Controlled dissolution of physically cross-linked locust bean gum - κ-carrageenan hydrogels.

Most hydrogels swell but do not dissolve in water since their chains are tied to each other. Nevertheless, some hydrogels disintegrate under physiological conditions, a property that could be beneficial in emerging applications, including sacrificial materials, 3D bioprinting, and wound dressings. This paper proposes a novel approach to control the dissolution rate of hydrogels based on the integration of kappa carrageenan nanoparticles (KCAR-NPs) into kappa carrageenan (KCAR) and locust bean gum (LBG) hydrogels to obtain a three-component hybrid system. KCAR and LBG are known to have synergistic interactions, where physical interactions and chain entanglements lead to their gelation. We hypothesized that integrating the bulky nanoparticles would disturb the three-dimensional network formed by the polysaccharide chains and enable manipulating the dissolution rate. Compression, water absorption, rheology, and cryo-scanning electron microscopy measurements were performed to characterize the physical properties and structure of the hydrogels. The hybrid hydrogels displayed much faster dissolution rates than a control system without nanoparticles, which did not completely dissolve within 50 days and offered a cutting-edge means to finely adjust hydrogel dissolution through modulation of KCAR and KCAR-NPs concentrations. The new hydrogels also exhibited shear-thinning and self-healing properties resulting from the weak and reversible nature of the physical bonds.

Crosslinking konjac-glucomannan with kappa-carrageenan nanogels: A step toward the design of sacrificial materials.

The challenge in designing sacrificial materials is to obtain materials that are both mechanically stable and easily dissolvable. This research aimed to meet this challenge by fabricating a new polymer-nanogel hydrogel based solely on hydrogen bonds between two polysaccharides. The study focused on hydrogels formed from soluble konjac-glucomannan and nanogels synthesized from kappa-carrageenan. This novel hydrogel exhibited self-healing and shear-thinning properties due to its weak physical interactions. The hydrogel dissolved simultaneously with its swelling. Changes in temperature or nanogel concentration, or the addition of potassium ions, altered the swelling and dissolution rates. Furthermore, adding KCl to the as-prepared hydrogel increased its compression and tensile moduli and its strength. The new formulation opens numerous possibilities as a potential sacrificial material for different applications since it is mechanically stable yet rapidly dissolves in physiological conditions without applying high temperatures or using chelating agents.

Change of colloidal and surface properties of Mytilus edulis foot protein 1 in the presence of an oxidation (NaIO4) or a complex-binding (Cu2+) agent.

Quartz crystal microbalance with dissipation monitoring (QCM-D) was used to study the viscoelastic properties of the blue mussel, Mytilus edulis, foot protein 1 (Mefp-1) adsorbed on modified hydrophobic gold surfaces. The change in viscoelasticity was studied after addition of Cu2+ and Mn2+, which theoretically could induce metal complex formation with 3,4-dihydroxyphenylalanine (DOPA) moieties. We also used NaIO4, a nonmetal oxidative agent known to induce di-DOPA formation. Reduction in viscoelasticity of adsorbed Mefp-1 followed the order of NaIO4 > Cu2+ > buffer control > Mn2+. We also studied the formation of molecular aggregates of Mefp-1 in solution with the use of dynamic light scattering (DLS). We found that addition of Cu2+, but not Mn2+, induced the formation of larger DLS-detectable aggregates. Minor aggregate formation was found with NaIO4. With the analytical resolution of small angle X-ray scattering (SAXS), we could detect differences in the molecular structure between NaIO4- and Cu2+-treated Mefp-1 aggregates. We concluded from this study that Cu2+ could participate in intermolecular cross-linking of the Mefp-1 molecule via metal complex formation. Metal incorporation in the protein most likely increases the abrasion resistance of the Mefp-1 layer. NaIO4, on the other hand, resulted in mainly intramolecular formation of di-DOPA, but failed to induce larger intermolecular aggregation phenomena. The described methodological combination of surface sensitive methods, like QCM-D, and bulk sensitive methods, like DLS and SAXS, generates high resolution results and is an attractive platform to investigate intra- and intermolecular aspects of assembly and cross-linking of the Mefp proteins.

Ligand accessibility as means to control cell response to bioactive bilayer membranes.

We report a new method to create a biofunctional surface in which the accessibility of a ligand is used as a means to influence the cell behavior. Supported bioactive bilayer membranes were created by Langmuir-Blodgett (LB) deposition of either a pure poly(ethylene glycol) (PEG) lipid, having PEG head groups of various lengths, or 50 mol % binary mixtures of a PEG lipid and a novel collagen-like peptide amphiphile on a hydrophobic surface. The peptide amphiphile contains a peptide synthetically lipidated by covalent linkage to hydrophobic dialkyl tails. The amphiphile head group lengths were determined using neutron reflectivity. Cell adhesion and spreading assays showed that the cell response to the membranes depends on the length difference between head groups of the membrane components. Cells adhere and spread on mixtures of the peptide amphiphile with the PEG lipids having PEG chains of 120 and 750 molecular weight (MW). In contrast, cells adhered but did not spread on the mixture containing the 2000 MW PEG. Cells did not adhere to any of the pure PEG lipid membranes or to the mixture containing the 5000 MW PEG. Selective masking of a ligand on a surface is one method of controlling the surface bioactivity.