title: Modular and Versatile Spatial Functionalization of Tissue Engineering Scaffolds through Fiber-Initiated Controlled Radical Polymerization.
abstract: Native tissues are typically heterogeneous and hierarchically organized, and generating scaffolds that can mimic these properties is critical for tissue engineering applications. By uniquely combining controlled radical polymerization (CRP), end-functionalization of polymers, and advanced electrospinning techniques, a modular and versatile approach is introduced to generate scaffolds with spatially organized functionality. Poly-ε-caprolactone is end functionalized with either a polymerization-initiating group or a cell-binding peptide motif cyclic Arg-Gly-Asp-Ser (cRGDS), and are each sequentially electrospun to produce zonally discrete bilayers within a continuous fiber scaffold. The polymerization-initiating group is then used to graft an antifouling polymer bottlebrush based on poly(ethylene glycol) from the fiber surface using CRP exclusively within one bilayer of the scaffold. The ability to include additional multifunctionality during CRP is showcased by integrating a biotinylated monomer unit into the polymerization step allowing postmodification of the scaffold with streptavidin-coupled moieties. These combined processing techniques result in an effective bilayered and dual-functionality scaffold with a cell-adhesive surface and an opposing antifouling non-cell-adhesive surface in zonally specific regions across the thickness of the scaffold, demonstrated through fluorescent labelling and cell adhesion studies. This modular and versatile approach combines strategies to produce scaffolds with tailorable properties for many applications in tissue engineering and regenerative medicine.
authors.affiliation: Department of Materials Imperial College London London SW7 2AZ UK; Institute of Biomedical Engineering Imperial College London London SW7 2AZ UK; Department of Bioengineering Imperial College London London SW7 2AZ UK; Department of Plastic and Reconstructive Surgery Imperial College Healthcare NHS Trust Charing Cross Campus Fulham Palace Road London W6 8RF UK.
authors.forename: Rachael H
authors.initials: RH
authors.lastname: Harrison
authors.affiliation: Department of Materials Imperial College London London SW7 2AZ UK; Institute of Biomedical Engineering Imperial College London London SW7 2AZ UK; Department of Bioengineering Imperial College London London SW7 2AZ UK.
authors.forename: Joseph A M
authors.initials: JA
authors.lastname: Steele
authors.affiliation: Department of Materials Imperial College London London SW7 2AZ UK; Institute of Biomedical Engineering Imperial College London London SW7 2AZ UK; Department of Bioengineering Imperial College London London SW7 2AZ UK.
authors.forename: Robert
authors.initials: R
authors.lastname: Chapman
authors.affiliation: Department of Materials Imperial College London London SW7 2AZ UK; Institute of Biomedical Engineering Imperial College London London SW7 2AZ UK; Department of Bioengineering Imperial College London London SW7 2AZ UK.
authors.forename: Adam J
authors.initials: AJ
authors.lastname: Gormley
authors.affiliation: Department of Materials Imperial College London London SW7 2AZ UK; Institute of Biomedical Engineering Imperial College London London SW7 2AZ UK; Department of Bioengineering Imperial College London London SW7 2AZ UK.
authors.forename: Lesley W
authors.initials: LW
authors.lastname: Chow
authors.affiliation: Department of Materials Imperial College London London SW7 2AZ UK; Institute of Biomedical Engineering Imperial College London London SW7 2AZ UK; Department of Bioengineering Imperial College London London SW7 2AZ UK.
authors.forename: Muzamir M
authors.initials: MM
authors.lastname: Mahat
authors.affiliation: Department of Materials Imperial College London London SW7 2AZ UK; Institute of Biomedical Engineering Imperial College London London SW7 2AZ UK; Department of Bioengineering Imperial College London London SW7 2AZ UK.
authors.forename: Lucia
authors.initials: L
authors.lastname: Podhorska
authors.affiliation: Department of Chemistry University College London 20 Gordon Street London WC1H 0AJ UK.
authors.forename: Robert G
authors.initials: RG
authors.lastname: Palgrave
authors.affiliation: Department of Materials Imperial College London London SW7 2AZ UK.
authors.forename: David J
authors.initials: DJ
authors.lastname: Payne
authors.affiliation: Department of Plastic and Reconstructive Surgery Imperial College Healthcare NHS Trust Charing Cross Campus Fulham Palace Road London W6 8RF UK.
authors.forename: Shehan P
authors.initials: SP
authors.lastname: Hettiaratchy
authors.affiliation: Department of Materials Imperial College London London SW7 2AZ UK.
authors.forename: Iain E
authors.initials: IE
authors.lastname: Dunlop
authors.affiliation: Department of Materials Imperial College London London SW7 2AZ UK; Institute of Biomedical Engineering Imperial College London London SW7 2AZ UK; Department of Bioengineering Imperial College London London SW7 2AZ UK.
authors.forename: Molly M
authors.initials: MM
authors.lastname: Stevens
keywords: antifouling; bilayered materials; controlled polymerization; electrospinning; polymer bottlebrushes