Summary: By incorporation of surface‐modified superparamagnetic nanoparticles into shape memory polymer matrices, remote actuation of complex shape transitions by electromagnetic fields is possible. The composite thermosets of oligo(ε‐caprolactone)dimethacrylate/butyl acrylate contain between 2 and 12 wt.‐% magnetite nanoparticles serving as nanoantennas for magnetic heating. It is shown that the particles are dispersed homogenously within the matrix and that the basic thermal and mechanical properties of the polymer matrix are maintained. The specific loss power of the particles is determined to be 30 W · g−1 at 300 kHz and 5.0 W. During the shape transition at 43 °C, no further temperature increase is observed.
Droplet attraction: Surfactants responsive to magnetic fields are reported for the first time. This new class of magnetic ionic liquid surfactants (MILSs; see picture) shows remarkable effects on surface and interfacial tension and allows access to magneto‐responsive emulsions and new methods of separation, recovery, catalysis, and potential magnetophoretic applications.
Polymer networks showing a thermally induced shape-memory effect were prepared through the crosslinking of oligo(-caprolactone)dimethacrylates under photocuring with or without an initiator. The influence of the molecular weight of the oligo(-caprolactone)dimethacrylates and the initiator concentration on the macroscopic properties of the polymer networks was investigated. The isothermal and nonisothermal crystallization behavior of the polymer networks was evaluated as a basic principle of the functionalization process. Shape-memory properties such as the strain fixity and strain recovery rate were quantified with cyclic thermomechanical tensile experiments for different maximum elongations.
Ultrasmall superparamagnetic Fe(3)O(4) nanoparticles (USIRONs) were synthesized by a novel, easily scalable chemical reduction of colloidal iron hydroxide under hydrothermal conditions. The average crystallite size (5.1 ± 0.5 nm) and good crystallinity of the samples were supported by HR-TEM analysis and the saturation magnetization value (47 emu g(-1)). Vitamin C, used as a chemical reducing agent, also served as a capping agent in the oxidized form (dehydroascorbic acid, DHAA) to impart nanoparticles with exceptional solubility and stability in water, PBS buffer, and cell culture medium. Detailed physicochemical analysis of the USIRON suspensions provided insight into the magnetic ordering phenomena within the colloid, arising from the formation of uniform clusters displaying a hydrodynamic size of 41 nm. Phantom experiments on the contrast agent (clinical 3 T MRI scanner) revealed an enhanced r(2)/r(1) ratio of 36.4 (r(1)= 5 s(-1) mM(-1) and r(2)= 182 s(-1) mM(-1)) when compared to the clinically approved agents. The potential of the DHAA-Fe(3)O(4) nanoparticles as negative contrast agents for MRI with optimal hydrodynamic size for extended blood circulation times was confirmed by strong contrast observed in T(2)- and T(2)*-weighted images. The cell tests performed with primary human immune-competent cells confirmed the excellent biocompatibility of USIRONs.
In this work, we correlate network dynamics, supramolecular reversibility and the macroscopic surface scratch healing behavior for a series of elastomeric ionomers based on an amorphous backbone with varying fractions of carboxylate pendant groups completely neutralized by Na(+), Zn(2+) or Co(2+) as the counter ions. Our results based on temperature dependent dynamic rheology with simultaneous FTIR analysis clearly indicate that the effective supramolecular bond lifetime (τ(b)) is an important parameter to ascertain the ideal range of viscoelasticity for good macroscopic healing. The reversible coordination increased with higher valence metal ions and ionic content. Both rheological and spectroscopic analyses show a decrease in supramolecular assembly with temperature. The temperature dependent τ(b) was used to calculate the activation energy (Ea) of dissociation for the ionic clusters. According to self-healing experiments based on macroscale surface scratching, a supramolecular bond lifetime between 10 and 100 s results in samples with complete surface scratch healing and good mechanical robustness.
Ferrohydrogels are synthesized by incorporation of magnetic CoFe2O4 nanoparticles into a polyacylamide hydrogel network during the polymerization process by utilizing different cross-linking units. Conventional cross-linked ferrohydrogels, using a molecular cross-linker, are compared to those obtained by our new approach where the magnetic particles, surface-functionalized with methacylic groups, serve as sole, multifunctional cross-linkers. Both experimental series are analyzed with regard to their swelling behavior. The novel composite network is examined with respect to the cross-linkage, the network homogeneity, and the network architecture by various experimental techniques.
Little is known about the migration of mesenchymal stem cells (MSCs). Some therapeutic approaches had demonstrated that MSCs were able to regenerate injured tissues when applied from different sites of application. This implies that MSCs are not only able to migrate but also that the direction of migration is controlled. Factors that are involved in the control of the migration of MSCs are widely unknown. The migratory ability of isolated MSCs was tested in different conditions. The migratory capability was examined using Boyden chamber assay in the presence or absence of basic fibroblast growth factor (bFGF), erythropoietin, interleukin-6, stromal cell-derived factor-, and vascular endothelial growth factor. bFGF in particular was able to increase the migratory activity of MSCs through activation of the Akt/protein kinase B (PKB) pathway. The results were supported by analyzing the orientation of the cytoskeleton. In the presence of a bFGF gradient, the actin filaments developed a parallelized pattern that was strongly related to the gradient. Surprisingly, the influence of bFGF was not only an attraction but also routing of MSCs. The bFGF gradient experiment showed that low concentrations of bFGF lead to an attraction of the cells, whereas higher concentrations resulted in repulsion. This ambivalent effect of bFGF provides the possibility to a purposeful routing of MSCs.
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