2020, Mora-Boza, A., Włodarczyk-Biegun, M.K., Del Campo, A., Vázquez-Lasa, B., Román, J.S.

The fabrication of intricate and long-term stable 3D polymeric scaffolds by a 3D printing technique is still a challenge. In the biomedical field, hydrogel materials are very frequently used because of their excellent biocompatibility and biodegradability, however the improvement of their processability and mechanical properties is still required. This paper reports the fabrication of dual crosslinked 3D scaffolds using a low concentrated (<10 wt%) ink of gelatin methacryloyl (GelMA)/chitosan and a novel crosslinking agent, glycerylphytate (G1Phy) to overcome the current limitations in the 3D printing field using hydrogels. The applied methodology consisted of a first ultraviolet light (UV) photopolymerization followed by a post-printing ionic crosslinking treatment with G1Phy. This crosslinker provides a robust framework and avoids the necessity of neutralization with strong bases. The blend ink showed shear-thinning behavior and excellent printability in the form of a straight and homogeneous filament. UV curing was undertaken simultaneously to 3D deposition, which enhanced precision and shape fidelity (resolution ≈150 μm), and prevented the collapse of the subsequent printed layers (up to 28 layers). In the second step, the novel G1Phy ionic crosslinker agent provided swelling and long term stability properties to the 3D scaffolds. The multi-layered printed scaffolds were mechanically stable under physiological conditions for at least one month. Preliminary in vitro assays using L929 fibroblasts showed very promising results in terms of adhesion, spreading, and proliferation in comparison to other phosphate-based traditional crosslinkers (i.e. TPP). We envision that the proposed combination of the blend ink and 3D printing approach can have widespread applications in the regeneration of soft tissues.

2023, Ruthes, Jean G. A., Deller, Andrei E., Pameté, Emmanuel, Riegel‐Vidotti, Izabel C., Presser, Volker, Vidotti, Marcio

Developing new flexible and electroactive materials is a significant challenge to producing safe, reliable, and environmentally friendly energy storage devices. This study introduces a promising electrolyte system that fulfills these requirements. First, polypyrrole (PPy) nanotubes are electropolymerized in graphite-thread electrodes using methyl orange (MO) templates in an acidic medium. The modification increases the conductivity and does not compromise the flexibility of the electrodes. Next, flexible supercapacitors are built using hydrogel prepared from poly(vinyl alcohol) (PVA)/sodium alginate (SA) obtained by freeze–thawing and swollen with ionic solutions as an electrolyte. The material exhibits a homogenous and porous hydrogel matrix allowing a high conductivity of 3.6 mS cm−1 as-prepared while displaying great versatility, changing its electrochemical and mechanical properties depending on the swollen electrolyte. Therefore, it allows its combination with modified graphite-thread electrodes into a quasi-solid electrochemical energy storage device, achieving a specific capacitance (Cs) value of 66 F g−1 at 0.5 A g−1. Finally, the flexible device exhibits specific energy and power values of 19.9 W kg−1 and 3.0 Wh kg−1, relying on the liquid phase in the hydrogel matrix produced from biodegradable polymers. This study shows an environment friendly, flexible, and tunable quasi-solid electrolyte, depending on a simple swell experiment to shape its properties according to its application.

2022, de Miguel‐Jiménez, Adrián, Ebeling, Bastian, Paez, Julieta I., Fink‐Straube, Claudia, Pearson, Samuel, del Campo, Aránzazu

Hydrogel precursors that crosslink within minutes are essential for the development of cell encapsulation matrices and their implementation in automated systems. Such timescales allow sufficient mixing of cells and hydrogel precursors under low shear forces and the achievement of homogeneous networks and cell distributions in the 3D cell culture. The previous work showed that the thiol-tetrazole methylsulfone (TzMS) reaction crosslinks star-poly(ethylene glycol) (PEG) hydrogels within minutes at around physiological pH and can be accelerated or slowed down with small pH changes. The resulting hydrogels are cytocompatible and stable in cell culture conditions. Here, the gelation kinetics and mechanical properties of PEG-based hydrogels formed by thiol-TzMS crosslinking as a function of buffer, crosslinker structure and degree of TzMS functionality are reported. Crosslinkers of different architecture, length and chemical nature (PEG versus peptide) are tested, and degree of TzMS functionality is modified by inclusion of RGD cell-adhesive ligand, all at concentration ranges typically used in cell culture. These studies corroborate that thiol/PEG-4TzMS hydrogels show gelation times and stiffnesses that are suitable for 3D cell encapsulation and tunable through changes in hydrogel composition. The results of this study guide formulation of encapsulating hydrogels for manual and automated 3D cell culture.

2022, de Miguel-Jiménez, Adrián, Ebeling, Bastian, Paez, Julieta I., Fink-Straube, Claudia, Pearson, Samuel, del Campo, Aranzazu

Crosslinking chemistries that allow hydrogel formation within minutes are essential to achieve homogeneous networks and cell distributions in 3D cell culture. Thiol-methylsulfone (MS) crosslinking chemistry offers minutes-scale gelation under near-physiological conditions showing many desirable attributes for 3D cell encapsulation. Here we investigate the gelation kinetics and mechanical properties of PEG-based hydrogels formed by thiol-tetrazole methylsulfone (TzMS) crosslinking as a function of buffer, crosslinker structure, and degree of TzMS functionalization. Appropriate buffer selection ensured constant pH throughout crosslinking. The formulation containing cell adhesive ligand RGD and enzymatically-degradable peptide VPM gelled in ca. 4 min at pH 7.5, and stiffness could be increased from hundreds of Pascals to > 1 kPa by using excess VPM. The gelation times and stiffnesses for these hydrogels are highly suitable for 3D cell encapsulations, and pave the way for reliable 3D cell culture workflows in pipetting robots.