The development of materials for 3D printing adapted for tissue engineering represents one of the main concerns nowadays. Our aim was to obtain suitable 3D-printed scaffolds based on methacrylated gelatin (GelMA). In this respect, three degrees of GelMA methacrylation, three different concentrations of GelMA (10%, 20%, and 30%), and also two concentrations of photoinitiator (I-2959) (0.5% and 1%) were explored to develop proper GelMA hydrogel ink formulations to be used in the 3D printing process. Afterward, all these GelMA hydrogel-based inks/3D-printed scaffolds were characterized structurally, mechanically, and morphologically. The presence of methacryloyl groups bounded to the surface of GelMA was confirmed by FTIR and 1H-NMR analyses. The methacrylation degree influenced the value of the isoelectric point that decreased with the GelMA methacrylation degree. A greater concentration of photoinitiator influenced the hydrophilicity of the polymer as proved using contact angle and swelling studies because of the new bonds resulting after the photocrosslinking stage. According to the mechanical tests, better mechanical properties were obtained in the presence of the 1% initiator. Circular dichroism analyses demonstrated that the secondary structure of gelatin remained unaffected during the methacrylation process, thus being suitable for biological applications.
Hybrid nanomaterials based on zinc oxide were synthesized via the sol–gel method, using different silane coupling agents: (3-glycidyloxypropyl)trimethoxysilane (GPTMS), phenyltriethoxysilane (PhTES), octyltriethoxysilane (OTES), and octadecyltriethoxysilane (ODTES). Morphological properties and the silane precursor type effect on the particle size were investigated using dynamic light scattering (DLS), environmental scanning electron microscopy (ESEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and X-ray diffraction (XRD). The bonding characteristics of modified ZnO materials were investigated using Fourier transform infrared spectroscopy (FTIR). The final solutions were deposited on metallic substrate (aluminum) in order to realize coatings with various wettability and roughness. The morphological studies, obtained by ESEM and TEM analysis, showed that the sizes of the ZnO nanoparticles are changed as function of silane precursor used in synthesis. The thermal stability of modified ZnO materials showed that the degradation of the alkyl groups takes place in the 300–500 °C range. Water wettability study revealed a contact angle of 142 ± 5° for the surface covered with ZnO material modified with ODTES and showed that the water contact angle increases as the alkyl chain from the silica precursor increases. These modified ZnO materials, therefore, can be easily incorporated in coatings for various applications such as anti-corrosion and anti-icing.
The present work aims at comparatively studying the effects of the concentrations of a monomer (10–30 wt% based on the whole hydrogel composition), crosslinking agent (1–3 mol% based on the monomer), and reinforcing agent (montmorillonite–MMT, 1–3 wt.% based on the whole hydrogel composition) on the swelling and viscoelastic properties of the crosslinked hydrogels prepared from methacrylic acid (MAA) and N,N′-methylenebisacrylamide (BIS) in the presence of K2S2O8 in aqueous solution. The viscoelastic measurements, carried out on the as-prepared hydrogels, showed that the monomer concentration had the largest impact, its three-time enhancement causing a 30-fold increase in the storage modulus, as compared with only a fivefold increase in the case of the crosslinking agent and 1.5-fold increase for MMT in response to a similar threefold concentration increase. Swelling studies, performed at three pH values, revealed that the water absorption of the hydrogels decreased with increasing concentration of both the monomer and crosslinking agent, with the amplitude of the effect of concentration modification being similar at pH 5.4 and 7.4 in both cases, but very different at pH 1.2. Further, it was shown that the increased pH differently influenced the swelling degree in the case of the hydrogel series in which the concentrations of the monomer and crosslinking agent were varied. In contrast to the effect of the monomer and crosslinking agent concentrations, the increase in the MMT amount in the hydrogel resulted in an increased swelling degree at pH 5.4 and 7.4, while at pH 1.2, a slight decrease in the water absorption was noticed. The hydrogel crosslinking density determinations revealed that this parameter was most affected by the increase in the monomer concentration.
In this work, a synthetic effluent containing Methylene blue dye has been treated by novel membrane enriched with commercial gooseberry buds extract using a mini-laboratory electrodialysis cell. The electrodialysis system was operated at various time and constant voltage applied at electrodes. Methylene blue removal percentage (CR %) and energy consumption (E.C.) were calculated. The obtained results showed that pH increase in solution and lead to an increase of deprotonated methylene groups, which may favor methylene dichloride complex formation. The values of CR % and E.C. increased with time. The high value of CR % was obtained at 60 min(CR> 89 %). The membranes were characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Environmental Scanning Electron Microscopy (ESEM).
The present study investigated the possibility of obtaining 3D printed composite constructs using biomaterial-based nanocomposite inks. The biopolymeric matrix consisted of methacrylated gelatin (GelMA). Several types of nanoclay were added as the inorganic component. Our aim was to investigate the influence of clay type on the rheological behavior of ink formulations and to determine the morphological and structural properties of the resulting crosslinked hydrogel-based nanomaterials. Moreover, through the inclusion of nanoclays, our goal was to improve the printability and shape fidelity of nanocomposite scaffolds. The viscosity of all ink formulations was greater in the presence of inorganic nanoparticles as shear thinning occurred with increased shear rate. Hydrogel nanocomposites presented predominantly elastic rather than viscous behavior as the materials were crosslinked which led to improved mechanical properties. The inclusion of nanoclays in the biopolymeric matrix limited hydrogel swelling due the physical barrier effect but also because of the supplementary crosslinks induced by the clay layers. The distribution of inorganic filler within the GelMA-based hydrogels led to higher porosities as a consequence of their interaction with the biopolymeric ink. The present study could be useful for the development of soft nanomaterials foreseen for the additive manufacturing of customized implants for tissue engineering.
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