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Photocuring of chitosan has shown great promise in the extrusion-based 3D printing of scaffolds for advanced biomedical and tissue engineering applications. However, the poor mechanical stability of methacrylated chitosan photocuring ink restricts its applicability. The inclusion of co-networks by means of simultaneous polycomplex formation is an effective method by which to solve this drawback, but the formed hydrogel inks are not printable. This work aims to develop new photocurable chitosan inks based on the simultaneous photocrosslinking of methacrylated chitosan (CHIMe) with N,N′-methylenebisacrylamide, polyethylene glycol diacrylate, and acrylic acid to be applied in extrusion 3D printing. Interestingly, the polycomplex co-network corresponding to the acrylic-acid-based ink could be successfully printed by the here-presented simultaneous photocuring strategy. Further, the conversion of photocrosslinking was studied via photo-DSC analyses that revealed a clear dependence on the chemical structure of the employed crosslinking agents (from 40 to ~100%). In addition, the mechanical and rheological properties of the photocured hydrogels were comparatively studied, as well as the printing quality of the extruded scaffolds. The newly developed chitosan photocurable inks demonstrated extrusion printability (squareness ~0.90; uniformity factor ~0.95) and tunable mechanical properties (Young modulus 14–1068 Pa) by means of different crosslinking approaches according to the chemical architecture of the reactive molecules employed. This work shows the great potential of photocrosslinkable chitosan inks.

Cardiovascular disease (CVD), the leading cause of mortality worldwide is primarily caused by atherosclerosis, which is promoted by the accumulation of low-density lipoproteins into the intima of large arteries. Multiple nanoparticles mimicking natural HDL (rHDL) have been designed to remove cholesterol excess in CVD therapy. The goal of this investigation was to assess the cholesterol efflux efficiency of rHDLs with different lipid compositions, mimicking different maturation stages of high-density lipoproteins (HDLs) occurring in vivo. Methods: the cholesterol efflux activity of soybean PC (Soy-PC), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), DPPC:Chol:1-palmitoyl-2-hydroxy-sn-glycero-3-phosphocholine (LysoPC) and DPPC:18:2 cholesteryl ester (CE):LysoPC rHDLs was determined in several cell models to investigate the contribution of lipid composition to the effectiveness of cholesterol removal. Results: DPPC rHDLs are the most efficient particles, inducing cholesterol efflux in all cellular models and in all conditions the effect was potentiated when the ABCA1 transporter was upregulated. Conclusions: DPPC rHDLs, which resemble nascent HDL, are the most effective particles in inducing cholesterol efflux due to the higher physical binding affinity of cholesterol to the saturated long-chain-length phospholipids and the favored cholesterol transfer from a highly positively curved bilayer, to an accepting planar bilayer such as DPPC rHDLs. The physicochemical characteristics of rHDLs should be taken into consideration to design more efficient nanoparticles to promote cholesterol efflux.