Supramolecular Chemistry Empowers Vat Photopolymerization Mediated DLP-3D Printing of PVA-MA-AA Resin for pH-Responsive Drug Delivery Applications

Abstract

Vat photopolymerization (VP) offers exceptional precision by carefully directing light to materials that can be cross-linked or photopolymerized via photosensitive reactions. However, traditional photo-cross-linking forms a dense network that hinders the drug release. To overcome this, supramolecular interactions between photopolymer chains can be used instead of dense covalent bonding to achieve reversible noncovalent bonding. In this study, we introduce a photocurable resin through supramolecular chemistry empowered VP mediated DLP-3DP that can fabricate solid structures, provide a versatile release profile, and overcome the limitations of DLP 3D printing in personalized drug delivery systems. Supramolecular interactions between poly(vinyl alcohol)-methacrylate (PVA-MA) and acrylic acid (AA) were used to produce photocurable resins and DLP-mediated acetaminophen-loaded prototypes. ¹H NMR and FT-ATR analyses confirmed the successful integration of PVA-MA and AA into the photopolymer. Furthermore, acetaminophen-loaded prototypes were thoroughly investigated for solid-state characterization, drug content analysis, and in vitro release studies. Drug content analysis confirmed each 3D-printed prototype contains 0.42 ± 0.010% w/v of acetaminophen. In vitro, release studies showed pH-dependent release behavior of acetaminophen, reaching approximately 30 and 65% within 24.0 h in acidic and basic media, respectively. The findings of the current study highlight the widespread application of DLP-3D printing in creating patient-centric and stimuli-responsive solid oral dosage forms.