Abstract
Silk fibroin (SF), as a special natural polymer, is a good candidate for preparing flexible sensor due to its excellent biocompatibility, biodegradability and amphiphilic properties. However, the high and uncontrollable crystallization of SF makes it challenge to be utilized in excellent biomimetic SF hydrogel sensor. Neat SF hydrogel is brittle and not adhesive. Here, polyacrylamide (PAM) was introduced to the SF hydrogel to address this issue. Due to their strong intermolecular interaction, the network morphology of SF/PAM hydrogel was altered to non-Euclidean pore from Euclidean one. Meanwhile, its β-sheet crystallization was suppressed to nanoscale readily. These evolutions endow the SF/PAM hydrogel with not only enhanced mechanical properties but also excellent adhesion performance. Compared with that of neat PAM hydrogel, tensile strength, tensile failure strain, compressive strength (under 80% strain) and adhesion performance (on pig skin) of the SF8/PAM hydrogel are increased by 133.1%, 120.9%, 610.8% and 104.8%, respectively. Additionally, the amphiphilicity of SF could make the carbon nanotubes (CNTs) disperse well in hydrogel. CNT0.3/SF8/PAM hydrogel not only inherits but also improves the above properties. It exhibits excellent adhesive sensing performance with maximal gauge factor of 10.13, working strain range of 1000% and stability as long as over 500 cycles. The detection of six human activities was also demonstrated. This work affords a general strategy to achieve high-performance SF-based hydrogel and indicates that the SF/PAM hydrogel possesses great promise for applications in flexible wearable strain sensors.
摘要
素蛋白(SF)作为一种特殊的天然聚合物, 具有优异的生物相容 性、生物降解性和双亲性, 是制备柔性传感器的良好候选者. 然而, 丝 素蛋白的高结晶度和结晶不可控性使获得这种出色的仿生水凝胶传感 器具有挑战性. 纯SF水凝胶是脆性的, 没有黏性. 在此, 我们通过引入聚 丙烯酰胺(PAM)到SF水凝胶中来解决这一问题. 由于SF/PAM水凝胶具 有较强的分子间相互作用, 其网络形貌由欧几里得孔改变为非欧几里 得孔. 同时, 其β片结晶很容易被抑制到纳米尺度. 这些演变不仅使SF/PAM水凝胶具有优异的机械性能, 而且具有出色的黏附性能. 与纯 PAM水凝胶相比, SF8/PAM水凝胶的拉伸强度、拉伸破坏应变、抗压 强度(80%应变下)和黏附性能(在猪皮上)分别提高了133.1%、120.9%、 610.8%和104.8%. 此外, SF的双亲性可以使碳纳米管(CNTs)在水凝胶中 分散良好. 制备的CNT0.3/SF8/PAM水凝胶继承并进一步改善了上述性 能. 除此之外, 它还表现出优异的自黏附传感性能, 最大灵敏度因子高 达10.13, 工作应变范围超过1000%, 大应变下稳定循环拉伸达500次以 上. 同时, 六种人类活动的精确检测也得到了验证. 本工作为实现高性 能SF基水凝胶提供了新策略, 并证实SF/PAM水凝胶在柔性可穿戴应变 传感器中具有广阔的应用前景.
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References
Meng K, Xiao X, Wei W, et al. Wearable pressure sensors for pulse wave monitoring. Adv Mater, 2022, 34: 2109357
Guo Y, Li H, Li Y, et al. Wearable hybrid device capable of interactive perception with pressure sensing and visualization. Adv Funct Mater, 2022, 32: 2203585
Niu H, Li H, Gao S, et al. Perception-to-cognition tactile sensing based on artificial-intelligence-motivated human full-skin bionic electronic skin. Adv Mater, 2022, 34: 2202622
Ge G, Lu Y, Qu X, et al. Muscle-inspired self-healing hydrogels for strain and temperature sensor. ACS Nano, 2020, 14: 218–228
Zhu T, Ni Y, Biesold GM, et al. Recent advances in conductive hydrogels: Classifications, properties, and applications. Chem Soc Rev, 2023, 52: 473–509
Wu F, Lin X, Xu Y, et al. Light-driven locomotive soft actuator and multi-functional sensors based on asymmetric PVA/carbon/PE bilayer film. Sci China Mater, 2023, 66: 4782–4793
Wang L, Chen Z, Yan Y, et al. Fabrication of injectable hydrogels from silk fibroin and angiogenic peptides for vascular growth and tissue regeneration. Chem Eng J, 2021, 418: 129308
Shi C, Hu F, Wu R, et al. New silk road: From mesoscopic reconstruction/functionalization to flexible meso-electronics/photonics based on cocoon silk materials. Adv Mater, 2021, 33: 2005910
Zhang Y, Sheng R, Chen J, et al. Silk fibroin and sericin differentially potentiate the paracrine and regenerative functions of stem cells through multiomics analysis. Adv Mater, 2023, 35: 2210517
Shen J, Du P, Zhou B, et al. An anti-freezing biomineral hydrogel of high strain sensitivity for artificial skin applications. Nano Res, 2022, 15: 6655–6661
Zhu J, Tao J, Yan W, et al. Pathways toward wearable and high-performance sensors based on hydrogels: Toughening networks and conductive networks. Natl Sci Rev, 2023, 10: nwad180
Wu S, Wang B, Chen D, et al. Highly sensitive and self-healing conductive hydrogels fabricated from cationic cellulose nanofiber-dispersed liquid metal for strain sensors. Sci China Mater, 2023, 66: 1923–1933
Qin Z, Sun X, Yu Q, et al. Carbon nanotubes/hydrophobically associated hydrogels as ultrastretchable, highly sensitive, stable strain, and pressure sensors. ACS Appl Mater Interfaces, 2020, 12: 4944–4953
Tropp J, Collins CP, Xie X, et al. Conducting polymer nanoparticles with intrinsic aqueous dispersibility for conductive hydrogels. Adv Mater, 2024, 36: 2306691
Ye Y, Jiang F. Highly stretchable, durable, and transient conductive hydrogel for multi-functional sensor and signal transmission applications. Nano Energy, 2022, 99: 107374
Wang Q, Ling S, Liang X, et al. Self-healable multifunctional electronic tattoos based on silk and graphene. Adv Funct Mater, 2019, 29: 1808695
Wang C, Xia K, Zhang Y, et al. Silk-based advanced materials for soft electronics. Acc Chem Res, 2019, 52: 2916–2927
Liang X, Li H, Dou J, et al. Stable and biocompatible carbon nanotube ink mediated by silk protein for printed electronics. Adv Mater, 2020, 32: 2000165
Yang S, Zhao C, Yang Y, et al. The fractal network structure of silk fibroin molecules and its effect on spinning of silkworm silk. ACS Nano, 2023, 17: 7662–7673
Zhao W, Gan D, Qu X, et al. Bioinspired wet-resistant organogel for highly sensitive mechanical perception. Sci China Mater, 2022, 65: 2262–2273
Tavsanli B, Okay O. Mechanically robust and stretchable silk/hyaluronic acid hydrogels. Carbohydrate Polyms, 2019, 208: 413–420
Cao L, Ye C, Zhang H, et al. An artificial motion and tactile receptor constructed by hyperelastic double physically cross-linked silk fibroin ionoelastomer. Adv Funct Mater, 2023, 33: 2301404
Hasturk O, Jordan KE, Choi J, et al. Enzymatically crosslinked silk and silk-gelatin hydrogels with tunable gelation kinetics, mechanical properties and bioactivity for cell culture and encapsulation. Biomaterials, 2020, 232: 119720
Sahoo JK, Hasturk O, Falcucci T, et al. Silk chemistry and biomedical material designs. Nat Rev Chem, 2023, 7: 302–318
Chang H, Meng L, Shao C, et al. Physically cross-linked silk hydrogels with high solid content and excellent mechanical properties via a reverse dialysis concentrated procedure. ACS Sustain Chem Eng, 2019, 7: 13324–13332
Zhu Z, Ling S, Yeo J, et al. High-strength, durable all-silk fibroin hydrogels with versatile processability toward multifunctional applications. Adv Funct Mater, 2018, 28: 1704757
Li G, Li C, Li G, et al. Development of conductive hydrogels for fabricating flexible strain sensors. Small, 2022, 18: 2101518
Wang W, Liu Y, Wang S, et al. Physically cross-linked silk fibroin-based tough hydrogel electrolyte with exceptional water retention and freezing tolerance. ACS Appl Mater Interfaces, 2020, 12: 25353–25362
Wang J, Zhang N, Tan Y, et al. Sweat-resistant silk fibroin-based double network hydrogel adhesives. ACS Appl Mater Interfaces, 2022, 14: 21945–21953
Lu T, Chen Q. Independent gradient model based on Hirshfeld partition: A new method for visual study of interactions in chemical systems. J Comput Chem, 2022, 43: 539–555
Ming X, Sheng Y, Yao L, et al. Anti-swelling conductive polyampholyte hydrogels via ionic complexations for underwater motion sensors and dynamic information storage. Chem Eng J, 2023, 463: 142439
Kadumudi FB, Hasany M, Pierchala MK, et al. The manufacture of unbreakable bionics via multifunctional and self-healing silk-graphene hydrogels. Adv Mater, 2021, 33: 2100047
Yan S, Wang Q, Tariq Z, et al. Facile preparation of bioactive silk fibroin/hyaluronic acid hydrogels. Int J Biol Macromolecules, 2018, 118: 775–782
Han S, Tan H, Wei J, et al. Surface modification of super arborized silica for flexible and wearable ultrafast-response strain sensors with low hysteresis. Adv Sci, 2023, 10: 2301713
Su D, Yao M, Liu J, et al. Enhancing mechanical properties of silk fibroin hydrogel through restricting the growth of β-sheet domains. ACS Appl Mater Interfaces, 2017, 9: 17489–17498
Wang S, Yu L, Wang S, et al. Strong, tough, ionic conductive, and freezing-tolerant all-natural hydrogel enabled by cellulose-bentonite coordination interactions. Nat Commun, 2022, 13: 3408
Zheng H, Chen M, Sun Y, et al. Self-healing, wet-adhesion silk fibroin conductive hydrogel as a wearable strain sensor for underwater applications. Chem Eng J, 2022, 446: 136931
Lei B, Cao L, Qu X, et al. Thermal-sensitive ionogel with NIR-light controlled adhesion for ultrasoft strain sensor. Nano Res, 2023, 16: 5464–5472
Zhang R, Liu C, Wei C, et al. Thermoplastic charge-transfer hydrogels for highly sensitive strain and temperature sensors. J Mater Chem A, 2023, 11: 8320–8329
Wang Q, Ding H, Hu X, et al. A dual-trigger-mode ionic hydrogel sensor for contact or contactless motion recognition. Mater Horiz, 2020, 7: 2673–2682
Amjadi M, Kyung K, Park I, et al. Stretchable, skin-mountable, and wearable strain sensors and their potential applications: A review. Adv Funct Mater, 2016, 26: 1678–1698
Li Y, Yang D, Wu Z, et al. Self-adhesive, self-healing, biocompatible and conductive polyacrylamide nanocomposite hydrogels for reliable strain and pressure sensors. Nano Energy, 2023, 109: 108324
Liu Y, Xia M, Zhou Y, et al. Rational design of bioinspired gradient conductivity and stiffness for tactile sensors with high sensitivity and large linear range. Compos Sci Tech, 2022, 228: 109674
Acknowledgements
This work was supported by the National Key R&D Program of China (2019YFA0706802), Shenzhen Science and Technology Program (CJGJZD20210408092602006), and the Science and Technology Major Project of Henan Province (221100240400).
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Author contributions Yang D and Sun C conducted the experiments. Han Z, Yuan B, Chen J, and Pan D conducted the theoretical simulations and some experiments. Yang D, supervised by Xu H, Liu C, and Shen C, wrote and revised the manuscript. All authors contributed to the data analysis, discussed the results, and commented on the manuscript.
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Supplementary information Experimental details and supporting data are available in the online version of the paper.
Dezhen Yang is currently a graduate student of Zhengzhou University, China. He received his Bachelor’s degree in engineering from Chongqing University of Business and Technology, China in 2021. His current research interests focus on flexible strain hydrogel sensors.
Huajie Xu is currently an associate professor of Zhengzhou University, China. He received his doctor’s degree in engineering from the Northwestern Polytechnical University, China in 2015. His current research interests focus on composites, polymers and hydrogels.
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Intermolecular interaction simultaneously mediated network morphology and β-sheet crystallization of silk fibroin/polyacrylamide hydrogel for its excellent adhesive strain sensing performances
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Yang, D., Sun, C., Han, Z. et al. Intermolecular interaction simultaneously mediated network morphology and β-sheet crystallization of silk fibroin/polyacrylamide hydrogel for its excellent adhesive strain sensing performances. Sci. China Mater. 67, 1533–1542 (2024). https://doi.org/10.1007/s40843-023-2849-6
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DOI: https://doi.org/10.1007/s40843-023-2849-6