Hydrothermal Synthesis and Properties of Nanostructured Silica Containing Lanthanide Type Ln-SiO2 (Ln = La, Ce, Pr, Nd, Eu, Gd, Dy, Yb, Lu).

The nanostructured lanthanide-silica materials of the Ln-SiO2 type (Ln = La, Ce, Pr, Nd, Eu, Gd, Dy, Yb, Lu) were synthesized by the hydrothermal method at 100 °C, using cetyltrimethylammonium as a structural template, silica gel and sodium silicate as a source of silicon, and lanthanide oxides, with Si/Ln molar ratio = 50. The resulting materials were calcined at 500 °C using nitrogen and air, and characterized by X-ray diffraction (XRD), Fourier-Transform infrared absorption spectroscopy, scanning electron microscopy, thermogravimetry (TG), surface area by the BET method and acidity measurements by n-butylamine adsorption. The XRD and chemical analysis indicated that the SiO2 presented a hexagonal structure and the incorporation of lanthanides in the structure changes the properties of the Ln-SiO2 materials. The heavier the lanthanide element, the higher the Si/Ln ratio. The TG curves showed that the decomposition of the structural template occurs in the materials at temperatures below 500 °C. The samples showed variations in specific surface area, mean pore diameter and silica wall thickness, depending on the nature of the lanthanide. The incorporation of different lanthanides in the silica generated acid sites of varied strength. The hydrothermal stability of the Ln-SiO2 materials evaluated at high temperatures, evidenced that the properties can be controlled for application in adsorption and catalysis processes.

Tropical climate effect on the toxic heavy metal pollutant course of road-deposited sediments.

In modern society, the intense vehicle traffic and the lack of effective mitigating strategies may adversely impact freshwater systems. Road-deposited sediments (RDS) accumulate a variety of toxic substances which are transported into nature during hydrologic events, mainly affecting water bodies through stormwater runoff. The aim of this study was to evaluate the RDS metal enrichment ratio between the end of wet season and the middle of the dry season for Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in samples from Natal, Brazil. Twenty RDS, drainage system and river sediment samples were collected in the wet and dry seasons using a stainless-steel pan, brush and spatula. In the laboratory, the samples were submitted to acid digestion and heavy metal concentrations were measured by atomic absorption spectrometry (AAS). A consistent RDS enrichment by heavy metals in dry season samples was followed by an increase in the finest particle size fraction (D < 63 µm). Maximum concentrations were 5, ND, 108, 23810, 83, ND, 77 and 150 mg kg-1 for Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn, respectively. The RDS enrichment ratio was Cr(1.3 × ), Cu(2.6 × ), Fe(3.3 × ), Mn(1.5 × ), Pb(1.5 × ) and Zn(2.1 × ). The Geo-accumulation Index values showed that RDS were moderately polluted for Cu and slighted polluted for Zn and Pb. Principal Component Analysis (PCA) showed that the accumulation of toxic heavy metals decreased according to water flow.

Peroxidase catalytic cycle of MCM-41-entrapped microperoxidase-11 as a mechanism for phenol oxidation.

The encapsulation of microperoxidases (MPs) into molecular sieves with controlled pore size, such as the mesoporous silica MCM-41, represents a nanotechnology strategy to control the catalytic properties of MPs and mimic the enzymatic activity of hemoproteins. In this work, the ferric microperoxidase-11 (MP-11), obtained from trypsin-catalyzed hydrolysis of horse-heart cytochrome c, was entrapped in MCM-41, thus resulting in a catalyst (Fe(III)MP11MCM41) with catalase and monooxygenase properties. The entrapment of MP-11 inside MCM-41 was confirmed by elemental analysis and UV-visible spectrum, with a red shift in the Soret band indicating that the heme group was in a hydrophobic microenvironment. Similarly to catalase, the catalyst Fe(III)MP11MCM41 exhibited specificity for hydrogen peroxide to be converted to a high-valence oxidized intermediate, Compound II. Also mimicking catalase, the cleavage of hydrogen peroxide by MP11MCM41 resulted in O2 production detected by a Clark electrode. Phenol was able to act as reducing agent of MP11MCM41 Compound II leading to the completion of a peroxidase cycle, as confirmed by UV-visible spectrometry and EPR measurements. The analysis of the reaction products by high performance liquid chromatogram coupled to tandem mass spectrometry (HPLC/MS) revealed 2,4-dihydroxyphenol as the product of phenol oxidation by MP11MCM41. Therefore, in addition to catalase activity, the catalyst MP11MCM41 also displayed monooxygenase properties, which was possible because the MP-11 heme iron promotes homolytic cleavage of the hydrogen peroxide generating hydroxyl radicals. With such characteristics, MCM-41-entrapped MP-11 is a promising catalyst for nanobiotechnological devices.