Gold-Hydrogel Nanocomposites for High-Resolution Laser-Based 3D Printing of Scaffolds with SERS-Sensing Properties

Year: 2024

Authors: Ventisette I., Mattii F., Dallari C., Capitini C., Calamai M., Muzzi B., Pavone FS., Carpi F., Credi C.

Autors Affiliation: Univ Florence, Dept Ind Engn, I-50121 Florence, Italy; Univ Florence, European Lab Nonlinear Spect, I-50019 Sesto Fiorentino, Italy; CNR, Natl Inst Opt, I-50019 Sesto Fiorentino, Italy; Univ Florence, Dept Phys & Astron, I-50019 Sesto Fiorentino, Italy; CNR, Inst Chem Organometall Cpds, I-50019 Sesto Fiorentino, Italy.

Abstract: Although visible light-based stereolithography (SLA) represents an affordable technology for the rapid prototyping of 3D scaffolds for in vitro support of cells, its potential could be limited by the lack of functional photocurable biomaterials that can be SLA-structured at micrometric resolution. Even if innovative photocomposites showing biomimetic, bioactive, or biosensing properties have been engineered by loading inorganic particles into photopolymer matrices, main examples rely on UV-assisted extrusion-based low-resolution processes. Here, SLA-printable composites were obtained by mixing a polyethylene glycol diacrylate (PEGDA) hydrogel with multibranched gold nanoparticles (NPs). NPs were engineered to copolymerize with the PEGDA matrix by implementing a functionalization protocol involving covalent grafting of allylamine molecules that have C & boxH;C pendant moieties. The formulations of gold nanocomposites were tailored to achieve high-resolution fast prototyping of composite scaffolds via visible light-based SLA. Furthermore, it was demonstrated that, after mixing with a polymer and after laser structuring, gold NPs still retained their unique plasmonic properties and could be exploited for optical detection of analytes through surface-enhanced Raman spectroscopy (SERS). As a proof of concept, SERS-sensing performances of 3D printed plasmonic scaffolds were successfully demonstrated with a Raman probe molecule (e.g., 4-mercaptobenzoic acid) from the perspective of future extensions to real-time sensing of cell-specific markers released within cultures. Finally, biocompatibility tests preliminarily demonstrated that embedded NPs also played a key role by inducing physiological cell-cytoskeleton rearrangements, further confirming the potentialities of such hybrid nanocomposites as groundbreaking materials in laser-based bioprinting.

Journal/Review: ACS APPLIED BIO MATERIALS

Volume: 7 (7)      Pages from: 4497  to: 4509

More Information: Financial support was provided by CNR-FOE-LENS-2023, by the Integrated infrastructure initiative in photonic and quantum sciences-I-PHOQS (CUP B53C22001750006) project finances by the EU next generation PNRR action, by the Italian Ministry of Education, University and Research in the framework of PNRR projects AGE-IT-Ageing well in an ageing society and in the framework of the Advance Lightsheet Microscopy Italian Mode of Euro-bioimaging ERIC. The authors would also like to thank the Centre for Electron Microscopies (Ce.ME) and the Centro di competenza RISE funded by FAS Regione Toscana. The authors also wish to acknowledge Prof. Andrea Trabocchi for technical advice and Prof. Rosanna Rizzo for fruitful mathematical discussions.
KeyWords: stereolithography; PEGDA; nanocomposites; gold nanoparticles (AuNPs); surface enhanced Raman spectroscopy; allylamine-conjugated NPs; optical sensing
DOI: 10.1021/acsabm.4c00379

Citations: 1
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