Fibrillar biocompatible colloidal gels based on cellulose nanocrystals and poly(N-isopropylacrylamide) for direct ink writing.

HYPOTHESIS: Hydrogels based on cellulose nanocrystals (CNC) have attracted great interest because of their sustainability, biocompatibility, mechanical strength and fibrillar structure. Gelation of colloidal particles can be induced by the introduction of polymers. Existing examples include gels based on CNC and derivatives of cellulose or poly(vinyl alcohol), however, gel structure and their application for extrusion printing were not shown. Hence, we rationalize formation of colloidal gels based on mixture of poly(N-isopropylacrylamide) (PNIPAM) and CNC and control their structure and mechanical properties by variation of components ratio. EXPERIMENTS: State diagram for colloidal system based on mixture of PNIPAM and CNC were established at 25 and 37 °C. Biocompatibility, fiber diameter and rheological properties of the gels were studied for different PNIPAM/CNC ratio. FINDINGS: We show that depending on the ratio between PNIPAM and CNC, colloidal system could be in sol or gel state at 25 °C and at gel state or phase separated at 37 °C. Physically crosslinked hydrogels were thermosensitive and could reversibly change it transparency from translucent to opaque in biologically relevant temperature range. These colloidal hydrogels were biocompatible, had fibrillar structure and demonstrate shear-thinning behavior, which makes them a promising material for bioapplications related to extrusion printing.

Thermosensitive Chitosan-Containing Hydrogels: Their Formation, Properties, Antibacterial Activity, and Veterinary Usage.

Mixtures of aqueous solutions of chitosan hydrochloride (CS·HCl, 1-4 wt.%) and Pluronic F-127 (Pl F-127, 25 wt.%) were studied using vibrational and rotational viscometry; the optimal aminopolysaccharide concentration (3 wt.%) and the CS·HCl:Pl F-127 ratio (30:70) to obtain a thermosensitive hydrogel were found. It was shown that at 4 °C, such mixed compositions were viscous liquids, while at 37 °C for 1-2 min, they undergo a thermally reversible transition to a shape-stable hydrogel with a developed level of structure formation, satisfactory viscosity and high mucoadhesive parameters (maximum pull-off force Fmax = 1.5 kN/m2; work of adhesion W = 66.6 × 10-3 J). Adding D-ascorbic acid to the hydrogel led to orientational ordering of the supramolecular structure of the mixed system and significantly improved mucoadhesion (Fmax = 4.1 kN/m2, W = 145.1 × 10-3 J). A microbiological study revealed the high antibacterial activity of the hydrogel against Gram-negative and Gram-positive bacterial strains. The treatment of mixed bacterial infection in cows demonstrated the possibility of the in situ formation of a viscoelastic gel and revealed its high therapeutic effect. It has been suggested that our thermosensitive mucoadhesive CS·HCl:Pl F-127 hydrogels could be considered as independent veterinary drugs and pharmaceuticals.

Hierarchical Porous Magnetite Structures: From Nanoparticle Assembly to Monolithic Aerogels.

The development of universal methods to synthesize materials with different structures is always in the researchers' focus. Despite the fact that various structures based on magnetite have already been obtained, synthetic approaches that allow to synthesize materials with a wide range of texture and functional properties are still very poorly presented. In this work, we demonstrate that a stable magnetite hydrosol can be easily converted into monolithic structures of xero-, cryo- and aerogel by careful varying concentrations and drying conditions. We have also theoretically explained the observed effects by studying the percolation threshold at the sol-gel transition by means of controlled assembly of magnetite nanoparticles. At the calculated percolation point three types of materials different in porous organization were obtained. Due to the high biocompatibility of magnetite nanoparticles, the materials obtained were evaluated for cytotoxicity on HeLa cells line. All synthesized magnetite structures show excellent biocompatibility and minor cytotoxic effects at concentrations up to 1 µg mL-1. Considering that the porosity of materials can influence the manifestation of the hemostatic effect, whole-blood clotting study revealed the hemostatic potential of magnetite aerogel. That fact can be explained by presence spongy structure of the aerogel that allowed blood to be rapidly absorbed through full contact.