Highly efficient removal of mercury(II) ions (Hg(II)) from water has been reported by employing polymer-brush-functionalized magnetic nanoparticles (MNPs). Surface-initiated conventional radical polymerization (SI-cRP) was used to grow poly(2-aminoethyl methacrylate hydrochloride) (poly-AEMA·HCl) polymer chains on magnetite nanoparticles (Fe3O4), followed by the transformation of pendant amino groups into dithiocarbamate (DTC) groups, which showed high chelating affinity toward Hg(II) ions. This polymer-brush-based DTC-functionalized MNP (MNPs-polyAEMA·DTC) platform showed the complete removal of Hg(II) from aqueous solutions. The Hg(II) ion removal capacity and efficiency of MNPs-polyAEMA·DTC were compared with its monolayer analogue, which was derived from the direct transformation of amino groups of (3-aminopropyl) triethoxysilane (APTES)-functionalized MNPs (MNPs-APTES) to DTC functional groups (MNPs-DTC). The surface chemical modifications and higher chelating functional group density, in the case of MNPs-polyAEMA·DTC, were ascertained by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), physical property measurement system (PPMS), attenuated total reflectance infrared (ATR-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The Hg(II) ion removal capacity and efficiency of monolayer and polymer-brush-based DTC-functionalized MNPs (MNPs-DTC and MNPs-polyAEMA·DTC, respectively) were evaluated and compared by studying the effect of various factors on the percentage removal of Hg(II) such as adsorbent amount, temperature, and contact time. Furthermore, the adsorption behavior of MNPs-DTC and MNPs-polyAEMA·DTC was analyzed by applying Langmuir and Freundlich adsorption isotherm models. In addition, the adsorption thermodynamics, as well as the adsorption kinetics, were also evaluated in detail. The higher surface functional group density of MNPs-polyAEMA·DTC led to superior remediation characteristics toward Hg(II) ions than its monolayer analogue.
The amalgamation of natural polysaccharides with synthetic polymers often produces fruitful results in the area of drug delivery due to their biodegradable and biocompatible nature. In this study, a series of blend films composed of chitosan (CS)/poly(allylamine hydrochloride) (PAH) in different compositions were prepared as smart drug delivery matrices. The properties of these polymeric films were then explored. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) analysis confirmed an intermolecular hydrogen bonding between CS and PAH. Atomic force microscopy (AFM) revealed improvements in surface morphology as the percentage of PAH in the blend films increased up to 60% (w/w). Water contact angle (WCA) ranged between 97° to 115°, exhibiting the hydrophobic nature of the films. Two films were selected, CTH-1 (90% CS and 10% PAH) and CTH-2 (80% CS and 20% PAH), to test for in vitro cumulative drug release (%) at 37 ± 0.5 °C as a function of time. It was revealed that for simulated gastric fluid (SGF) with pH 1.2, the cumulative drug release (CDR) for CTH-1 and CTH-2 was around 88% and 85% in 50 min, respectively. Both films converted into gel-like material after 30 min. On the other hand, in pH 7.4 phosphate buffer saline (PBS) solution, the maximum CDR for CTH-1 and CTH-2 was 93% in 90 min and 98% in 120 min, respectively. After 120 min, these films became fragments. Sustained drug release was observed in PBS, as compared to SGF, because of the poor stability of the films in the latter. These results demonstrate the excellent potential of blend films in sustained-release drug delivery systems for hydrophilic or unstable drugs.
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