Optimized Photoclick (Bio)Resins for Fast Volumetric Bioprinting

Adv Mater. 2021 Dec;33(49):e2102900. doi: 10.1002/adma.202102900. Epub 2021 Oct 5.

Abstract

Volumetric printing (VP) is a light-mediated technique enabling printing of complex, low-defect 3D objects within seconds, overcoming major drawbacks of layer-by-layer additive manufacturing. An optimized photoresin is presented for VP in the presence of cells (volumetric bioprinting) based on fast thiol-ene step-growth photoclick crosslinking. Gelatin-norbornene (Gel-NB) photoresin shows superior performance, both in physicochemical and biocompatibility aspects, compared to (meth-)acryloyl resins. The extremely efficient thiol-norbornene reaction produces the fastest VP reported to date (≈10 s), with significantly lower polymer content, degree of substitution (DS), and radical species, making it more suitable for cell encapsulation. This approach enables the generation of cellular free-form constructs with excellent cell viability (≈100%) and tissue maturation potential, demonstrated by development of contractile myotubes. Varying the DS, polymer content, thiol-ene ratio, and thiolated crosslinker allows fine-tuning of mechanical properties over a broad stiffness range (≈40 Pa to ≈15 kPa). These properties are achieved through fast and scalable methods for producing Gel-NB with inexpensive, off-the-shelf reagents that can help establish it as the gold standard for light-mediated biofabrication techniques. With potential applications from high-throughput bioprinting of tissue models to soft robotics and regenerative medicine, this work paves the way for exploitation of VPs unprecedented capabilities.

Keywords: bioprinting; gelatin; photoclick; thiol-ene; volumetric.

MeSH terms

  • Bioprinting*
  • Gelatin / chemistry
  • Hydrogels
  • Norbornanes
  • Polymers
  • Printing, Three-Dimensional
  • Sulfhydryl Compounds
  • Tissue Engineering
  • Tissue Scaffolds

Substances

  • Hydrogels
  • Norbornanes
  • Polymers
  • Sulfhydryl Compounds
  • Gelatin