Brønsted-acid sites promoted degradation of phthalate esters over MnO2: Mineralization enhancement and aquatic toxicity assessment.

Advanced oxidation processes (AOPs) are important technologies for aqueous organics removal. Despite organic pollutants can be degraded via AOPs generally, high mineralization of them is hard to achieve. Herein, we synthesized a manganese oxide nanomaterial (H2-OMS-2) with abundant Brønsted-acid sites via ion-exchange of cryptomelane-type MnO2 (OMS-2), and tested its catalytic performance for the degradation of phthalate esters via peroxymonosulfate (PMS) activation. About 99% of dimethyl phthalate (DMP) at a concentration of 20 mg/L could be degraded within 90 min and 82% of it could be mineralized within 180 min over 0.6 g/L of catalyst and 1.8 g/L of PMS. The catalyst could activate PMS to generate SO4-˙ and ·OH as the dominant reactive oxygen species to reach complete degradation of DMP. Especially, the higher TOC removal rate was obtained due to the rich Brønsted-acid sites and surface oxygen vacancies on the catalyst. Kinetics and mechanism study showed that MnII/MnIII might work as the active sites during the catalytic process with a lower reaction energy barrier of 55.61 kJ/mol. Furthermore, the catalyst could be reused for many times through the regeneration of the catalytic ability. The degradation and TOC removal efficiencies were still above 98% and 65% after seven consecutive cycles, respectively. Finally, H2-OMS-2-catalyzed AOPs significantly reduced the organismal developmental toxicity of the DMP wastewater through the investigation of zebrafish model system. The present work, for the first time, provides an idea for promoting the oxidative degradation and mineralization efficiencies of aqueous organic pollutants by surface acid-modification on the catalysts.

Reductant free green synthesis of magnetically recyclable MnFe2O4@SiO2-Ag coreshell nanocatalyst for the direct reduction of organic dye pollutants.

The present paper describes in situ green immobilization of silver nanoparticles on MnFe2O4@SiO2 nanospheres using Epilobium parviflorum (EP) without using any other toxic chemicals and reducing or stabilizing agents. The morphology, composition, and magnetic properties of the resulting MnFe2O4@SiO2-Ag core-shell nanocatalyst were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). The catalytic performance of the synthesized MnFe2O4@SiO2-Ag was employed on the organic pollutants dyes such as rhodamine B (RhB) and methylene blue (MB). The results revealed significant reduction performances for the MB (116.28 s-1 g-1) and RhB (27.12 s-1 g-1) over the existing literature. Furthermore, the MnFe2O4@SiO2-Ag exhibited high stability for the completion of the reduction of RhB between the reaction times of 13.1 (first) and 19.8 min (final) with the 100% decolorization efficiency even after several cycles with an excellent magnetic separation. Overall, this work demonstrates a simple and practical green synthetic route for the preparation of magnetic recyclable core-shell nanocatalyst that can be a good candidate for the treatment of organic contaminants in wastewater adhering to green chemistry principles for the environmental pollution concerns.

Poly(amidoamine) dendrimer-coated magnetic nanoparticles for the fast purification and selective enrichment of glycopeptides and glycans.

Glycosylated proteins modulate various important functions of organisms. To reveal the functions of glycoproteins, in-depth characterization studies are necessary. Although mass spectrometry is a very efficient tool for glycoproteomic and glycomic studies, efficient sample preparation methods are required prior to analyses. In the study, poly(amidoamine) dendrimer-coated magnetic nanoparticles were presented for the specific enrichment and fast purification of glycopeptides and glycans. The enrichment and purification performance of the developed method was evaluated both at the glycopeptide, and the glycan level using several standard glycoprotein digests and released glycan samples. The poly(amidoamine) dendrimer-coated magnetic nanoparticles not only showed selective affinity (Immunoglobulin G/Bovine Serum Albumin, 1/10 by weight) to glycopeptides and released glycans but also good sensitivity (0.4 ng/µL for Immunoglobulin G) for glycoproteomic and glycomic applications. Thirty-five glycopeptides of Immunoglobulin G were detected after enrichment with poly(amidoamine) dendrimer-coated magnetic nanoparticles. In addition, 55 18 O tagged deamidated glycopeptides belonging to human plasma glycoproteome were confirmed. Finally, fifty 2-aminobenzoic acid, and 30 procainamide-labelled human plasma N-glycans released from human plasma glycoproteins were determined after purifications. The results indicate that the proposed enrichment and purification method using poly(amidoamine) dendrimer-coated magnetic nanoparticles could be simply adjusted to sample preparation methods.

Water oxidation catalysis by birnessite@iron oxide core-shell nanocomposites.

In this work, magnetic nanocomposite particles were prepared for water oxidation reactions. The studied catalysts consist of maghemite (γ-Fe2O3), magnetite (Fe3O4), and manganese ferrite (MnFe2O4) nanoparticles as cores coated in situ with birnessite-type manganese oxide shells and were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermal, chemical, and surface analyses, and magnetic measurements. The particles were found to be of nearly spherical core-shell architectures with average diameter of 150 nm. Water oxidation catalysis was examined using Ce(4+) as the sacrificial oxidant. All core-shell particles were found to be active water oxidation catalysts. However, the activity was found to depend on a variety of factors like the type of iron oxide core, the structure and composition of the shell, the coating characteristics, and the surface properties. Catalysts containing magnetite and manganese ferrite as core materials displayed higher catalytic activities per manganese ion (2650 or 3150 mmolO2 molMn(-1) h(-1)) or per mass than nanoiron oxides (no activity) or birnessite alone (1850 mmolO2 molMn(-1) h(-1)). This indicates synergistic effects between the MnOx shell and the FeOx core of the composites and proves the potential of the presented core-shell approach for further catalyst optimization. Additionally, the FeOx cores of the particles allow magnetic recovery of the catalyst and might also be beneficial for applications in water-oxidizing anodes because the incorporation of iron might enhance the overall conductivity of the material.