3D Printed Hierarchical Porous Poly(ε-caprolactone) Scaffolds from Pickering High Internal Phase Emulsion Templating

In the realm of biomaterials, particularly bone tissue engineering, there has been a great increase in interest in scaffolds with hierarchical porosity and customizable multifunctionality. Recently, the three-dimensional (3D) printing of biopolymer-based inks (solutions or emulsions) has gained high popularity for fabricating tissue engineering scaffolds, which optimally satisfies the desired properties and performances. Herein, therefore, we explore the fabrication of 3D printed hierarchical porous scaffolds of poly(ε-caprolactone) (PCL) using the water-in-oil (w/o) Pickering PCL high internal phase emulsions (HIPEs) as the ink in 3D printer. The Pickering PCL HIPEs stabilized using hydrophobically modified nanoclay comprised of aqueous poly(vinyl alcohol) (PVA) as the dispersed phase. Rheological measurements suggested the shear thinning behavior of Pickering HIPEs having a dispersed droplet diameter of 3-25 μm. The pore morphology resembling the natural extracellular matrix and the mechanical properties of scaffolds were customized by tuning the emulsion composition and 3D printing parameters. In vitro biomineralization and drug release studies proved the scaffolds' potential in developing the apatite-rich bioactive interphase and controlled drug delivery, respectively. During in vitro osteoblast (MG63) growth experiments for up to 7 days, good adhesion and proliferation on PCL scaffolds confirmed their cytocompatibility, assessed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) analysis. This study suggests that the assembly of HIPE templates and 3D printing is a promising approach to creating hierarchical porous scaffolds potentially suitable for bone tissue engineering and can be stretched to other biopolymers as well.