Biomaterials for Regenerative Cranioplasty: Current State of Clinical Application and Future Challenges.

Acquired cranial defects are a prevalent condition in neurosurgery and call for cranioplasty, where the missing or defective cranium is replaced by an implant. Nevertheless, the biomaterials in current clinical applications are hardly exempt from long-term safety and comfort concerns. An appealing solution is regenerative cranioplasty, where biomaterials with/without cells and bioactive molecules are applied to induce the regeneration of the cranium and ultimately repair the cranial defects. This review examines the current state of research, development, and translational application of regenerative cranioplasty biomaterials and discusses the efforts required in future research. The first section briefly introduced the regenerative capacity of the cranium, including the spontaneous bone regeneration bioactivities and the presence of pluripotent skeletal stem cells in the cranial suture. Then, three major types of biomaterials for regenerative cranioplasty, namely the calcium phosphate/titanium (CaP/Ti) composites, mineralised collagen, and 3D-printed polycaprolactone (PCL) composites, are reviewed for their composition, material properties, and findings from clinical trials. The third part discusses perspectives on future research and development of regenerative cranioplasty biomaterials, with a considerable portion based on issues identified in clinical trials. This review aims to facilitate the development of biomaterials that ultimately contribute to a safer and more effective healing of cranial defects.

Selective and Functional-Group-Tolerant Photoalkylation of Imines by Energy-Transfer Photocatalysis.

Basic amines show broad bioactivity and remain a promising source of new medicines. The direct photoalkylation of imines offers a promising strategy for complex amines. However, the lack of efficient imine photoreactivity hinders this reaction and remains a fundamental limitation in organic photochemistry. We report an efficient photoalkylation of imines that provides primary amines directly without protecting or leaving groups. The transformation effects C-H addition across N-H imines under energy-transfer photocatalysis by a ketone. Our method is distinguished from organometallic, metal-catalyzed, and photoredox approaches to imine alkylation by its lack of protecting groups and its broad scope, which includes unactivated alkanes, protic substrates, basic amines, heterocycles, and ketone imines. We highlight this scope through the condensation and alkylation of two pharmaceutical ketones, providing complex amines succinctly. Our mechanistic analysis supports a three-step process, involving hydrogen-atom transfer to an imine triplet excited state, intersystem crossing, and radical recombination, with photocatalytic enhancement through energy transfer. We further show that N-H imines are more photoreactive than N-substituted imines, a distinction partially explained by sterics and side reactions. To fully explain this distinction, we introduce the thermodynamic parameter excited-state hydrogen-atom affinity, which is highly effective at predicting the photoreactivity of imines.

Additive Manufacturing of Bioactive Glass and Its Polymer Composites as Bone Tissue Engineering Scaffolds: A Review.

Bioactive glass (BG) and its polymer composites have demonstrated great potential as scaffolds for bone defect healing. Nonetheless, processing these materials into complex geometry to achieve either anatomy-fitting designs or the desired degradation behavior remains challenging. Additive manufacturing (AM) enables the fabrication of BG and BG/polymer objects with well-defined shapes and intricate porous structures. This work reviewed the recent advancements made in the AM of BG and BG/polymer composite scaffolds intended for bone tissue engineering. A literature search was performed using the Scopus database to include publications relevant to this topic. The properties of BG based on different inorganic glass formers, as well as BG/polymer composites, are first introduced. Melt extrusion, direct ink writing, powder bed fusion, and vat photopolymerization are AM technologies that are compatible with BG or BG/polymer processing and were reviewed in terms of their recent advances. The value of AM in the fabrication of BG or BG/polymer composites lies in its ability to produce scaffolds with patient-specific designs and the on-demand spatial distribution of biomaterials, both contributing to effective bone defect healing, as demonstrated by in vivo studies. Based on the relationships among structure, physiochemical properties, and biological function, AM-fabricated BG or BG/polymer composite scaffolds are valuable for achieving safer and more efficient bone defect healing in the future.

Recovery of Carbon Fibre from Waste Prepreg via Microwave Pyrolysis.

Management of waste from carbon fibre composites has become a significant societal issue as the application of composite grows across many industries. In this study, carbon fibres (CF) were successfully recovered from cured carbon fibre/epoxy (CF/EP) prepreg under microwave pyrolysis at 450, 550 and 650 °C followed by oxidation of any residual char. The recovered fibres were investigated for their tensile properties, surface morphologies and the elements/functional groups presented on the surface. The chemical compositions of gaseous and oil pyrolysis products were also analysed. The microwave pyrolysis effectively pyrolyzed the epoxy (EP) resin. Char residue remained on the fibre surface and the amount of char reduced as the pyrolysis temperature increased. Compared to virgin fibres, the recovered fibre suffered from a strength reduction by less than 20%, and this reduction could be mitigated by reducing the pyrolysis temperature. The surface of recovered fibre remained clean and smooth, while the profile of elements and functional groups at the surface were similar to those of virgin fibres. The main gaseous products were CO, H2, CO2 and CH4, whilst the liquid product stream included phenolic and aromatic compounds.

Additive-Manufactured Gyroid Scaffolds of Magnesium Oxide, Phosphate Glass Fiber and Polylactic Acid Composite for Bone Tissue Engineering.

Composites of biodegradable phosphate glass fiber and polylactic acid (PGF/PLA) show potential for bone tissue engineering scaffolds, due to their ability to release Ca, P, and Mg during degradation, thus promoting the bone repair. Nevertheless, glass degradation tends to acidify the surrounding aqueous environment, which may adversely affect the viability and bone-forming activities of osteoblasts. In this work, MgO was investigated as a neutralizing agent. Porous network-phase gyroid scaffolds were additive-manufactured using four different materials: PLA, MgO/PLA, PGF/PLA, and (MgO + PGF)/PLA. The addition of PGF enhanced compressive properties of scaffolds, and the resultant scaffolds were comparably strong and stiff with human trabecular bone. While the degradation of PGF/PLA composite induced considerable acidity in degradation media and intensified the degradation of PGF in return, the degradation media of (MgO + PGF)/PLA maintained a neutral pH close to a physiological environment. The experiment results indicated the possible mechanism of MgO as the neutralizing agent: the local acidity was buffered as the MgO reacted with the acidic degradation products thereby inhibiting the degradation of PGF from being intensified in an acidic environment. The (MgO + PGF)/PLA composite scaffold appears to be a candidate for bone tissue engineering.