4.7 Article

Fabricating Robust Constructs with Internal Phase Nanostructures via Liquid-in-Liquid 3D Printing

Journal

MACROMOLECULAR RAPID COMMUNICATIONS
Volume 42, Issue 22, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/marc.202100445

Keywords

3D printing; interfaces; nanostructured constructs; self-assembly; surfactants

Funding

  1. University of Missouri-Kansas City
  2. National Science Foundation (NSF)
  3. Division of Materials Research Polymers Program (CAREER) [DMR-1942508]
  4. Air Force Office of Scientific Research under the Young Investigator Prize [18RT0680]

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This study introduces a new liquid-in-liquid 3D printing approach to create constructs with internal nanostructures, overcoming limitations of traditional additive manufacturing methods. The mechanical properties of the printed materials can be tuned based on the composition of the aqueous solution, expanding the possibilities for low-viscosity materials in 3D printing and offering broad applications in regenerative medicine.
The ability to print soft materials into predefined architectures with programmable nanostructures and mechanical properties is a necessary requirement for creating synthetic biomaterials that mimic living tissues. However, the low viscosity of common materials and lack of required mechanical properties in the final product present an obstacle to the use of traditional additive manufacturing approaches. Here, a new liquid-in-liquid 3D printing approach is used to successfully fabricate constructs with internal nanostructures using in situ self-assembly during the extrusion of an aqueous solution containing surfactant and photocurable polymer into a stabilizing polar oil bath. Subsequent photopolymerization preserves the nanostructures created due to surfactant self-assembly at the immiscible liquid-liquid interface, which is confirmed by small-angle X-ray scattering. Mechanical properties of the photopolymerized prints are shown to be tunable based on constituent components of the aqueous solution. The reported 3D printing approach expands the range of low-viscosity materials that can be used in 3D printing, and enables robust constructs production with internal nanostructures and spatially defined features. The reported approach has broad applications in regenerative medicine by providing a platform to print self-assembling biomaterials into complex tissue mimics where internal supramolecular structures and their functionality control biological processes, similar to natural extracellular matrices.

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