Core-shell microgels were synthesized via a free radical emulsion polymerization of thermoresponsive poly-(N-isopropyl acrylamide), pNipam, on the surface of silica nanoparticles. Pure pNipam microgels have a lower critical solution temperature (LCST) of about 32 °C. The LCST varies slightly with the crosslinker density used to stabilize the gel network. Including a silica core enhances the mechanical robustness. Here we show that by varying the concentration gradient of the crosslinker, the thermoresponsive behaviour of the core-shell microgels can be tuned. Three different temperature scenarios have been detected. First, the usual behaviour with a decrease in microgel size with increasing temperature exhibiting an LCST; second, an increase in microgel size with increasing temperature that resembles an upper critical solution temperature (UCST), and; third, a decrease with a subsequent increase of size reminiscent of the presence of both an LCST, and a UCST. However, since the chemical structure has not been changed, the LCST should only change slightly. Therefore we demonstrate how to tune the particle size independently of the LCST.
Magnetic hyperthermia is a technique that describes the heating of material through an external magnetic field. Classic hyperthermia is a medical condition where the human body overheats, being usually triggered by a heat stroke, which can lead to severe damage to organs and tissue due to the denaturation of cells. In modern medicine, hyperthermia can be deliberately induced to specified parts of the body to destroy malignant cells. Magnetic hyperthermia describes the way that this overheating is induced and it has the inherent advantage of being a minimal invasive method when compared to traditional surgery methods. This work presents a particle system that offers huge potential for hyperthermia treatments, given its good loss value, i.e., the particles dissipate a lot of heat to their surroundings when treated with an ac magnetic field. The measurements were performed in a low-cost custom hyperthermia setup. Additional toxicity assessments on Jurkat cells show a very low short-term toxicity on the particles and a moderate low toxicity after two days due to the prevalent health concerns towards nanoparticles in organisms.
16 August 2024 in The Journal of Physical Chemistry C
Goethite is a naturally anisotropic, antiferromagnetic iron oxide. Following its atomic structure, crystals grow into a fine needle shape that has interesting properties in a magnetic field. The needles align parallel to weak magnetic fields and perpendicular when subjected to high fields. We synthesized goethite nanorods with lengths between 200 nm and 650 nm in a two-step process. In a first step we synthesized precursor particles made of akaganeite (β-FeOOH) rods from iron(III)chloride. The precursors were then treated in a hydrothermal reactor under alkaline conditions with NaOH and polyvinylpyrrolidone (PVP) to form goethite needles. The aspect ratio was tunable between 8 and 15, based on the conditions during hydrothermal treatment. The orientation of these particles in a magnetic field was investigated by small angle X-ray scattering (SAXS). We observed that the field strength required to trigger a reorientation is dependent on the length and aspect ratio of the particles and could be shifted from 85 mT for the small particles to about 147 mT for the large particles. These particles could provide highly interesting magnetic properties to nanocomposites, that could then be used for sensing applications or membranes.
In this study, a triblock copolymer was used as additive to fabricate new dual layer hollow fiber membranes with a hydrophilic active inner surface in order to improve their fouling resistance. The polymeric components of the solutions for membrane fabrication were poly(ether sulfone), poly(N-vinyl pyrrolidone), and the triblock copolymer. The additive consists of three blocks: a middle hydrophobic poly(ether sulfone) block and two outer hydrophilic alkyl poly(ethylene glycol) blocks. By varying the additive concentration in the solutions, it was possible to fabricate dual layer hollow fiber membranes that are characterized by a hydrophilic inner layer, a pure water permeance of over 1800 L/(m2 bar h) and a molecular weight cut-off of 100 kDa similar to commercial membranes. Contact angle and composition determination by XPS measurements revealed the hydrophilic character of the membranes, which improved with increasing additive concentration. Rheological, dynamic light scattering, transmission, and cloud point experiments elucidated the molecular interaction, precipitation, and spinning behavior of the solutions. The low-molecular weight additive reduces the solution viscosity and thus the average relaxation time. On the contrary, slow processes appear with increasing additive concentration in the scattering data. Furthermore, phase separation occurred at a lower non-solvent concentration and the precipitation time increased with increasing additive content. These effects revealed a coupling mechanism of the triblock copolymer with poly(N-vinyl pyrrolidone) in solution. The chosen process parameters as well as the additive solutions provide an easy and inexpensive way to create an antifouling protection layer in situ with established recipes of poly(ether sulfone) hollow fiber membranes. Therefore, the membranes are promising candidates for fast integration in the membrane industry.