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Ionically, cross-linked alginate gels have a potential to be used in a wide range of biomedical, environmental and catalytic applications. The study deals with preparation of alginate hydrogels cross-linked with various cations and the analysis of their equilibrium swelling and mechanical properties. It is shown that the type of cations used in the cross-linking process affects the elastic moduli and the equilibrium degree of swelling of the gels. The experimental data in small-amplitude oscillatory tests are fitted with a model that involves two material parameters: the elastic modulus of a polymer network and a measure of its inhomogeneity. The influence of cations on these quantities is studied numerically. It is revealed that the dependence of the elastic modulus of ionically cross-linked alginate gels on their equilibrium degree of swelling differs from that predicted by the conventional theory for covalently cross-linked gels.
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Alginate organohydrogels prepared in water/alcohol mixtures play an important role in electronic and superconductor applications in low-temperature environments. The study deals with the preparation of Ca-alginate organohydrogels and the analysis of their equilibrium swelling and mechanical properties at sub-zero temperatures. It is shown that the equilibrium degree of swelling at room temperature is noticeably affected by the concentration of co-solvents (methanol, ethanol, and 2-propanol) in the mixtures and the number of carbon atoms in the co-solvent molecules. Mechanical properties are studied in small-amplitude oscillatory tests. The data are fitted with a model that involves three material parameters. The influence of temperature is investigated in temperature-sweep oscillatory tests under a cooling-heating program, where a noticeable difference is observed between the storage and loss moduli under cooling and heating (the hysteresis curves). The hysteresis areas are affected by the cooling/heating rate and the number of carbon atoms in the co-solvents.
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A new two-step method is suggested for the preparation of homogeneous alginate gels. In the first step, alginate chains are weakly bonded by Ca2+ ions in an aqueous solution with a low pH. In the next step, the gel is immersed into a strong solution of CaCl2 to finalize the cross-linking process. Homogeneous alginate gels preserve their integrity in aqueous solutions with a pH ranging from 2 to 7 and ionic strength in the interval from 0 to 0.2 M, at temperatures ranging from room temperature up to 50 °C, and can be used in biomedical applications. The immersion of these gels into aqueous solutions with low pH induces the partial breakage of ionic bonds between chains (treated as gel degradation). This degradation affects the equilibrium and transient swelling of homogeneous alginate gels and makes them sensitive to the history of loading and environmental conditions (pH, ionic strength and temperature of aqueous solutions). As sensitivity to the environmental stimuli is a characteristic feature of polymer networks connected by catch bonds, homogeneous alginate gels may serve as a simple model, mimicking the behavior of more sophisticated structures in living matter.
Assuntos
Alginatos , Hidrogéis , Alginatos/química , Géis , Hidrogéis/química , Íons , TemperaturaRESUMO
The processes of growth, proliferation and differentiation of stem cells encapsulated in 3D hydrogel microenvironments are strongly affected by the viscoelastic properties of the platforms. As the viscoelastic response of a hydrogel is determined by the rates of thermally induced dissociation of reversible cross-links, its modulation by introduction of several types of supramolecular and/or dynamic covalent bonds with different characteristic lifetimes has recently become a hot topic. To reduce the number of experiments needed for design of hydrogel microenvironments with required mechanical properties, a model is developed for the viscoelastic and viscoplastic responses of hydrogels with multiple networks bridged by covalent and physical bonds. An advantage of the model is that it (i) involves a small number of material parameters, (ii) describes observations in rheological and mechanical tests in a unified manner, and (iii) predicts conventional measures of viscoelasticity used in the analysis of viability of cells.
Assuntos
Hidrogéis , Células-Tronco , Diferenciação Celular , Hidrogéis/química , ViscosidadeRESUMO
Copolymer gels prepared by polymerization of thermo-responsive and anionic monomers demonstrate strong sensitivity to several triggers such as temperature, pH and ionic strength of aqueous solutions. For biomedical applications of these materials (as on-off switches in controlled drug delivery and release), fine tuning of their volume phase transition temperature (VPTT) and a sharp decay in degree of swelling upon transition from the swollen to the collapsed state are needed. These requirements are fulfilled under swelling of copolymer gels and microgels in water under acidic conditions, but are violated when tests are conducted under alkaline conditions or in aqueous solutions of salts with physiological salinity. A model is developed for equilibrium swelling of multi-stimuli-responsive copolymer gels in aqueous solutions with arbitrary pH and molar fractions of a monovalent salt. Unlike conventional approaches, the model accounts for secondary interactions between chains (hydrogen bonding) to describe the kinetics of aggregation of hydrophobic segments above VPTT. Material constants are determined by fitting experimental swelling diagrams on poly(N-isopropylacrylamide-co-sodium acrylate) gels with various molar fractions of ionic monomers. The effects of temperature, pH and molar fraction of salt on the equilibrium degree of swelling below and above VPTT are studied numerically.
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Polímeros , Géis , Transição de Fase , Temperatura , Temperatura de TransiçãoRESUMO
Because of the bioactivity and biocompatibility of protein-based gels and the reversible nature of bonds between associating coiled coils, these materials demonstrate a wide spectrum of potential applications in targeted drug delivery, tissue engineering, and regenerative medicine. The kinetics of rearrangement (association and dissociation) of the physical bonds between chains has been traditionally studied in shear relaxation tests and small-amplitude oscillatory tests. A characteristic feature of recombinant protein gels is that chains in the polymer network are connected by temporary bonds between the coiled coil complexes and permanent cross-links between functional groups of amino acids. A simple model is developed for the linear viscoelastic behavior of protein-based gels. Its advantage is that, on the one hand, the model only involves five material parameters with transparent physical meaning and, on the other, it correctly reproduces experimental data in shear relaxation and oscillatory tests. The model is applied to study the effects of temperature, the concentration of proteins, and their structure on the viscoelastic response of hydrogels.