Core-Shell Structure of Photopolymer-Grafted Polyurethane as a Controlled Drug Delivery Vehicle for Biomedical Application.

Functionalized ultraviolet photocurable bisphenol A-glycerolate dimethacrylates with tailorable size have been synthesized as the core, which have further been grafted using the diisocyanate chain end of polyurethane (PU) as the shell to create a core-shell structure of tunable size for a controlled drug delivery vehicle. The core-shell structure has been elucidated through spectroscopic techniques like 1H NMR, FTIR, and UV-vis and their relative shape and size through TEM and AFM morphology. The greater cross-link density of the core is reflected in the higher glass transition temperature, and the improved thermal stability of the graft copolymer is proven from its thermogravimetric analyses. The flow behavior and enhanced strength of the graft copolymers have been revealed from rheological measurements. The graft copolymer exhibits sustained release of the drug, as compared to pure polyurethane and photopolymer, arising from its core-shell structure and strong interaction between the copolymer and drug, as observed through a significant shifting of absorption peaks in FTIR and UV-vis measurements. Biocompatibility has been tested for the real application of the novel graft copolymer in medical fields, as revealed from MTT assay, cell imaging, and cell adhesion studies. The efficacy of controlled release from a graft copolymer has been verified from the gradual cell killing and ∼70% killing in 3 days vs meager cell killing of ∼25% very quickly in 1 day, followed by the increased cell viability of the system treated with the pure drug. The mechanism of slow and controlled drug release from the core-shell structure has been explored. The fluorescence images support the higher cell-killing efficiency as opposed to a pure drug or a drug embedded in polyurethane. Cells seeded on 3D scaffolds have been developed by embedding a graft copolymer, and fluorescence imaging confirms the successful growth of cells within the scaffold, realizing the potential of the core-shell graft copolymer in the biomedical arena.

3D Printing of a Biocompatible Nanoink Derived from Waste Animal Bones.

Direct ink writing (DIW) additive manufacturing is a versatile 3D printing technique for a broad range of materials. DIW can print a variety of materials provided that the ink is well-engineered with appropriate rheological properties. DIW could be an ideal technique in tissue engineering to repair and regenerate deformed or missing organs or tissues, for example, bone and tooth fracture that is a common problem that needs surgeon attention. A critical criterion in tissue engineering is that inserts must be compatible with their surrounding environment. Chemically produced calcium-rich materials are dominant in this application, especially for bone-related applications. These materials may be toxic leading to a rejection by the body that may need secondary surgery to repair. On the other hand, there is an abundance of biowaste building blocks that can be used for grafting with little adverse effect on the body. In this work, we report a bioderived ink made entirely of calcium derived from waste animal bones using a benign process. Calcium nanoparticles are extracted from the bones and the ink prepared by mixing with different biocompatible binders. The ink is used to print scaffolds with controlled porosity that allows better growth of cells. DIW printed parts show better mechanical properties and biocompatibility that are important for the grafting application. Degradation tests and a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay study were done to examine the biocompatibility of the extracted materials. In addition, discrete element modeling and computational fluid dynamics numerical methods are used in Rocky and Ansys software programs. This work shows that biowaste materials if well-engineered can be a never-ending source of raw materials for advanced application in orthopedic grafting.