Adsorption of transition-metal ions in ethanol solution by a nanomaterial based on modified silsesquioxane

The material octakis[3-(3-amino- 1,2,4-triazole)propyl]octasilsesquioxane (ATZ-SSQ) was synthesized and its potential was assessed for Cu(II), Ni(II), Co(II), Zn(II) and Fe(III) from their ethanol solutions and compared with related 3-amino-1,2,4-triazole-propyl modified silica gel (ATZ-SG). The adsorption was performed using a batchwise process and both organofunctionalized surfaces showed the ability to adsorb the metal ions from ethanol solution. The Langmuir model allowed to describe the sorption of the metal ions on ATZ-SSQ and ATTZ-SG in a satisfactory way. The equilibrium is reached very quickly Q min) for ATZ-SSQ, indicating that the adsorption sites are well exposed. The maximum metal ion uptake values for Cu(II), Co(II), Zn(II), Ni(II) and Fe(III) were 0.86, 0.09, 0.19, 0.09 and 0.10 mmol g(-1), respectively, for the ATZ-SSQ, which were higher than the corresponding values 0.21, 0.04, 0.14, 0.05 and 0.07 mmol g(-1) achieved with the ATZ-SG. In order to obtain more information on the metal-ligand interaction of the complexes on the surface of the ATZ-SSQ, Cu(II) was used as a probe to determine the arrangements of the ligands around the central metal ion by electron spin resonance (ESR). The ATZ-SSQ was used for the separation and determination (in flow using a column technique) of the metal ions present in commercial ethanol. (c) 2008 Elsevier B.V. All rights reserved.

Nanostructured hybrid films containing nanophosphor: Fabrication and electronic spectral properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nanoparticles of octakis [3-(3-amino-1,2,4-triazole)propyl] octasilsesquioxane as ligands for Cu(II), Ni(II), Cd(II), Zn(II), and Fe(III) in aqueous solution

Nanoparticles of octakis[3-(3-amino-1,2,4-triazole)propyl]octasilsesquioxane (ATZ-SSQ) were tested as ligands, for transition-metal ions in aqueous solution with a special attention to sorption isotherms, ligand-metal interaction, and determination of metal ions in natural waters. The adsorption potential of the material ATZ-SSQ was compared with related [3(3-amino-1,2,4-triazole)propyl]silica gel (ATZ-SG). The adsorption was performed using a batchwise process and both organofunctionalized surfaces showed the ability to adsorb the metal ions from aqueous solution. The Langmuir model was used to simulate the sorption isotherms. The results suggest that the sorption of these metals on ATZ-SSQ and ATZ-SG occurs mainly by surface complexation. The equilibrium condition is reached at time lower than 3 min for ATZ-SSQ, while for ATZ-SG is only reached at time of 25 min. The maximum metal ion uptake values for ATZ-SSQ were higher than the corresponding values achieved with the ATZ-SG. In order to obtain more information on the ligand-metal interaction of the complexes on the surface of the ATZ-SSQ nanomaterial, ESR study with various degrees of copper loadings was carried out. The ATZ-SSQ was tested for the determination (in flow using a column technique) of the metal ions present in natural waters. (C) 2007 Elsevier B.V. All rights reserved.

Preconcentration and determination of metal ions in commercial ethanol used as fuel for automotive engines

The present investigation reports the synthesis, characterization, and adsorption properties of a new nanomaterial based on organomodified silsesquioxane nanocages. The adsorption isotherms for CuCl,, CoCl2, ZnCl2, NiCl2, and FeCl3 from ethanol solutions were performed by using the batchwise method. The equilibrium condition is reached very quickly (3 min), indicating that the adsorption sites are well exposed. The results obtained in the flow experiments, showed a recovery of ca. 100% of the metal ions adsorbed in a column packed with 2 g of the nanomaterial, using 5 mL of 1.0 mol L-1 HCl solution as eluent. The sorption-desorption of the metal ions made possible the development of a method for preconcentration and determination of metal ions at trace level in commercial ethanol, used as fuel for car engines. The values determined by recommended method for plants 1, 2, and 3 indicated an amount of copper of 51, 60, and 78 mu g L-1, and of iron of 2, 15, and 13 mu g L-1, respectively. These values are very close to those determined by conventional analytical methods. Thus, these similar values demonstrated the accuracy of the determination by recommended method.

Study on soluble heavy metals with preconcentration by using a new modified oligosilsesquioxane sorbent

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Fullerene and omega-3 and omega-6 fatty acids on fish brain antioxidant status

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Study of structural and photoluminescent properties of Ca8Eu2(PO4)(6)O-2

In this work it is presented for the first time the nanostructured hydroxyapatites doped with 0.5, 1.0 and 2.0 wt% of Eu3+ prepared at room temperature by the mechanical alloying technique. X-ray diffraction powder (XRD), infrared (IR) and Raman scattering spectroscopy, scanning electron microscopy (SEM), microhardness measurements as well as luminescent data of Eu3+ were used to investigate the structural and optical properties of these nanomaterials. The electrical and dielectrical analyses were used with the intention of having a better comprehension about the electromagnetic fields in pure and doped hydroxyapatites.

Inorganic UV filters

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

On the application of nanostructured electrodes prepared by Ti/TiO2/WO3 template : A case study of removing toxicity of indigo using visible irradiation

New assays with HepG2 cells indicate that Indigo Carmine (IC), a dye that is widely used as additive in many food and pharmaceutical industries exhibited cytotoxic effects. This work describes the development of a bicomponent nanostructured Ti/TiO2/WO3 electrode prepared by template method and investigates its efficiency in a photoelectrocatalytic method by using visible light irradiation and applied potential of 1V. After 2h of treatment there are reduction of 97% discoloration, 62% of mineralization and formation of three byproducts assigned as: 2-amine-5-sulfo-benzoic acid, 2,3-dioxo-14-indole-5-sulfonic acid, and 2-amino-α-oxo-5-sulfo-benzeneacetic acid were identified by HPLC-MS/MS. But, cytotoxicity was completely removed after 120min of treatment. © 2013 Elsevier Ltd.

Adsorption of heavy metal ions and epoxidation catalysis using a new polyhedral oligomeric silsesquioxane

The objective of this research was the preparation of a silsesquioxane functionalized with eight chloropropyl chains (T8-PrCl) and of a new derivative functionalized with a pendant linear chain (2-amino-1,3,4-thiadiazole - ATD; T8-Pr-ATD). The two nanostructured materials were characterized by 13C and 29Si NMR, FTIR and elemental analysis. The new nanostructured material, octakis[3-(2-amino-1,3,4-thiadiazole)propyl] octasilsesquioxane (T8-Pr-ATD), was tested as a ligand for transition-metal ions with a special attention to adsorption isotherms. The adsorption was performed using a batchwise process and the organofunctionalized surface showed the ability to adsorb the metal ions Cu (II), Co (II), and Ni (II) from water and ethanol. The adsorption isotherms were fitted by Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) model. The kinetics of adsorption of metals were performed using three models such as pseudo-first order, pseudo-second order and Elovich. The Langmuir and Elovich models were the most appropriate to describe the adsorption and kinetic data, respectively. Furthermore, the T8-Pr-ATD was successfully applied to the analysis of environmental samples (river and sea water). Subsequently, a new nanomaterial was prepared by functionalization of the T8-Pr-ATD with a Mo (II) organometallic complex (T8-Pr-ATD-Mo). Only a few works in the literature have reported this type of substitution, and none dealt with ATD and Mo (II) complexes. The new Mo-silsesquioxane organometallic nanomaterial was tested as precursor in the epoxidation of cyclooctene and styrene. © 2012 Elsevier B.V.

Immunosensor based on immobilization of antigenic peptide NS5A-1 from HCV and silk fibroin in nanostructured films

The peptide NS5A-1 (PPLLESWKDPDYVPPWHG), derived from hepatitis C virus (HCV) NS5A protein, was immobilized into layer-by-layer (LbL) silk fibroin (SF) films. Deposition was monitored by UV-vis absorption measurements at each bilayer deposited. The interaction SF/peptide film induced secondary structure in NS5A-1 as indicated by fluorescence and circular dichroism (CD) measurements. Voltammetric sensor (SF/NS5A-1) properties were observed when the composite film was tested in the presence of anti-HCV. The peptide-silk fibroin interaction studied here showed new architectures for immunosensors based on antigenic peptides and SF as a suitable immobilization matrix. © 2013 American Chemical Society.

Osteogenesis-inducing calcium phosphate nanoparticle precursors applied to titanium surfaces

This study investigated the effects of the morphology and physicochemical properties of calcium phosphate (CaP) nanoparticles on osteogenesis. Two types of CaP nanoparticles were compared, namely amorphous calcium phosphate (ACP) nano-spheres (diameter: 9-13 nm) and poorly crystalline apatite (PCA) nano-needles (30-50 nm x 2-4 nm) that closely resemble bone apatite. CaP particles were spin-coated onto titanium discs and implants; they were evaluated in cultured mouse calvarial osteoblasts, as well as after implantation in rabbit femurs. A significant dependence of CaP coatings was observed in osteoblast-related gene expression (Runx2, Col1a1 and Spp1). Specifically, the PCA group presented an up-regulation of the osteospecific genes, while the ACP group suppressed the Runx2 and Col1a1 expression when compared to blank titanium substrates. Both the ACP and PCA groups presented a more than three-fold increase of calcium deposition, as suggested by Alizarin red staining. The removal torque results implied a slight tendency in favour of the PCA group. Different forms of CaP nanostructures presented different biologic differences; the obtained information can be used to optimize surface coatings on biomaterials. © 2013 IOP Publishing Ltd.

ZnO nanostructures directly grown on paper and bacterial cellulose substrates without any surface modification layer

In this report, hierarchical ZnO nano- and microstructures were directly grown for the first time on a bacterial cellulose substrate and on two additional different papers by hydrothermal synthesis without any surface modification layer. Compactness and smoothness of the substrates are two important parameters that allow the growth of oriented structures. © 2013 The Royal Society of Chemistry.

Síntese e caracterização de híbridos inorgânico-orgânicos funcionalizados com tiouréia e 2,2’-dipiridilamina: aplicação em adsorção de íons metálicos, pré-concentração e catálise

Pós-graduação em Ciência dos Materiais - FEIS

Estudo de materiais nanoestruturados baseados em silsesquioxanos organomodificados: síntese, caracterização, formação de complexos e sorção de íons metálicos

Pós-graduação em Ciência e Tecnologia de Materiais - FC