Influence of magnetite incorporation into chitosan on the adsorption of the methotrexate and in vitro cytotoxicity.

Emerging pollutants are a group of substances involved in environmental contamination resulting mostly from incomplete drug metabolism, associated with inadequate disposal and ineffective effluent treatment techniques. Methotrexate (MTX), for instance, is excreted at high concentrations in unchanged form through the urine. Although the MTX is still effective in cancer and autoimmune disease treatment, this drug shows the ability of bioaccumulation and toxicity to the organism. Thus, the present work aimed to evaluate the adsorption of the MTX drug onto magnetic nanocomposites containing different amounts of incorporated magnetite (1:1, 1:5, and 1:10 wt%), combining the theoretical-experimental study as well as the in vitro cytotoxicity. Moreover, equilibrium studies (Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, Hill, Redlich-Peterson, and Sips), kinetic (PFO, PSO, and IPD), and thermodynamic (ΔG°, ΔH°, and ΔS°) were used to describe the experimental data, and ab initio simulations were employed in the theoretical study. Magnetic nanocomposites were synthesized by the co-precipitation method using only FeCl2 as the iron precursor. Adsorbents were characterized by FTIR, XRD, Raman, SEM-EDS, BET, and VSM analysis. Meanwhile, cytotoxic effects on L929 and A375 cell lines were evaluated through MTT, NR, and LDH assays. The adsorption of the MTX was carried out in a typical batch system, exploring the different experimental conditions. The theoretical study suggests the occurrence of chemisorption between CS·Fe3O4-MTX. The maximum adsorption capacity of MTX was 285.92 mg g-1, using 0.125 g L-1 of CS·Fe3O4 1:1, with an initial concentration of the MTX (50 mg L-1), pH 4.0 at 293 ± 1.00 K. The best adjustment of equilibrium and kinetic data were the Sips (low values for statistical errors) and PSO (qe = 96.73 mg g-1) models, respectively. Thermodynamic study shows that the adsorption occurred spontaneously (ΔG° < 0), with exothermic (ΔH° = - 4698.89 kJ mol-1) and random at the solid-solution interface (ΔS° = 1,476,022.00 kJ mol-1 k-1) behavior. Finally, the in vitro study shows that magnetic nanomaterials exhibit higher cytotoxicity in melanoma cells. Therefore, the magnetic nanocomposite reveals to be not only an excellent tool for water remediation studies but also a promising platform for drug delivery.

Adhesion to Y-TZP ceramic: study of silica nanofilm coating on the surface of Y-TZP.

This study evaluated the influence of silica-based film coatings on the surface of yttrium-stabilized tetragonal zirconia polycrystal (Y-TZP), in particular on the durability of the bond strength between the ceramic and resin cement. Eighty Y-TZP (In-Ceram YZ, Vita) blocks (4 × 4 × 3 mm) were obtained and divided into four groups according to the surface treatments (n = 20): tribochemical silica coating (TBS; Cojet, 3M/ESPE), 5 nm SiO2 nanofilm and silanization (F-5), 500 nm SiO2 nanofilm and silanization (F-500), and 500 nm SiO2 nanofilm + hydrofluoric-acid-etching + silanization (F-500HF). Specimens of composite resin (3.25 mm in diameter and 3 mm in height) were cemented to Y-TZP blocks using resin cement (Relyx ARC). Half of the specimens from each group were tested 24 h after adhesion (B: baseline condition), and the other half were subjected to aging (A: storage for 90 days and 10,000 thermal cycles). The specimens were subjected to shear testing (SBS) (1 mm/min). After testing, the surfaces were analyzed with a stereomicroscope and scanning electron microscope. Micromorphologic and elemental chemical analyses of the treated Y-TZP surface were made by X-ray energy dispersive spectroscopy. Bond strength data were statistically analyzed by Kruskal-Wallis/Mann-Whitney tests (α = 0.05). The surface treatment showed significant differences for B (p = 0.0001) and A (p = 0.0000) conditions. In both storage conditions, TBS and F-5 groups promoted the significantly highest bond strength. Most of the specimens presented adhesive failure. The X-ray energy dispersive spectroscopy analysis depicted the highest peak of silica in the TBS, F-5, and F-500 groups. The adhesion to zirconia can be improved if the surface receives a 5 nm layer of SiO2 nanofilm or is subjected to sandblasting with silica particles, followed by silanization.