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A three dimensional biopolymer network structure with incorporated nano-porous calcium phosphate (CaP) balls was fabricated by using gelatin-chitosan (GC) polymer blend and GC stabilized olive/silicone oil Janus emulsions, respectively. The emulsions were freeze-dried, and the oil droplets were washed out in order to prepare porous scaffolds with larger surface area. The morphology, pore size, chemical composition, thermal and swelling behavior was studied by Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR) and micro-Differential Scanning Calorimetry (micro-DSC). Microscopic analysis confirmed that the pore size of the GC based sponges after freeze-drying may be drastically reduced by using Janus emulsions. Besides, the incorporation of nanoporous calcium phosphate balls is also lowering the pore size and enhancing thermal stability. (C) 2016 Elsevier B.V. All rights reserved.
Janus emulsions, formed by mixing two oil components (i.e., olive oil (OO) and silicone oil (SiO)) with water in the presence of two surface active biopolymers, i.e., gelatin and chitosan, are investigated in more detail. The stability of Janus droplets formed strongly depends on the polymer components used. The mixture of both biopolymers represents an extraordinary effect which can be related to the complex formation of gelatin and chitosan. Taken into account that under the given pH conditions, in the acidic pH range between 4 and 6, below the isoelectric point of gelatin, both polymers are polycations, one can conclude that non-Coulombic interactions are of relevance for the enhanced surface activity of the complexes. Dynamic interfacial tension (gamma) measurements by using the drop profile analysis tensiometry (PAT) indicate a strong adsorption of the polymer complexes at the olive oil/water interface in contrast to the silicone/water interface. In a first step, the polymer complexes are adsorbed at the interface, and in a second step, a more rigid skin-like polymer layer is formed. This first example of a polymer-stabilized Janus emulsion opens new perspectives for the application, e.g., in food emulsions or for making scaffold materials.
Janus emulsions, containing olive oil (OO) and silicone oil (SiO), were formed in presence of polyelectrolyte complex particles, i.e., gelatin-sodium polyacrylate (NaPAA) complexes. The diameter of completely engulfed Janus droplets can be tuned between 50 and 200 mu m by varying the gelatin/NaPAA complex particle size between 200 and 400 nm. The gelatin/NaPAA complex particles adsorbed at the olive oil interface decrease the interfacial tension and stabilize the resulting completely engulfed Pickering Janus emulsions. Long-term stable Janus gels can be synthesized in presence of gelatin/sodium carboxymethylcellulose (NaCMC) mixtures. In that case Coulombic forces are of relevance with regard to the stabilization of the Janus droplets embedded in a gelatin/NaCMC gel matrix. Janus gels show elastic reological behavior and thixotropic properties.