Preparation and Characterization of a Coordination Polymer Based on Iron (III)-Cyamelurate as a Superior Catalyst for Heterogeneous Fenton-Like Processes.

We report on a new iron (iii)-cyamelurate-based coordination polymer. The new material based on a heptazine derivative was prepared in aqueous medium and characterized by a variety of techniques including TGA, FTIR, XRD, HRTEM, and STEM. Due to the high structural stability of the complex in aqueous media, its heterogeneous Fenton-like catalytic activity was evaluated using a model molecule. The results obtained showed a high catalytic activity in both in basic and acid media. The pseudo-first-order rate constants normalized by iron(III) concentrations was approximately 1000 times higher than the result obtained for traditional heterogeneous catalysts based on iron(III) oxyhydroxides. The best observed catalytic activities were attributed to the increase in the binding sites of Fe3+ ions, in parallel with the increased exposure of the catalytic sites, leading to a higher atomic efficiency of the reaction.

Iron Oxide Nanomaterials for the Removal of Cr(VI) and Pb(II) from Contaminated River After Mariana Mining Disaster.

If not properly treated, water contaminated with chromium (Cr(VI)) and lead (Pb(II)) can cause severe damage to health due to the accumulation of those toxic metals in the human body. Therefore, in this work, three iron oxides, i.e., δ-FeOOH, cystine-functionalized δ-FeOOH (Cys-δ-FeOOH), and Fe3O4, were synthesized and used as adsorbents for Cr(VI) and Pb(II) in water. The results indicated that the Cr(VI) is best adsorbed on cys-δ-FeOOH followed by δ-FeOOH and Fe3O4. It was because of the enhanced interaction between Cr(VI) and the cysteine functional groups on the δ-FeOOH surface. The Cr(VI) adsorption capacity of cys-δ-FeOOH, δ-FeOOH, and Fe3O4 was 217, 14, and 8 mg g-1, respectively. On the other hand, Pb(II) was preferentially adsorbed directly on δ-FeOOH achieving a maximum Pb(II) adsorption capacity of 174 mg g-1. The Pb(II) adsorption capacity of cys-δ-FeOOH and Fe3O4 was 97 and 74 mg g-1, respectively. The Cr(VI) adsorption on cys-δ-FeOOH was best described by the Langmuir-Freundlich model, whereas Pb(II) adsorption on δ-FeOOH followed the Langmuir model. Both Cr(VI) and Pb(II) adsorption on the adsorbents was well-fitted to pseudo-second-order kinetics. The Cr(VI) was more quickly adsorbed by cys-δ-FeOOH (h0 = 0.10 mg g-1 min-1) while the initial adsorption rate of Pb(II) onto δ-FeOOH was significantly faster (h0 = 16.34 mg g-1 min-1). Finally, the synthesized adsorbents were efficient to remove Cr(VI) and Pb(II) from water samples of the Doce river after the environmental disaster of Mariana city, Brazil, thus showing its applicability to remediate real water samples.

Removal of mercury(II) from contaminated water by gold-functionalised Fe3O4 magnetic nanoparticles.

Fe3O4 nanoparticles were prepared by co-precipitation of Fe2+ and Fe3+ and then modified with Au to produce an effective adsorbent (Fe3O4/Au) for aqueous Hg(II) in contaminated water. Rietveld refinement on the XRD pattern confirmed that the Fe3O4/Au was synthesised. Mössbauer spectra exhibited broad and asymmetric resonance lines with two sextets which can be assigned to tetrahedral Fe3+; and octahedral Fe3+/Fe2+. The quantitative analysis of magnetite confirms that the sample shows around 3 wt.% Au and 97 wt.% partially oxidised Fe3O4. High surface area: 121 m2 g-1, average pore sizes: 6.3 nm and pore volume: 1.64 cm3 g-1. The kinetics data were better fitted with a pseudo-second-order and Dubinin-Radushkevich isotherm suggests the Hg(II) adsorption onto Fe3O4/Au nanoparticles was mainly by chemical adsorption forming complex with the Au metal immobilised on Fe3O4 surfaces. Adsorption capacity of 79.59 mg g-1. Ionic strength and co-existing ions had a slight influence on the adsorption capacity.

A perspective of mitochondrial dysfunction in rats treated with silver and titanium nanoparticles (AgNPs and TiNPs).

Nanotechnology is a growing branch of science that deals with the development of structural features bearing at least one dimension in the nano range. More specifically, nanomaterials are defined as objects with dimensions that range from 1 to 100 nm, which give rise to interesting properties. In particular, silver and titanium nanoparticles (AgNPs and TiNPs, respectively) are known for their biological and biomedical properties and are often used in consumer products such as cosmetics, food additives, kitchen utensils, and toys. This situation has increased environmental and occupational exposure to AgNPs and TiNPs, which has placed demand for the risk assessment of NPs. Indeed, the same properties that make nanomaterials so attractive could also prove deleterious to biological systems. Of particular concern is the effect of NPs on mitochondria because these organelles play an essential role in cellular homeostasis. In this scenario, this work aimed to study how AgNPs and TiNPs interact with the mitochondrial respiration chain and to analyze how this interaction interferes in the bioenergetics and oxidative state of the organelles after sub-chronic exposure. Mitochondria were exposed to the NPs by gavage treatment for 21 days to check whether co-exposure of the organelles to the two types of NPs elicited any mitochondrion-NP interaction. More specifically, male Wistar rats were randomly assigned to four groups. Groups I, II, III, and IV received mineral oil, TiNPs (100 µg/kg/day), AgNPs (100 µg/kg/day), and TiNPs + AgNPs (100 µg/kg/day), respectively, by gavage. The liver was immediately removed, and the mitochondria were isolated and used within 3 h. Exposure of mitochondria to TiNPs + AgNPs lowered the respiratory control ratio, causing an uncoupling effect in the oxidative phosphorylation system. Moreover, both types of NPs induced mitochondrial swelling. Extended exposure of mitochondria to the NPs maintained increased ROS levels and depleted the endogenous antioxidant system. The AgNPs and TiNPs acted synergistically-the intensity of the toxic effect on the mitochondrial redox state was more significant in the presence of both types of NPs. These findings imply that the action of the NPs on mitochondria underlie NP toxicity, so future application of NPs requires special attention.

Controlling the morphology and pore size of mesostructured silica nanoparticles: the role of the iron oxidation state.

We demonstrate morphology and pore size dependence of silica nanoparticles (SNPs) synthesized via control of the iron oxidation state. In the absence of any Fe species, only spherical SNPs are produced, whereas in the presence of Fe³âº and Fe²âº ions, SNPs with rod-like and nanosheet morphologies, respectively, are formed. The average pore size increases from 1.7 nm in the absence of iron to 3.2 and 5.9 nm as Fe³âº and Fe²âº, respectively, were used during the synthesis. Both samples of SNPs synthesized in the presence of Fe²âº and Fe³âº have 0.2 wt% of tetrahedral iron in the silica framework, whereas most of the iron is in the silica extraframework, as verified by Mössbauer spectroscopy, UV-vis diffuse reflectance, FTIR, XRD data and TPR analysis. These Fe²âº and Fe³âº cations play a fundamental role in controlling these properties because they change the curvature and the surface charge density of CTAB micelles, thus favoring the spherical to rod-like transition. The rod-like shape was retained in Fe-containing samples, whereas a nanosheet-like morphology was produced in Fe²âº-containing samples due to the breakage of silica walls during the thermal treatment to remove the template. The control of the textural properties is interesting to allow the fabrication of selective photocatalysts for oxidation of different organic substrates.