The Effect of Cross-Linker Concentration in the Physical Properties of Shape Memory Gel. In: Proceedings of SPIE, 2015, 9432, 94320Q. Conference on Behavior and Mechanics of Multifunctional Materials and Composites, San Diego, CA, MAR 09–11, 2015. doi: 10.1117/12.2084181
23. [23]
  Andersson, M.; Jia, Q.; Abella, A.; Lee, X.-Y.; Landreh, M.; Purhonen, P.; Hebert, H.; Tenje, M.; Robinson, C. V.; Meng, Q. Nat. Chem. Biol. 2017, 13, 262. doi: 10.1038/NCHEMBIO.2269
24. [24]
  Wei, P.; Hou, K.; Chen, T.; Chen, G.; Mugaanire, I. T.; Zhu, M. Mater. Horiz. 2020, 7, 811. doi: 10.1039/C9MH01390C
25. [25]
  Jin, Y.; Zhang, Y.; Hang, Y.; Shao, H.; Hu, X. J. Mater. Res. 2013, 28, 2897. doi: 10.1557/jmr.2013.276
26. [26]
  Sun, M.; Zhang, Y.; Zhao, Y.; Shao, H.; Hu, X. J. Mater. Chem. 2012, 22, 18372. doi: 10.1039/C2JM32576D
27. [27]
  Yue, X.; Zhang, F.; Wu, H.; Ming, J.; Fan, Z.; Zuo, B. Mater. Lett. 2014, 128, 175. doi: 10.1016/j.matlet.2014.04.116
28. [28]
  Liao, X.; Dulle, M.; e Silva, J. M. d. S.; Wehrspohn, R. B.; Agarwal, S.; Förster, S.; Hou, H.; Smith, P.; Greiner, A. Science 2019, 366, 1376. doi: 10.1126/science.aay903
29. [29]
  Xue, J.; Wu, T.; Dai, Y.; Xia, Y. Chem. Rev. 2019, 119, 5298. doi: 10.1021/acs.chemrev.8b00593
30. [30]
  Kang, E.; Choi, Y. Y.; Chae, S. K.; Moon, J. H.; Chang, J. Y.; Lee, S. H. Adv. Mater. 2012, 24, 4271. doi: 10.1002/adma.201201232
31. [31]
  Mittal, N.; Benselfelt, T.; Ansari, F.; Gordeyeva, K.; Roth, S. V.; Wågberg, L.; Söderberg, L. D. Angew. Chem. Int. Ed. 2019, 131, 18735. doi: 10.1002/ange.201910603
32. [32]
  Tamayol, A.; Akbari, M.; Zilberman, Y.; Comotto, M.; Lesha, E.; Serex, L.; Bagherifard, S.; Chen, Y.; Fu, G.; Ameri, S. K. Adv. Healthc. Mater. 2016, 5, 711. doi: 10.1002/adhm.201670027
33. [33]
  Huang, H. M.; Li, Z.; Wang, C. Solid State Phenomena 2007, 121, 579. doi: 10.4028/www.scientific.net/SSP.121-123.579
34. [34]
  Lu, H.; Zhang, L.; Xing, W.; Wang, H.; Xu, N. Macromol. Chem. Phys. 2005, 94, 322. doi: 10.1039/C9TA14082D
35. [35]
  Hou, K.; Hu, Z.; Mugaanire, I. T.; Li, C.; Chen, G.; Zhu, M. Polymer 2019, 183, 121903. doi: 10.1016/j.polymer.2019.121903
36. [36]
  Hou, K.; Wang, H.; Lin, Y.; Chen, S.; Yang, S.; Cheng, Y.; Hsiao, B. S.; Zhu, M. Macromol. Rapid Commun. 2016, 37, 1795. doi: 10.1002/marc.201600430
37. [37]
  Song, J.; Chen, S.; Sun, L.; Guo, Y.; Zhang, L.; Wang, S.; Xuan, H.; Guan, Q.; You, Z. Adv. Mater. 2020, 32, 1906994. doi: 10.1002/adma.201906994
38. [38]
  Chen, G.; Wang, G.; Tan, X.; Hou, K.; Meng, Q.; Zhao, P.; Wang, S.; Zhang, J.; Zhou, Z.; Chen, T. Natl. Sci. Rev. 2021, 8, nwaa209. doi: 10.1093/nsr/nwaa209
39. [39]
  Duan, X.; Yu, J.; Zhu, Y.; Zheng, Z.; Liao, Q.; Xiao, Y.; Li, Y.; He, Z.; Zhao, Y.; Wang, H. ACS Nano 2020, 14, 14929. doi: 10.1021/acsnano.0c04382
40. [40]
  Ju, M., Wu, B., Sun, S., Wu, P. Adv. Funct. Mater. 2020, 30, 1910387. doi: 10.1002/adfm.201910387
41. [41]
  Wu, L.; Li, L.; Fan, M.; Tang, P.; Yang, S.; Pan, L.; Wang, H.; Bin, Y. Composites Part A: Appl. Sci. Manufacturing 2020, 138, 106050. doi: 10.1016/j.compositesa.2020.106050
42. [42]
  Bettahar, F.; Bekkar, F.; Pérez-Álvarez, L.; Ferahi, M. I.; Meghabar, R., Vilas-Vilela, J. L.; Ruiz-Rubio, L. Polymer 2021, 13, 972. doi: 10.3390/polym13060972
43. [43]
  Yang, Y.; Wang, C.; Wiener, C. G.; Hao, J.; Shatas, S.; Weiss, R., Vogt, B. D. ACS Appl. Mater. Interfaces 2016, 8, 22774. doi: 10.1021/acsami.6b08255
44. [44]
  Chen, T.; Wei, P.; Chen, G.; Liu, H.; Mugaanire, I. T.; Hou, K.; Zhu, M. J. Mater. Chem. A 2021, 9, 12265. doi: 10.1039/d1ta02422a
45. [45]
  An, Y.; Gao, L.; Wang, T. ACS Appl. Nano Mater. 2020, 3, 5079. doi: 10.1021/acsanm.0c00351
46. [46]
  Chu, C. K.; Joseph, A. J.; Limjoco, M. D.; Yang, J.; Bose, S.; Thapa, L. S.; Langer, R.; Anderson, D. G. J. Am. Chem. Soc. 2020, 142, 19715. doi: 10.1021/jacs.0c09691
47. [47]
  Zhao, X.; Chen, F.; Li, Y.; Lu, H.; Zhang, N.; Ma, M. Nat. Commun. 2018, 9, 1. doi: 10.1038/s41467-018-05904-z
48. [48]
  Naficy, S.; Le, T. Y. L.; Oveissi, F.; Lee, A.; Hung, J. C.; Wise, S. G.; Winlaw, D. S.; Dehghani, F. Adv. Mater. Interfaces 2020, 7, 1901770. doi: 10.1002/admi.201901770
49. [49]
  Peng, L., Liu, Y., Huang, J., Li, J., Gong, J., Ma, J. Eur. Poly. J. 2018, 103, 335. doi: 10.1016/j.eurpolymj.2018.04.019
50. [50]
  Zhou, M.; Gong, J.; Ma, J. e-Polymers 2019, 19, 215. doi: 10.1515/epoly-2019-0022

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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

石墨烯诱导水凝胶成核的高强韧人造蛛丝

通讯作者: 刘遵峰, liuzunfeng@nankai.edu.cn; 陈永胜, yschen99@nankai.edu.cn

English

Graphene-Oxide Seeds Nucleate Strong and Tough Hydrogel-Based Artificial Spider Silk

Corresponding author: Email: liuzunfeng@nankai.edu.cn (Z.L.); yschen99@nankai.edu.cn (Y.C.)

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

石墨烯诱导水凝胶成核的高强韧人造蛛丝

通讯作者: 刘遵峰, liuzunfeng@nankai.edu.cn; 陈永胜, yschen99@nankai.edu.cn

English

Graphene-Oxide Seeds Nucleate Strong and Tough Hydrogel-Based Artificial Spider Silk

Corresponding author: Email: liuzunfeng@nankai.edu.cn (Z.L.); yschen99@nankai.edu.cn (Y.C.)

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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