Biomaterials: unlocking new frontiers from biomedicine to additive manufacturing

This manuscript provides an overview of the research I conducted during my PhD at the Industrial Chemistry Department “Toso Montanari” within the ASOM (Advanced Smart Organic Materials) research group under the supervision of Professor Mauro Comes Franchini. My work has focused on synthesising, functionalising, and applying biomaterials in additive manufacturing, nanomedicine and smart hydrogels. Accordingly, the manuscript is divided into three chapters, each summarising the key findings achieved throughout my PhD. Following an introduction to biomaterials and their potential as sustainable alternatives to traditional reagents, the thesis is outlined as follows: 1. The first chapter, “Additive Manufacturing”, focuses on the synthesis and formulation of biobased reins for vat photopolymerisation. Five projects are presented, exploiting itaconic acid as a sustainable alternative to petroleum-based compounds. Liquid resins entirely synthesised from renewable or biodegradable materials were developed, achieving up to 97% biobased content. These include biobased polycaprolactone star-macromers, terpene-based polyesters, a liquid biobased diurethanediol, and nanocellulose modified with safflower fatty acid as a bio-additive to improve mechanical properties. Overall, these advancements offer greener, high-performance alternatives to fossil-based resins for 3D printing. 2. The second chapter, “Nanomedicine”, highlights three biobased nanosystems for nanomedicine applications. Two of them were drug delivery systems aptamer-functionalised efficiently targeting triple-negative breast cancer (TNBC). Both were designed with biobased or biodegradable materials, like casein and poly(lactic-co-glycolic)-block-polyethylene glycol (PLGA-b-PEG), to deliver lipophilic drugs or hydrophilic small interfering RNA (siRNA), respectively. The third project combines a luminescent Iridium (III) complex with microcrystalline cellulose, showing potential for biomedicine, bioimaging, and photocatalysis. 3. The last chapter, “Smart Hydrogel”, outlines two renewable-based hydrogel systems for biomedical applications. The first is a smart FDA-approved hydrogel for post-surgery use, developed during my time as a visiting PhD student at Imperial College London. The second is a nanocellulose-based hydrogel for glioblastoma treatment. Both projects are ongoing.