Deep eutectic solvents (DESs) represent an emergent class of green designer solvents that find numerous applications in different aspects of chemical synthesis. A particularly appealing aspect of DES systems is their simplicity of preparation, combined with inexpensive, readily available starting materials to yield solvents with appealing properties (negligible volatility, non-flammability and high solvation capacity). In the context of polymer science, DES systems not only offer an appealing route towards replacing hazardous volatile organic solvents (VOCs), but can serve multiple roles including those of solvent, monomer and templating agent—so called “polymerizable eutectics.” In this review, we look at DES systems and polymerizable eutectics and their application in polymer materials synthesis, including various mechanisms of polymer formation, hydrogel design, porous monoliths, and molecularly imprinted polymers. We provide a comparative study of these systems alongside traditional synthetic approaches, highlighting not only the benefit of replacing VOCs from the perspective of environmental sustainability, but also the materials advantage with respect to mechanical and thermal properties of the polymers formed.
We report the preparation of thermoresponsive hydrogels via free-radical polymerization and crosslinking of NIPAM based deep eutectic monomer solvents (DEMs).
Magnetic polymer particles have attracted much attention because of their ubiquitous use in biomedical field such as biomolecule separation, drug carriers, imaging and etc. Iron oxide magnetic nanoparticles were incorporated into temperature responsive poly (N-isopropylacrylamide) (PNIPAAm) polymer hydrogel by a seed polymerization following a surface modification step. Iron oxide magnetic nanoparticles (50-100 nm) prepared by co-precipitation method were modified with silica (SiO 2 ) and 3-(trimethoxysilyl) propyl methacrylate (MPS) to introduce polymerizable vinyl group (−CH=CH 2 ) at the surface of the nanoparticles. Then, the Fe 3 O 4 /SiO 2 /MPS particles were used as seed in polymerization of N-isopropylacrylamide (NIPAAm) and acrylic acid (AA). Here N, N'-methylenebisacrylamide (MBA) and potassium persulphate (KPS) were used as a cross-linker and initiator respectively. Dynamic Light scattering (DLS) results indicated a decrease of hydrodynamic diameter of magnetic Fe 3 O 4 /SiO 2 /MPS/poly (NIPAAm-AA) polymer particles with increasing temperature. Surface functionality and polymer coating, morphology, chemical composition and presence of iron oxide in the magnetic polymer particles were evaluated by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and X-ray diffraction (XRD) respectively. The content of magnetic part was more than 50 wt.% determined by TGA, satisfactory for separation of the final particles from a dispersed media by external magnet. Therefore, the magnetic polymer particles prepared here could be a potential candidate for separation technology.
Functionalized iron oxide nanoparticles (IONPs) have unique physical and chemical properties, which make them potential candidates for biomedical applications. In this study, a facile one-pot method is reported for the preparation of poly(acrylic acid) (PAA) functionalized IONPsthrough in situ free radical solution polymerization of AA and subsequent coprecipitation of Fe 3+ and Fe 2+ ions. The FTIR spectroscopic and TGA results indicated the successful formation and surface functionalization of IONPs with PAA. Electron micrographs showed that the prepared particles were of nano-sized and their shape is dependent on the concentration of PAA. pH-dependent variation of average hydrodynamic diameter confirmed the pH-responsivity of PAA-functionalized IONPs. Magnetic measurement suggested that the PAA functionalized IONPs were strongly paramagnetic (53.0 emug −1 ). Fenton-like catalytic generation is carried out to measure toxicity associated with the nanoparticles. The suppression ability for reactive oxygen species (ROS) generation associated with PAA-functionalized IONPs was studied via methylene blue degradation assay to address their toxicity profile. PAA-functionalized IONPs exhibited better suppression ability than that of the bare IONPs. The adsorption behavior of trypsin was also studied at different pH levels and a maximum adsorption is occurred on PAA-functionalized IONPs at pH 5.0. Catalytic behavior study confirmed higher activity of trypsin immobilized on PAA-functionalized IONPs than that of the reference IONPs. Therefore, the functionalized IONPs can be of high interest for magnetically recyclable biocatalyst carrier.
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