Hydrogels Based on Polyacrylamide and Calcium Alginate: Thermodynamic Compatibility of Interpenetrating Networks, Mechanical, and Electrical Properties.

The synthesis and physicochemical properties of hydrogels with interpenetrated physical and chemical networks were considered in relation to their prospective application as biomimetic materials in biomedicine and bioengineering. The study was focused on combined hydrogels based on natural polysaccharide-calcium alginate (CaAlg) and a synthetic polymer-polyacrylamide (PAAm). The series of hydrogels with varying proportions among alginate and polyacrylamide have been synthesized, and their water uptake has been characterized depending on their composition. The equilibrium swelling and re-swelling in water after drying were considered. The compatibility of alginate and polyacrylamide in the combined blend was studied by the thermodynamic approach. It showed a controversial combination of negative enthalpy of mixing among PAAm and CaAlg with positive Gibbs energy of mixing. Mechanical and electrical properties of the combined gels with double networking were studied as relevant for their prospective use as scaffolds for tissue regeneration and working bodies in actuators. The storage modulus and the loss modulus were determined in the oscillatory compression mode as a function of proportions among natural and synthetic polymers. Both moduli substantially increased with the content of CaAlg and PAAm. The electrical (Donnan) potential of hydrogels was measured using the capillary electrode technique. The Donnan potential was negative at all compositions of hydrogels, and its absolute values increased with the content of CaAlg and PAAm.

Echogenic Advantages of Ferrogels Filled with Magnetic Sub-Microparticles.

Ultrasonic imaging of ferrogels (FGs) filled with magnetic nanoparticles does not reflect the inner structure of FGs due to the small size of particles. To determine whether larger particle size would improve the acoustic properties of FGs, biocompatible hydrogels filled with 100-400 nm iron oxide magnetic sub-microparticles with weight fraction up to 23.3% were synthesized and studied. Polymeric networks of synthesized FGs were comprised of chemically cross-linked polyacrylamide with interpenetrating physical network of natural polysaccharide-Guar or Xanthan. Cylindrical samples approximately 10 mm in height and 13 mm in diameter were immersed in a water bath and examined using medical ultrasound (8.5 MHz). The acoustic properties of FGs were characterized by the intensity of reflected echo signal. It was found that the echogenicity of sub-microparticles provides visualization not only of the outer geometry of the gel sample but of its inner structure as well. In particular, the echogenicity of FGs interior depended on the concentration of magnetic particles in the FGs network. The ultrasound monitoring of the shape, dimensions, and inner structure of FGs in the applied external magnetic field is demonstrated. It is especially valuable for the application of FGs in tissue engineering and regenerative medicine.

Magnetic Properties of Iron Oxide Nanoparticles Do Not Essentially Contribute to Ferrogel Biocompatibility.

Two series of composite polyacrylamide (PAAm) gels with embedded superparamagnetic Fe2O3 or diamagnetic Al2O3 nanoparticles were synthesized, aiming to study the direct contribution of the magnetic interactions to the ferrogel biocompatibility. The proliferative activity was estimated for the case of human dermal fibroblast culture grown onto the surfaces of these types of substrates. Spherical non-agglomerated nanoparticles (NPs) of 20-40 nm in diameter were prepared by laser target evaporation (LTE) electrophysical technique. The concentration of the NPs in gel was fixed at 0.0, 0.3, 0.6, or 1.2 wt.%. Mechanical, electrical, and magnetic properties of composite gels were characterized by the dependence of Young's modulus, electrical potential, magnetization measurements on the content of embedded NPs. The fibroblast monolayer density grown onto the surface of composite substrates was considered as an indicator of the material biocompatibility after 96 h of incubation. Regardless of the superparamagnetic or diamagnetic nature of nanoparticles, the increase in their concentration in the PAAm composite provided a parallel increase in the cell culture proliferation when grown onto the surface of composite substrates. The effects of cell interaction with the nanostructured surface of composites are discussed in order to explain the results.

Ferrogels Ultrasonography for Biomedical Applications.

Ferrogels (FG) are magnetic composites that are widely used in the area of biomedical engineering and biosensing. In this work, ferrogels with different concentrations of magnetic nanoparticles (MNPs) were synthesized by the radical polymerization of acrylamide in stabilized aqueous ferrofluid. FG samples were prepared in various shapes that are suitable for different characterization techniques. Thin cylindrical samples were used to simulate the case of targeted drug delivery test through blood vessels. Samples of larger size that were in the shape of cylindrical plates were used for the evaluation of the FG applicability as substitutes for damaged structures, such as bone or cartilage tissues. Regardless of the shape of the samples and the conditions of their location, the boundaries of FG were confidently visualized over the entire range of concentrations of MNPs while using medical ultrasound. The amplitude of the reflected echo signal was higher for the higher concentration of MNPs in the gel. This result was not related to the influence of the MNPs on the intensity of the reflected echo signal directly, since the wavelength of the ultrasonic effect used is much larger than the particle size. Qualitative theoretical model for the understanding of the experimental results was proposed while taking into account the concept that at the acoustic oscillations of the hydrogel, the macromolecular net, and water in the gel porous structure experience the viscous Stocks-like interaction.

The Contribution of Magnetic Nanoparticles to Ferrogel Biophysical Properties.

Iron oxide γ-Fe2O3 magnetic nanoparticles (MNPs) were fabricated by laser target evaporation technique (LTE) and their structure and magnetic properties were studied. Polyacrylamide (PAAm) gels with different cross-linking density of the polymer network and polyacrylamide-based ferrogel with embedded LTE MNPs (0.34 wt.%) were synthesized. Their adhesive and proliferative potential with respect to human dermal fibroblasts were studied. At the same value of Young modulus, the adhesive and proliferative activities of the human dermal fibroblasts on the surface of ferrogel were unexpectedly much higher in comparison with the surface of PAAm gel. Properties of PAAm-100 + γ-Fe2O3 MNPs composites were discussed with focus on creation of a new generation of drug delivery systems combined in multifunctional devices, including magnetic field assisted delivery, positioning, and biosensing. Although exact applications are still under development, the obtained results show a high potential of LTE MNPs to be applied for cellular technologies and tissue engineering. PAAm-100 ferrogel with very low concentration of γ-Fe2O3 MNPs results in significant improvement of the cells' compatibility to the gel-based scaffold.

Effect of cytoskeletal elastic properties on the mechanoelectrical transduction in excitable cells.

This paper addresses the possible mechanism of stretch on cell electrochemical potential change, based on the physicochemical properties of cytoskeletal network. Synthetic polyelectrolyte gel was used as an experimental model of the cytoskeleton. Gel samples with different density of network cross linking were studied. Triangular axial deformations of samples were applied. Simultaneously, the electrochemical (Donnan) potential of the gel was measured between a micropipette electrode pinned into the swollen gel, and a reference electrode in the outer solution. We found that axial deformation shifts the gel potential toward depolarization. The extent of gel depolarization showed a close negative correlation with the Young modulus of the gel. We suggest that the underlying mechanism is likely to be a universal process of counterion adsorption on charged polymer filaments due to the decrease of distance between polymer filaments owing to gel elongation.