Green Fabrication of High-strength Silk Fibroin Hydrogels <italic style="font-style: italic">via</italic> Thermal Oscillation in All-aqueous Media

Yu-Si Long; Mei-Yi Lu; Jia-Wei Qi; Geng Chen; Yu Sun; Xiu-Xia He; Tian-Hui Zhang; Li-Guo Cui; Jun-Li Hu; Yi-Chun Liu

doi:10.1007/s10118-026-3645-2

Your Location：

Home >

Browse articles >

Green Fabrication of High-strength Silk Fibroin Hydrogels via Thermal Oscillation in All-aqueous Media

RESEARCH ARTICLE | Updated：2026-07-27

- Green Fabrication of High-strength Silk Fibroin Hydrogels via Thermal Oscillation in All-aqueous Media
- Chinese Journal of Polymer Science Vol. 44, Issue 8, Pages: 2549-2560(2026)
- Affiliations：
  
  a.State Key Laboratory of Integrated Optoelectronics, Key Laboratory of UV Light-Emitting Materials and Technology of Ministry of Education, School of Physics, Northeast Normal University, Changchun 130024, China
  b.School of Life Science and Technology, Changchun University of Science and Technology, Changchun 130013, China
  c.Changchun SinoBiomaterials Co., Ltd., Changchun 130103, China
- Author bio：
  
  hujl100@nenu.edu.cn
- Funds：
- DOI：10.1007/s10118-026-3645-2
  CLC：
- Received：18 December 2025，
  
  Revised：2026-03-05，
  
  Accepted：11 March 2026，
  
  Online First：02 July 2026，
  
  Published：15 August 2026
- Accepted：
Scan QR Code
Long, Y. S.; Lu, M. Y.; Qi, J. W.; Chen, G.; Sun, Y.; He, X. X.; Zhang, T. H.; Cui, L. G.; Hu, J. L.; Liu, Y. C. Green fabrication of high-strength silk fibroin hydrogels via thermal oscillation in all-aqueous media. Chinese J. Polym. Sci. 2026, 44, 2549–2560

Yu-Si Long, Mei-Yi Lu, Jia-Wei Qi, et al. Green Fabrication of High-strength Silk Fibroin Hydrogels via Thermal Oscillation in All-aqueous Media[J]. Chinese Journal of Polymer Science, 2026, 44(8): 2549-2560. DOI: 10.1007/s10118-026-3645-2.
Long, Y. S.; Lu, M. Y.; Qi, J. W.; Chen, G.; Sun, Y.; He, X. X.; Zhang, T. H.; Cui, L. G.; Hu, J. L.; Liu, Y. C. Green fabrication of high-strength silk fibroin hydrogels via thermal oscillation in all-aqueous media. Chinese J. Polym. Sci. 2026, 44, 2549–2560 DOI： 10.1007/s10118-026-3645-2.

Yu-Si Long, Mei-Yi Lu, Jia-Wei Qi, et al. Green Fabrication of High-strength Silk Fibroin Hydrogels via Thermal Oscillation in All-aqueous Media[J]. Chinese Journal of Polymer Science, 2026, 44(8): 2549-2560. DOI: 10.1007/s10118-026-3645-2. DOI：

摘要

A thermal oscillation strategy was developed for the fabrication of high-strength silk fibroin hydrogels exclusively from all-aqueous silk fibroin solutions

eliminating the need for toxic chemicals or non-degradable materials.

Abstract

Silk fibroin hydrogels frequently exhibit insufficient mechanical strength for biomedical applications. Conventional enhancement strategies often rely on toxic crosslinkers or nondegradable components

thereby compromising biocompatibility and biodegradability. Recently emerged organic solvent-based methods represent an advance

but their associated environmental toxicity remains a concern. In this work

we present a novel thermal oscillation strategy for fabricating high-strength silk fibroin hydrogels exclusively from all-aqueous silk fibroin solutions

eliminating the need for toxic chemicals or non-degradable materials. The resulting hydrogels exhibit outstanding mechanical properties

tensile strength of 2.6 MPa

elongation rate of 152.6%

and toughness of 3.0 MJ/m

which not only surpass the organic solvent-derived silk fibroin hydrogels but also rival the dual-crosslinked

double-networked or composite systems. The silk fibroin hydrogels also exhibit a minimal swelling ratio

outstanding long-term integrity

and excellent biocompatibility. The robust

biocomp

atible

and biodegradable silk fibroin hydrogels are promising for biomedical applications such as load-bearing tissue scaffolds

long-term implantable drug delivery systems

and durable wound dressings.

关键词

Keywords

references

Reizabal, A.; Costa, C. M.; Perez-Alvarez, L.; Vilas-Vilela, J. L.; Lanceros-Mendez, S. Silk fibroin as sustainable advanced material: material properties and characteristics, processing, and applications. Adv. Funct. Mater. 2023 , 33 , 2210764..

Huang, W.; Ling, S.; Li, C.; Omenetto, F. G.; Kaplan, D. L. Silkworm silk-based materials and devices generated using bio-nanotechnology. Chem. Soc. Rev. 2018 , 47 , 6486−6504..

Zheng, H.; Zuo, B. Functional silk fibroin hydrogels: preparation, properties and applications. J. Mater. Chem. B 2021 , 9 , 1238−1258..

Zhao, Y.; Zhu, Z. S.; Guan, J.; Wu, S. J. Processing, mechanical properties and bio-applications of silk fibroin-based high-strength hydrogels. Acta Biomater. 2021 , 125 , 57−71..

Correa, S.; Grosskopf, A. K.; Hernandez, H. L.; Chan, D.; Yu, A. C.; Stapleton, L. M.; Appel, E. A. Translational applications of hydrogels. Chem. Rev. 2021 , 121 , 11385−11457..

Wang, X.; Kluge, J. A.; Leisk, G. G.; Kaplan, D. L. Sonication-induced gelation of silk fibroin for cell encapsulation. Biomaterials 2008 , 29 , 1054−1064..

Yuan, T.; Li, Z.; Zhang, Y.; Shen, K.; Zhang, X.; Xie, R.; Liu, F.; Fan, W. Injectable ultrasonication-induced silk fibroin hydrogel for cartilage repair and regeneration. Tissue Eng., Part A 2021 , 27 , 1213−1224..

Yucel, T.; Cebe, P.; Kaplan, D. L. Vortex-Induced injectable silk fibroin hydrogels. Biophys. J. 2009 , 97 , 2044−2050..

Numata, K.; Katashima, T.; Sakai, T. State of water, molecular structure, and cytotoxicity of silk hydrogels. Biomacromolecules 2011 , 12 , 2137−2144..

Costa, A. M. S.; Mano, J. F. Extremely strong and tough hydrogels as prospective candidates for tissue repair - a review. Eur. Polym. J. 2015 , 72 , 344−364..

Fu, Y.; Lin, Q.; Lan, R.; Shao, Z. Ultra-Strong protein-based hydrogels via promoting intermolecular entanglement of the amorphous region. Small 2024 , 20 , 2403376..

Gong, D.; Lin, Q.; Shao, Z.; Chen, X.; Yang, Y. Preparing 3D-printable silk fibroin hydrogels with robustness by a two-step crosslinking method. RSC Adv. 2020 , 10 , 27225−27234..

Wang, K.; Ma, Q.; Zhang, Y.-M.; Han, G.-T.; Qu, C.-X.; Wang, S.-D. Preparation of bacterial cellulose/silk fibroin double-network hydrogel with high mechanical strength and biocompatibility for artificial cartilage. Cellulose 2020 , 27 , 1845−1852..

Chen, F.; Lu, S.; Zhu, L.; Tang, Z.; Wang, Q.; Qin, G.; Yang, J.; Sun, G.; Zhang, Q.; Chen, Q. Conductive regenerated silk-fibroin-based hydrogels with integrated high mechanical performances. J. Mater. Chem. B 2019 , 7 , 1708−1715..

Luo, K.; Yang, Y.; Shao, Z. Physically crosslinked biocompatible silk-fibroin-based hydrogels with high mechanical performance. Adv. Funct. Mater. 2016 , 26 , 872−880..

Balu, R.; Reeder, S.; Knott, R.; Mata, J.; de Campo, L.; Dutta, N. K.; Choudhury, N. R. Tough photocrosslin ked silk fibroin/graphene oxide nanocomposite hydrogels. Langmuir 2018 , 34 , 9238−9251..

Dorishetty, P.; Balu, R.; Athukoralalage, S. S.; Greaves, T. L.; Mata, J.; de Campo, L.; Saha, N.; Zannettino, A. C. W.; Dutta, N. K.; Choudhury, N. R. Tunable biomimetic hydrogels from silk fibroin and nanocellulose. ACS Sustainable Chem. Eng. 2020 , 8 , 2375−2389..

Zhu, Z.; Ling, S.; Yeo, J.; Zhao, S.; Tozzi, L.; Buehler, M. J.; Omenetto, F.; Li, C.; Kaplan, D. L. High-Strength, durable all-silk fibroin hydrogels with versatile processability toward multifunctional applications. Adv. Funct. Mater. 2018 , 28 , 1704757..

Chen, L.; Sun, L.; Yao, J.; Zhao, B.; Shao, Z.; Chen, X. Robust silk protein hydrogels made by a facile one-step method and their multiple applications. ACS Appl. Bio Mater. 2022 , 5 , 3086−3094..

Hu, X.; Kaplan, D; Cebe, P. Determining beta-sheet crystallinity in fibrous proteins by thermal analysis and infrared spectroscopy. Macromolecules 2006 , 39 , 6161−6170..

Wang, H. ; Zhang, Y. P.; Shao, H. L.; Hu, X. C. A study on the flow stability of regenerated silk fibroin aqueous solution. Int. J. Biol. Macromol. 2005 , 36 , 66−70..

Matsumoto, A.; Chen, J.; Collette, A. L.; Kim, U. J.; Altman, G. H.; Cebe, P.; Kaplan, D. L. Mechanisms of silk fibroin sol-gel transitions. J. Phys. Chem. B 2006 , 110 , 21630−21638..

Li, X. G.; Wu, L. Y.; Huang, M. R.; Shao, H. L.; Hu, X. C. Conformational transition and liquid crystalline state of regenerated silk fibroin in water. Biopolymers 2008 , 89 , 497−505..

Kim, U. J.; Park, J. Y.; Li, C. M.; Jin, H. J.; Valluzzi, R.; Kaplan, D. L. Structureand properties of silk hydrogels. Biomacromolecules 2004 , 5 , 786−792..

Yan, S.; Zhao, C.; Wu, X.; Zhang, Q.; Li, M. Gelation behavior of Antheraea Pernyi silk fibroin. Sci. China Chem. 2010 , 53 , 535−541..

Yarger, J. L.; Cherry, B. R.; van der Vaart A. Uncovering the structure–function relationship in spider silk. Nat. Rev. Mater. 2018 , 3 , 18008..

Ye, C.; Zhang, H.; Yang, Y.; Shan, Y.; Fu, J.; Gao, W.; Ren, J.; Cao, L.; Ling, S. Sustainable silk fibroin ionic touch screens for flexible biodegradable electronics with integrated AI and IoT functionality. Adv. Mater. 2025 , 37 , 2412972..

Li, Z.; Dong, W.; Ren, J.; Gao, W.; Cao, L.; Gu, Y.; Ling, S. Mechanically trained calcium alginate ionic hydrogels for enhanced abdominal wall defect repair. Adv. Funct. Mater. 2025 , 35 , 2419151..

Zhang, F.; Lu, Q.; Ming, J.; Dou, H.; Liu, Z.; Zuo, B.; Qin, M.; Li, F.; Kaplan, D. L.; Zhang, X. Silk dissolution and regeneration at the nanofibril scale. J. Mater. Chem. B 2014 , 2 , 3879−3885..

Su, D.; Yao, M.; Liu, J.; Zhong, Y.; Chen, X.; Shao, Z. Enhancing mechanical properties of silk fibroin hydrogel through restricting the growth of β -sheet domains. ACS Appl. Mater. Interfaces 2017 , 9 , 17490−17499..

Sui, Z.; King, W. J.; Murphy, W. L. Protein-based hydrogels with tunable dynamic responses. Adv. Funct. Mater. 2008 , 18 , 1824−1831..

Li, K.; Zhao, J.; Zhang, J.; Ji, J.; Ma, Y.; Liu, X.; Xu, H. Direct in vivo functionalizing silkworm fibroin via molecular recognition. ACS Biomater. Sci. Eng. 2015 , 1 , 494−503..

Ling, S.; Qi, Z.; Knight, D. P.; Shao, Z.; Chen, X. Synchrotron FTIR microspectroscopy of single natural silk fibers. Biomacromolecules 2011 , 12 , 3344−3349..

Boulet-Audet, M.; Vollrath, F.; Holland, C. Identification and classification of silks using infrared spectroscopy. J. Exp. Biol. 2015 , 218 , 3138−3149..

Wang, X.; Partlow, B.; Liu, J.; Zheng, Z.; Su, B.; Wang, Y.; Kaplan, D. L. Injectable silk-polyethylene glycol hydrogels. Acta Biomater. 2015 , 12 , 51−61..

Cai, B.; Gu, H.; Wang, F.; Printon, K.; Gu, Z.; Hu, X. Ultrasound regulated flexible protein materials: Fabrication, structure and physical-biological properties. Ultrason. Sonochem. 2021 , 79 , 105800..

Nara, S.; Komiya, T. Studies on the Relationship between water-satured state and crystallinity by the diffraction method for moistened potato starch. Starch - Stärke 1983 , 35 , 407−410..

Guerette, P. A.; Hoon, S.; Ding, D.; Amini, S.; Masic, A.; Ravi, V.; Venkatesh, B.; Weaver, J. C.; Miserez, A. Nanoconfined β -sheets mechanically reinforce the supra-biomolecular network of robust squid sucker ring teeth. ACS Nano 2014 , 8 , 7170−7179..

Whittaker, J. L.; Balu, R.; Knott, R.; de Campo, L.; Mata, J. P.; Rehm, C.; Hill, A. J.; Dutta, N. K.; Choudhury, N. R. Structural evolution of photocrosslinked silk fibroin and silk fibroin-based hybrid hydrogels: A small angle and ultra-small angle scattering investigation. Int. J. Biol. Macromol. 2018 , 114 , 998−1007..

McDowall, D.; Adams, D. J.;Seddon, A. M. Using small angle scattering to understand low molecular weight gels. Soft Matter 2022 , 18 , 1577..

Mitropoulos, A. N.; Burpo, F. J.; Nguyen, C. K.; Nagelli, E. A.; Ryu, M. Y.; Wang, J.; Sims, R. K.; Woronowicz, K.; Wickiser, J. K. Noble metal composite porous silk fibroin aerogel fibers. Materials 2019 , 12 , 894..

Ling, S.; Qin, Z.; Li, C.; Huang, W.; Kaplan, D. L.; Buehler, M. J. Polymorphic regenerated silk fibers assembled through bioinspired spinning. Nat. Commun. 2017 , 8 , 1387..

Zhang, F.; You, X.; Dou, H.; Liu, Z.; Zuo, B.; Zhang, X. Facile fabrication of robust silk nanofibril films via direct dissolution of silk in CaCl 2 -formic acid solution. ACS Appl. Mater. Interfaces 2015 , 7 , 3352−3361..

Yan, S.; Han, G.; Wang, Q.; Zhang, S.; You, R.; Luo, Z.; Xu, A.; Li, X.; Li, M.; Zhang, Q.; Kaplan, D. L. Directed assembly of robust and biocompatible silk fibroin/hyaluronic acid composite hydrogels. Composites, Part B 2019 , 176 , 107204..

Richbourg, N. R.; Peppas, N. A. The swollen polymer network hypothesis: quantitative models of hydrogel swelling, stiffness, and solute transport. Prog. Polym. Sci. 2020 , 105 , 101243..

Views

111

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Polyoxometalate-doped Chitosan Quaternary Ammonium/Polyacrylamide Interpenetrating Hydrogels with Enhanced Mechanical and Tribological Properties

Direct Ink Writing 3D Printing of Hydrogel Bioelectronics

Anti-biofouling Hydrogels: Surface Hydration, Classification, and Biomedical Applications

Interface-engineered Ionically Conductive Polyoxometalate-based Hydrogels with High Stretchability and Notch-insensitivity for Wearable Sensors

One-handed Helical Poly(m-terphenyl acetylene)s with Broad Optical Activity Range from Ultraviolet-Visible to Near-infrared Regions

Related Author

Fang Xu

Xin-Bao Han

Hao-Hao Ren

Wei-Tao Gong

Rong-Sheng Cai

Yu Li

Ming Zhang

Wen-Bo Sheng

Related Institution

Shandong Laboratory of Advanced Materials and Green Manufacturing at Yantai

School of Stomatology, Lanzhou University

College of Chemistry and Chemical Engineering, Lanzhou University

State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences

Department of Mechanical and Energy Engineering, Southern University of Science and Technology

⁰

Green Fabrication of High-strength Silk Fibroin Hydrogels via Thermal Oscillation in All-aqueous Media

DOI：10.1007/s10118-026-3645-2

摘要

Abstract

关键词

Keywords

references