Voltage and concentration gradients across membraneless interface generated next to hydrogels: relation to glycocalyx.

Next to many hydrophilic surfaces, including those of biological cells and tissues, a layer of water that effectively excludes solutes and particles can be generated. This interfacial water is the subject of research aiming for practical applications such as removal of salts, pathogens or manipulation of biomolecules. However, the exact mechanism of its creation is still elusive because its persistence and extension contradict hydrogen-bond dynamics and electric double layer predictions. The experimentally recorded negative voltage of this interfacial water remains to be properly explained. Even less is known about the nature of such water layers in biological systems. We present experimental evidence for ion and particle exclusion as a result of separation of ionic charges with distinct diffusion rates across a liquid junction at the gel/water interface and the subsequent repulsion of ions of a given sign by a like-charged gel surface. Gels represent features of biological interfaces (in terms of functional groups and porosity) and are subject to biologically relevant chemical triggers. Our results show that gels with -OSO3- and -COO- groups can effectively generate ion- and particle-depleted regions of water reaching over 100 µm and having negative voltage up to -30 mV. Exclusion distance and electric potential depend on the liquid junction potential at the gel/water interface and on the concentration gradient at the depleted region/bulk interface, respectively. The voltage and extension of these ion- and particle-depleted water layers can be effectively modified by CO2 (respiratory gas) or KH2PO4 (cell metabolite). Possible implications pertain to biologically unstirred water layers and a cell's bioenergetics.

Native Spider Silk-Based Antimicrobial Hydrogels for Biomedical Applications.

Novel antimicrobial natural polymeric hybrid hydrogels based on hyaluronic acid (HA) and spider silk (Ss) were prepared using the chemical crosslinking method. The effects of the component ratios on the hydrogel characteristics were observed parallel to the primary physicochemical characterization of the hydrogels with scanning electron microscopic imaging, Fourier-transform infrared spectroscopy, and contact angle measurements, which confirmed the successful crosslinking, regular porous structure, exact composition, and hydrophilic properties of hyaluronic acid/spider silk-based hydrogels. Further characterizations of the hydrogels were performed with the swelling degree, enzymatic degradability, viscosity, conductivity, and shrinking ability tests. The hyaluronic acid/spider silk-based hydrogels do not show drastic cytotoxicity over human postnatal fibroblasts (HPF). Hydrogels show extraordinary antimicrobial ability on both gram-negative and gram-positive bacteria. These hydrogels could be an excellent alternative that aids in overcoming antimicrobial drug resistance, which is considered to be one of the major global problems in the biomedical industry. Hyaluronic acid/spider silk-based hydrogels are a promising material for collaborated antimicrobial and anti-inflammatory drug delivery systems for external use. The rheological properties of the hydrogels show shear-thinning properties, which suggest that the hydrogels could be applied in 3D printing, such as in the 3D printing of antimicrobial surgical meshes.