Direct Ink Writing of Biodegradable Elastic Scaffolds <italic style="font-style: italic">via</italic> Rapid Thiol-Acrylate Photocrosslinking

Xiao-Yu Li; Chong-Guang Li; Kai Chen; Yan Xiao; Xin-Xin Li; Mei-Dong Lang

doi:10.1007/s10118-026-3582-0

Your Location：

Home >

Browse articles >

Direct Ink Writing of Biodegradable Elastic Scaffolds via Rapid Thiol-Acrylate Photocrosslinking

RESEARCH ARTICLE | Updated：2026-04-30

- Direct Ink Writing of Biodegradable Elastic Scaffolds via Rapid Thiol-Acrylate Photocrosslinking
- Chinese Journal of Polymer Science Vol. 44, Issue 5, Pages: 1489-1501(2026)
- Affiliations：
  
  a.Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
  b.Key Laboratory of Specially Functional Polymeric and Related Technology (Ministry of Education), School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
- Author bio：
  
  yxiao@ecust.edu.cn (Y.X.)
  xinxinli@ecust.edu.cn (X.X.L.)
  mdlang@ecust.edu.cn (M.D.L.)
- Funds：
- DOI：10.1007/s10118-026-3582-0
  CLC：
- Received：21 December 2025，
  
  Accepted：20 January 2026，
  
  Online First：07 April 2026，
  
  Published：05 May 2026
- Accepted：
Scan QR Code
Li, X. Y.; Li, C. G.; Chen, K.; Xiao, Y.; Li, X. X.; Lang, M. D. Direct ink writing of biodegradable elastic scaffolds via rapid thiol-acrylate photocrosslinking. Chinese J. Polym. Sci. 2026, 44, 1489–1501

Xiao-Yu Li, Chong-Guang Li, Kai Chen, et al. Direct Ink Writing of Biodegradable Elastic Scaffolds via Rapid Thiol-Acrylate Photocrosslinking[J]. Chinese Journal of Polymer Science, 2026, 44(5): 1489-1501. DOI: 10.1007/s10118-026-3582-0.
Li, X. Y.; Li, C. G.; Chen, K.; Xiao, Y.; Li, X. X.; Lang, M. D. Direct ink writing of biodegradable elastic scaffolds via rapid thiol-acrylate photocrosslinking. Chinese J. Polym. Sci. 2026, 44, 1489–1501 DOI： 10.1007/s10118-026-3582-0.

Xiao-Yu Li, Chong-Guang Li, Kai Chen, et al. Direct Ink Writing of Biodegradable Elastic Scaffolds via Rapid Thiol-Acrylate Photocrosslinking[J]. Chinese Journal of Polymer Science, 2026, 44(5): 1489-1501. DOI: 10.1007/s10118-026-3582-0. DOI：

摘要

The incorporation of thiol-functionalized poly(ethylene glycol) (PEGSH) into acrylate-functionalized liquid poly(4-methyl-

-caprolactone) (PMCLDA) precursor afforded the mixed inks shear thinning behavior. The network structure of scaffolds was regulated by thiol-acrylate photopolymerization.

Abstract

Direct ink writing (DIW) has emerged as one of th

e most promising approaches for biomedical application

owing to its broad material compatibility

ease of operation

and high-resolution. However

the development of DIW inks with suitable rheological properties and excellent biocompatibility remains a significant challenge. Herein

an acrylate-functionalized liquid poly(4-methyl-

-caprolactone) (PMCLDA) was synthesized as the precursor of 3D printing ink

accompanied with thiol-functionalized polyethylene glycol (PEGSH) as a rheological modifier. It was indicated from rheology study that the incorporation of PEGSH with PMCLDA precursor afforded the mixt inks shear thinning behavior. Moreover

it was verified by

in situ

Fourier transform infrared spectroscopy and photo-rheology that the mixed ink could rapidly cure through thiol-acrylate crosslinking under UV light. Various inks formulations were successfully utilized for printing 3D scaffolds

via

UV-assisted DIW

with the optimized printability for SH75 ink. Moreover

the 3D-printed scaffolds exhibited excellent elasticity and degradability.

In vitro

cytocompatibility assessments showed that the scaffolds exhibited good cytocompatibility and supported the proliferation of L929 mouse fibroblasts for a duration of 7 days. Therefore

it is demonstrated that the 3D-printed scaffolds crosslinked

via

thiol-acrylate crosslinking have great potential for applications in tissue engineering.

关键词

Keywords

references

Gillispie, G.; Prim, P.; Copus, J.; Fisher, J.; Mikos, A. G.; Yoo, J. J.; Atala, A.; Lee, S. J. Assessment methodologies for extrusion-based bioink printability. Biofabrication 2020 , 12 , 022003..

Yuan, X.; Zhu, W.; Yang, Z.; He, N.; Chen, F.; Han, X.; Zhou, K. Recent advances in 3D printing of smart scaffolds for bone tissue engineering and regeneration. Adv. Mater. 2024 , 36 , 2403641.

Sadeghianmaryan, A.; Ahmadian, N.; Wheatley, S.; Alizadeh, S. H.; Nasrollah, S. A. S.; Naseri, E.; Ahmadi, A. Advancements in 3D-printable polysaccharides, proteins, and synthetic polymers for wound dressing and skin scaffolding — a review. Int. J. of Biol. Macromol. 2024 , 266 , 131207.

Ligon, S. C.; Liska, R.; Stampfl, J.; Gurr, M.; Mülhaupt, R. Polymers for 3D printing and customized additive manufacturing. Chem. Rev. 2017 , 117 , 10212−10290..

Truby, R. L.; Lewis, J. A. Printing soft matter in three dimensions. Nature 2016 , 540 , 371−378..

Chartrain, N. A.; Williams, C. B.; Whittington, A. R. A Review on fabricating tissue scaffolds using vat photopolymerization. Acta Biomater. 2018 , 74 , 90−111..

[Zhang, M.; Lin, R.; Wang, X.; Xue, J.; Deng, C.; Feng, C.; Zhuang, H.; Ma, J.; Qin, C.; Wan, L.; Chang, J.; Wu, C. 3D Printing of haversian bone-mimicking scaffolds for multicellular delivery in bone regeneration. Sci. Adv . 2020 , 6 , eaaz6725..

[Zhu, S.; Liao, X.; Xu, Y.; Zhou, N.; Pan, Y.; Song, J.; Zheng, T.; Zhang, L.; Bai, L.; Wang, Y.; Zhou, X.; Gou, M.; Tao, J.; Liu, R. 3D Bioprinting of high-performance hydrogel with in-situ birth of stem cell spheroids. Bioact. Mater . 2025 , 43 , 392-405..

[Wang, W.; Zhang, B.; Li, M.; Li, J.; Zhang, C.; Han, Y.; Wang, L.; Wang, K.; Zhou, C.;Liu, L.; Fan, Y.; Zhang, X. 3D Printing of PLA/n-HA Composite scaffolds with customized mechanical properties and biological functions for bone tissue engineering. Compos. Part B Eng . 2021 , 224 , 109192..

[Cano-Vicent, A.; Tambuwala, M. M.; Hassan, S. S.; Barh, D.; Aljabali, A. A. A.; Birkett, M.; Arjunan, A.; Serrano-Aroca, Á. fused deposition modelling: current status, methodology, applications and future prospects. Addit. Manuf . 2021 , 47 , 102378..

Baniasadi, H.; Abidnejad, R.; Fazeli, M.; Lipponen, J.; Niskanen, J.; Kontturi, E.; Seppälä, J.; Rojas, O. J. Innovations in hydrogel-based manufacturing: a comprehensive review of direct ink writing technique for biomedical applications. Adv. Colloid Interface Sci. 2024 , 324 , 103095..

Ajdary, R.; Huan, S.; Zanjanizadeh Ezazi, N.; Xiang, W.; Grande, R.; Santos, H. A.; Rojas, O. J. Acetylated nanocellulose for single-component bioinks and cell proliferation on 3D-printed scaffolds. Biomacromolecules 2019 , 20 , 2770−2778..

Rau, D. A.; Williams, C. B.; Bortner, M. J. Rheology and printability: a survey of critical relationships for direct ink write materials design. Prog. Mater. Sci. 2023 , 140 , 101188..

Zhou, Y.; Wei, G.; Yuan, J.; Sang, X.; Miao, J. T.; Liu, R. UV-assisted direct ink writing 4D printing of benzoxazine/epoxy thermosets. Chem. Eng. J. 2023 , 477 , 147221..

Zhang, B.; Chung, S. H.; Barker, S.; Craig, D.; Narayan, R. J.; Huang, J. Direct ink writing of polycaprolactone/polyethylene oxide based 3D constructs. Prog. Nat. Sci. Mater. Int. 2021 , 31 , 180−191..

Lei, D.; Yang, Y.; Liu, Z.; Chen, S.; Song, B.; Shen, A.; Yang, B.; Li, S.; Yuan, Z.; Qi, Q.; Sun, L.; Guo, Y.; Zuo, H.; Huang, S.; Yang, Q.; Mo, X.; He, C.; Zhu, B.; Jeffries, E. M.; Qing, F.-L.; Ye, X.; Zhao, Q.; You, Z. A general strategy of 3D printing thermosets for diverse applications. Mater. Horiz. 2019 , 6 , 394−404..

Hausladen, M. M.; Gorbea, G. D.; Francis, L. F.; Ellison, C. J. UV-assisted direct ink writing of dual-cure polyurethanes. ACS Appl. Polym. Mater. 2024 , 6 , 2253−2265..

Liu, B.; Duan, T.; Wang, T.; Ren, X.; Gao, G. Direct ink-writable tough polyurethane acrylate elastomers for underwater intelligent monitoring equipment. Chem. Eng. J. 2025 , 509 , 161448..

Li, Y.; Liu, T.; Ambrogi, V.; Rios, O.; Xia, M.; He, W.; Yang, Z. Liquid crystallin e elastomers based on click chemistry. ACS Appl. Mater. Interfaces 2022 , 14 , 14842−14858..

O’Brien, A. K.; Cramer, N. B.; Bowman, C. N. Oxygen inhibition in thiol-acrylate photopolymerizations. J. Polym. Sci. A Polym. Chem. 2006 , 44 , 2007−2014..

Blasco, E.; Wegener, M.; Barner-Kowollik, C. Photochemically driven polymeric network formation: synthesis and applications. Adv. Mater. 2017 , 29 , 1604005..

Xiao, Y.; Lang, S.; Zhou, M.; Qin, J.; Yin, R.; Gao, J.; Heise, A.; Lang, M. A highly stretchable bioelastomer prepared by UV curing of liquid-like poly(4-methyl-epsilon-caprolactone) precursors. J. Mater. Chem. B. 2017 , 5 , 595−603..

[Xiao, Y.; Zhou, M. M.; Zhang, Liu, W.; Zhou, Y.; Lang, M.; Hepatocyte culture on 3D porous scaffolds of PCL/PMCL, Colloids Surf. B Biointerfaces 2019 , 173 , 185-193..

Watts, A.; Kurokawa, N.; Hillmyer, M. A. Strong, resilient, and sustainable aliphatic polyester thermoplastic elastomers. Biomacromolecules 2017 , 18 , 1845−1854..

Cai, X. Y.; Li, J. Z.; Li, N. N.; Chen, J. C.; Kang, E. T.; Xu, L. Q. PEG-based hydrogels prepared by catalyst-free thiol-yne addition and their post-antibacterial modification. Biomater. Sci. 2016 , 4 , 1663−1672..

Panja, S.; Siehr, A.; Sahoo, A.; Siegel, R. A.; Shen, W. Biodegradable elastomers enabling thermoprocessing below 100 °C. Biomacromolecules 2021 , 23 , 163−173..

Huang, W.; Xiao, Y.; Yin, W.; Yang, S.; Lang, M. An engineered cardiac patch based on biodegradable thermoplastic elastomer fabricated by 3D printing and in situ polymerization. Eur. Polym. J. 2024 , 209 , 112890..

Li, X.; Ren, N.; Xiao, Y.; Li, X.; Lang, M.; Zhu, X. Construction and regulation on thiol-acrylate networks through binary polymerization of thiol-ene polymerization and free radical polymerization. Macromolecules 2024 , 57 , 9867−9876..

Thijssen, Q.; Parmentier, L.; Augustyniak, E.; Mouthuy, P. A.; Van Vlierberghe, S. From chain growth to step growth polymerization of photoreactive poly- ε -caprolactone: the network topology of bioresorbable networks as tool in tissue engineering. Adv. Funct. Mater. 2022 , 32 , 2108869..

[Ivanoff, D. G.; Sung, J.; Butikofer, S. M.; Moore, J. S.; Sottos, N. R. Cross-linking agents for enhanced performance of thermosets prepared via frontal ring-opening metathesis polymerization. Macromolecules 2020 , 53 , 8360−8366..

Ding, R.; Xia, Y.; Mauldin, T. C.; Kessler, M. R. Biorenewable ROMP-based thermosetting copolymers from functionalized castor oil derivative with various cross-linking agents. Polymer 2014 , 55 , 5718−5726..

Ouyang, L.; Yao, R.; Zhao, Y.; Sun, W. Effect of bioink properties on printability and cell viability for 3D bioplotting of embryonic stem cells. Biofabrication 2016 , 8 , 035020..

Pielichowski, K.; Flejtuch, K. Differential scanning calorimetry studies on poly(ethylene glycol) with different molecular weights for thermal energy storage materials. Polym. Adv. Technol. 2003 , 13 , 690−696..

Cramer, N. B.; Reddy, S. K.; O’Brien, A. K.; Bowman, C. N. Thiol-ene photopolymerization mechanism and rate limiting step changes for various vinyl functional group chemistries. Macromolecules 2003 , 36 , 7964−7969..

Roquart, M.; Kharlamova, A.; Marcos, C. L.; Norvez, S.; Nicolay, R.; Corte, L. PEG-based photo-cross-linked networks with adjustable topologies and mechanical properties. Biomacromolecules 2023 , 24 , 4454−4464..

Hebner, T. S.; Fowler, H. E.; Herbert, K. M.; Skillin, N. P.; Bowman, C. N.; White, T. J. Polymer network structure, properties, and formation of liquid crystalline elastomers prepared via thiol-acrylate chain transfer reactions. Macromolecules 2021 , 54 , 11074−11082..

Seiffert, S. Origin of Nanostructural inhomogeneity in polymer-network gels. Polym. Chem. 2017 , 8 , 4472−4487..

Zhang, P.; Liu, X.; Guo, P.; Li, X.; He, Z.; Li, Z.; Stoddart, M. J.; Grad, S.; Tian, W.; Chen, D.; Zou, X.; Zhou, Z.; Liu, S. Effect of Cyclic Mechanical loading on immunoinflammatory microenvironment in biofabricating hydroxyapatite scaffold for bone regeneration. Bioact. Mater. 2021 , 6 , 3097−3108..

Rydholm, A. E.; Bowman, C. N.; Anseth, K. S. Degradable Thiol-acrylate photopolymers: polymerization and degradation behavior of an in situ forming biomaterial. Biomaterials 2005 , 26 , 4495−506..

Wang, Z.; Zhang, W.; Bai, G.; Lu, Q.; Li, X.; Zhou, Y.; Yang, C.; Xiao, Y.; Lang, M. Highly resilient and fatigue-resistant poly(4-methyl- ε -caprolactone) porous scaffold fabricated via thiol-yne photo-crosslinking/salt-templating for soft tissue regeneration. Bioact. Mater. 2023 , 28 , 311−325..

Lam, C. X. F.; Teoh, S. H.; Hutmacher, D. W. Comparison of the degradation of polycaprolactone and polycaprolactone-( β -tricalcium phosphate) scaffolds in alkaline medium. Polym. Int. 2007 , 56 , 718−728..

Views

110

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

A Paradigm for BF3 Co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature

Sliding Dynamics of Ring Chain on a Rod-Coil Block Copolymer in Rotaxane

End-to-End Neuron-inspired Signal Transduction Using Organic Electrochemical Transistors

Bioinspired Zinc-doped Nano Hydroxyapatite Reinforced Poly(lactic acid) Composites for Bone Repair

Enhancing Processability of Phenylethynyl-terminated Imide Oligomers and Properties of Cured Polyimides via ―CF3 Incorporation

Related Author

No data

Related Institution

No data

⁰

Direct Ink Writing of Biodegradable Elastic Scaffolds via Rapid Thiol-Acrylate Photocrosslinking

DOI：10.1007/s10118-026-3582-0

摘要

Abstract

关键词

Keywords

references