Sorption and preconcentration of metal ions in ethanol solution with a silica gel surface chemically modified with benzimidazole

The adsorption isotherms of MCl(2) (M = Mn, Ni, Cu, Zn and Cd) and FeCl3 by silica gel chemically modified with benzimidazole molecules (= SI(CH2)(3)-NC7H5N) were studied in ethanol solution at 298 K. A column made of modified silica was used to adsorb and preconcentrate the above metal ions from ethanol solution. Elution was done with 0.1 M hydrochloric acid in an ethanol/water mixture having a mole fraction of water of 0.8. The material was applied in the preconcentration of metal ions from commercial ethanol normally used as engine fuel.

ESR STUDY OF CUCL2 ADSORBED ON A CHEMICALLY-MODIFIED SILICA-GEL SURFACE WITH BENZIMIDAZOLE MOLECULE

The ESR spectrum of CuCl2 adsorbed onto a silica gel surface chemically modified with the benzimidazole molecule showed that the surface complex has an octahedral symmetry with tetragonal distortion. The measured ESR parameters were g(parallel to) = 2.287, g(perpendicular to) = 2.062, A(parallel to) = 153 G and superhyperfine splitting A(N) = 15 G. The fit of the theoretical expressions to the experimental data was very reasonable. The effective spin orbit coupling constant for Cu2+ was reduced from its normal free ion value of lambda = -828 cm(-1) by as much as 30%. This reduction of lambda is normal in the solid state and in frozen solution complexes.

XPS study on water corrosion of fluorzirconate glasses and their protection by a layer of surface modified tin dioxide nanoparticles

The surface corrosion process associated with the hydrolysis of fluorozirconate glass, Z-BLAN (53ZrF(4), 20BaF(2), 20NaF, 4LaF(2), 3AlF(3)), and the corrosion protection efficiency of a nanocrystalline transparent SnO2 layer were investigated by X-ray photoelectron spectroscopy. The tin oxide film was deposited by the sol-gel dip-coating process in the presence of Tiron(R) as particle surface modifier agent. The chemical bonding structure and composition of the surface region of coated and non-coated ZBLAN were studied before water contact and after different immersion periods (5-30 min). In contrast to the effects occurring for non-coated glass, where the surface undergoes a rapid selective dissolution of the most soluble species inducing the formation of a new surface phase consisting of stable zirconium oxyfluoride, barium fluoride and lanthanum fluoride species, the results for the SnO2-coated glass showed that the hydrolytic attack induces a filling of the film nanopores by dissolved glass material and the formation of tin oxylluoride and zirconium oxyfluoride species. This process results in a modified film, which acts as a hermetic diffusion barrier protecting efficiently the glass surface. (C) 2006 Elsevier B.V. All rights reserved.

Small angle X-ray scattering and IR spectroscopy study of metal carbonyl complexes immobilized on a silica gel surface chemically modified with piperazine

The carbonyl complexes [WCl(CO)(3)(bipy) (HgCl)] (1), [Fe(CO)(4)(HgCl)(2)] (2) and W(CO)(6)] (3) were immobilized on a silica gel surface organofunctionalized with piperazine groups. The products obtained were studied by IR spectroscopy and small angle X-ray scattering (SAXS) techniques. The IR data show that the immobilization of heterobimetallic compounds 1 and 2, on the functionalized surface, occurred through the mercury atom, while for 3 the displacement of one CO group by the nitrogen of a piperazine molecule was observed. The data obtained from SAXS indicate that particles have a uniform size and reveal suitable modifications on the functionalized surface after immobilization of metal carbonyl complexes. The average intermolecular distance (l(ij)) for piperazine ligands on support is 8.7 Angstrom, for the metal carbonyl complex 1 it is 18.8 Angstrom, for complex 2 it is 16.2 Angstrom and for complex 3 it is 15.3 Angstrom. Copyright (C) 1996 Elsevier B.V. Ltd

Thermo-Reversible Sol-Gel Transition of Surface Modified Titanium Poly Oxo Building Blocks

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

Thermo-reversible sol-gel transition of TiO2 nanoparticles with surface modified by p-toluene sulfonic acid

In this paper an unprecedent thermo-reversible sol-gel transition for titania nanoparticles dispersed in a solution of p-toluene sulfonic acid (PTSH) in isopropanol is reported. The sol formed by the thermo-hydrolysis at 60 degrees C of titanium tetraisopropoxide (Ti((OPr)-Pr-i)(4)) reversibly changes into a turbid gel upon cooling to room temperature. Turbidimetric measurements performed for samples containing different nominal acidity ratios (A = [PTSH]/[Ti]) have evidenced that the gel transformation temperature increases from 20 to 35 degrees C as the [PTSH]/[Ti] ratio increases from 0.2 to 2.0. SAXS results indicate that the thermo-reversible gelation is associated to a reversible aggregation of a monodisperse set of titania nanoparticles with average gyration radius of approximate to 2 nm. From the different PTSH species evidenced by Raman spectroscopy and TG/DTA of dried gels we proposed that the then-no-reversible gelation in this systems is induced by the formation of a supramolecular network, in which the protonated surface of nanoparticles is interconnected through cooperative hydrogen bonds between -SO3 groups of p-toluene sulfonic acid. (C) 2009 Elsevier Ltd. All rights reserved.

Effect of the surfactant nature on the thermo-stability of surface modified SnO2 nanoparticles

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Adsorption of MX2 (M = Mn, Ni, Cu, Zn, and Cd; X = Cl, Br, and I) and FeCl3 by modified silica surface with imidazolylpropyl group

Silica gel surface modified with imidazolylpropyl group was used to adsorb MX2 (M = Mn, Ni, Cu, Zn, and Cd; X = Cl, Br, and I) and FeCl3 from ethanol and acetone solution. The adsorption capacity and the intensity of the adsorption were determined by using the Langmuir equation. The influences of the solvent, temperature, and degree of functionalization on the adsorption were also studied. The infrared spectra of the functionalized silica were recorded between 1700-1300 cm-1. The bands of the imidazole skeletal vibrations are shifted to higher frequencies upon metal-to-base nitrogen interaction. © 1985.

Structure of cobalt (II) perchlorate adsorbed on silica gel surface chemically modified with benzimidazole molecule

Covalently attached benzimidazole molecules on silica gel surface, ≡SiL (where L = N-propyl-benzimidazole), adsorbs Co(ClO4)2 from non-aqueous solvent by forming a surface complex according to the reaction: m ≡SiL + Co(ClO4)2 → (≡SiL)mCo(ClO4)2. The equilibrium constant and the adsorption capacity, determined by applying the Langmuir equation were b = 3.0 × 103 L mol-1 and Ns= 0.098 × 10-3 mol g-1, respectively. The metal is bonded through the nitrogen atom and the perchlorate ion is not coordinated. The ESR study indicated that the complex has essentially an octahedral geometry with tetragonal distortion, with the electrons of the four nitrogen atoms interacting with the cobalt central metal ion in the equatorial plane. Only one complex species was detected on the surface.

Adsorption and structure of copper(II) complexes on a silica gel surface chemically modified with 2-aminothiazole

The isotherms of adsorption of CuX2 (X=Cl-, Br-, ClO- 4) by silica gel chemically modified with 2-aminothiazole were studied in acetone and EtOH solutions, at 25°C. The 2-aminothiazole molecule, covalently bond to the silica gel surface, adsorbs CuX2 from solvent by forming a surface complex. At low loading, the electronic and E.S.R. spectral parameters indicate that the Cu2+ complexes have a distorted tetragonal symmetry. The d-d eletronic transition spectra show that for ClO- 4 complex, the peak of absorption do not change for any degree of metal loading whilst for Cl- and Br- complexes, the peak maxima shift to higher energy with lower metal loading. © Elsevier Science Ltd.

Corrosion protection of fluorzirconate glasses coated by a layer of surface modified tin oxide nanoparticles

The protection efficiency against water corrosion of fluorozirconate glass, ZBLAN, dip-coated by nanocrystalline tin oxide film containing the organic molecule Tiron® was investigated by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The chemical bonding structure of the surface region and morphology were studied before and after two water exposure periods of 5 and 30 min. The results of the analysis for the as-grown sample revealed a SnO1.6 phase containing carbon and sulfur, related to Tiron®, and traces of elements related to ZBLAN (Zr, F, Ba). This fact and the clear evidence of the presence of tin oxifluoride specie (SnOxF y) indicates a diffusion of the glass components into the porous coating. After water exposure, the increase of the oxygen concentration accompanied by a strong increase of Zr, F, Ba and Na content is interpreted as filling of the nanopores of the film by glass compounds. The formation of a compact protective layer is supported by the morphological changes observed by AFM. © 2005 Elsevier B.V. All rights reserved.

Concentration of Cu(II) and Cd(II) from natural river water by Adsorption on a Modified Silica Surface

A high surface area silica gel (737 ± m2 g-1) was synthesized modified through a two-step reaction with a 4-amino-2-mercaptopyrimidine ligand and applied to Cu(II) and Cd(II) adsorption from an aqueous medium. The modified material was characterized by FTIR, which showed that attachment of the molecule occurred via thiol groups at 2547 and 2600 cm-1, and by elemental analysis that indicated the presence of 0.0102 mmol of ligand. The data from adsorption experiments were adjusted to a modified Langmuir equation and the maximum adsorption capacity was 6.6 and 3.8 μmol g-1 for Cu(II) and Cd(II), respectively. After adjusting several parameters, the material was applied in the preconcentration of natural river water using a continuous flow system before and after sample mineralization, and the results showed a 10-fold enrichment factor. The proposed method was validated through preconcentration and analysis of certified standard reference material (1643e), whose results were in agreement with the values provided by the manufacturer.

Biomedical Ti-Mo Alloys with Surface Machined and Modified by Laser Beam: Biomechanical, Histological, and Histometric Analysis in Rabbits

Purpose: In vivo bone response was assessed by removal torque, hystological and histometrical analysis on a recently developed biomedical Ti-15Mo alloy, after surface modification by laser beam irradiation, installed in the tibia of rabbits. Materials and Methods: A total of 32 wide cylindrical Ti-15Mo dental implants were obtained (10mm × 3.75mm). The implants were divided into two groups: 1) control samples (Machined surface - MS) and 2) implants with their surface modified by Laser beam-irradiation (Test samples - LS). Six implants of each surface were used for removal torque test and 10 of each surface for histological and histometrical analysis. The implants were placed in the tibial metaphyses of rabbits. Results: Average removal torque was 51.5Ncm to MS and >90Ncm to LS. Bone-to-implant-contact percentage was significantly higher for LS implants both in the cortical and marrow regions. Conclusions: The present study demonstrated that laser treated Ti-15Mo alloys are promising materials for biomedical application. © 2011 Wiley Periodicals, Inc.

Surface characterization and osteoblast-like cells culture on collagen modified PLDLA scaffolds

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