Sol-gel thin-film based mesoporous silica and carbon nanotubes for the determination of dopamine, uric acid and paracetamol in urine

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

Development of Vapor Deposited Silica Sol-Gel Particles for a Bioactive Materials System to Direct Osteoblast Behavior

Tissue engineering and regenerative medicine have emerged in an effort to generate replacement tissues capable of restoring native tissue structure and function, but because of the complexity of biologic system, this has proven to be much harder than originally anticipated. Silica based bioactive glasses are popular as biomaterials because of their ability to enhance osteogenesis and angiogenesis. Sol-gel processing methods are popular in generating these materials because it offers: 1) mild processing conditions; 2) easily controlled structure and composition; 3) the ability to incorporate biological molecules; and 4) inherent biocompatibility. The goal of this work was to develop a bioactive vaporization system for the deposition of silica sol-gel particles as a means to modify the material properties of a substrate at the nano- and micro- level to better mimic the instructive conditions of native bone tissue, promoting appropriate osteoblast attachment, proliferation, and differentiation as a means for supporting bone tissue regeneration. The size distribution, morphology and degradation behavior of the vapor deposited sol-gel particles developed here were found to be dependent upon formulation (H2O:TMOS, pH, Ca/P incorporation) and manufacturing (substrate surface character, deposition time). Additionally, deposition of these particles onto substrates can be used to modify overall substrate properties including hydrophobicity, roughness, and topography. Deposition of Ca/P sol particles induced apatite-like mineral formation on both two- and three-dimensional materials when exposed to body fluids. Gene expression analysis suggests that Ca/P sol particles induce upregulation osteoblast gene expression (Runx2, OPN, OCN) in preosteoblasts during early culture time points. Upon further modification-specifically increasing particle stability-these Ca/P sol particles possess the potential to serve as a simple and unique means to modify biomaterial surface properties as a means to direct osteoblast differentiation.

Characterizing the hierarchical structures of bioactive sol-gel silicate glass and hybrid scaffolds for bone regeneration

Bone is the second most widely transplanted tissue after blood. Synthetic alternatives are needed that can reduce the need for transplants and regenerate bone by acting as active temporary templates for bone growth. Bioactive glasses are one of the most promising bone replacement/regeneration materials because they bond to existing bone, are degradable and stimulate new bone growth by the action of their dissolution products on cells. Sol-gel-derived bioactive glasses can be foamed to produce interconnected macropores suitable for tissue ingrowth, particularly cell migration and vascularization and cell penetration. The scaffolds fulfil many of the criteria of an ideal synthetic bone graft, but are not suitable for all bone defect sites because they are brittle. One strategy for improving toughness of the scaffolds without losing their other beneficial properties is to synthesize inorganic/organic hybrids. These hybrids have polymers introduced into the sol-gel process so that the organic and inorganic components interact at the molecular level, providing control over mechanical properties and degradation rates. However, a full understanding of how each feature or property of the glass and hybrid scaffolds affects cellular response is needed to optimize the materials and ensure long-term success and clinical products. This review focuses on the techniques that have been developed for characterizing the hierarchical structures of sol-gel glasses and hybrids, from atomicscale amorphous networks, through the covalent bonding between components in hybrids and nanoporosity, to quantifying open macroporous networks of the scaffolds. Methods for non-destructive in situ monitoring of degradation and bioactivity mechanisms of the materials are also included. © 2012 The Royal Society.

Síntese e caracterização de pigmentos nanométricos encapsulados pelos métodos dos precursores poliméricos, hidrotermal de microondas e co-precipitação associado à química sol-gel convencional

The demand for materials with high consistency obtained at relatively low temperatures has been leveraging the search for chemical processes substituents of the conventional ceramic method. This paper aims to obtain nanosized pigments encapsulated (core-shell) the basis of TiO2 doped with transition metals (Fe, Co, Ni, Al) through three (3) methods of synthesis: polymeric precursors (Pechini); hydrothermal microwave, and co-precipitation associated with the sol-gel chemistry. The study was motivated by the simplicity, speed and low power consumption characteristic of these methods. Systems costs are affordable because they allow achieving good control of microstructure, combined with high purity, controlled stoichiometric phases and allowing to obtain particles of nanometer size. The physical, chemical, morphological, structural and optical properties of the materials obtained were analyzed using different techniques for materials characterization. The powder pigments were tested in discoloration and degradation using a photoreactor through the solution of Remazol yellow dye gold (NNI), such as filtration, resulting in a separation of solution and the filter pigments available for further UV-Vis measurements . Different calcination temperatures taken after obtaining the post, the different methods were: 400 º C and 1000 º C. Using a fixed concentration of 10% (Fe, Al, Ni, Co) mass relative to the mass of titanium technologically and economically enabling the study. By transmission electron microscopy (TEM) technique was possible to analyze and confirm the structural formation nanosized particles of encapsulated pigment, TiO2 having the diameter of 20 nm to 100 nm, and thickness of coated layer of Fe, Ni and Co between 2 nm and 10 nm. The method of synthesis more efficient has been studied in the work co-precipitation associated with sol-gel chemistry, in which the best results were achieved without the need for the obtainment of powders the calcination process

Physico-chemical properties of sol-gel synthesized titanosilicates for the uptake of radionuclides from aqueous solutions

Harnessing the power of nuclear reactions has brought huge benefits in terms of nuclear energy, medicine and defence as well as risks including the management of nuclear wastes. One of the main issues for radioactive waste management is liquid radioactive waste (LRW). Different methods have been applied to remediate LRW, thereunder ion exchange and adsorption. Comparative studies have demonstrated that Na2Ti2O3SiO4·2H2O titanosilicate sorption materials are the most promising in terms of Cs+ and Sr2+ retention from LRW. Therefore these TiSi materials became the object of this study. The recently developed in Ukraine sol-gel method of synthesizing these materials was chosen among the other reported approaches since it allows obtaining the TiSi materials in the form of particles with size ≥ 4mm. utilizing inexpensive and bulk stable inorganic precursors and yielded the materials with desirable properties by alteration of the comparatively mild synthesis conditions. The main aim of this study was to investigate the physico-chemical properties of sol-gel synthesized titanosilicates for radionuclide uptake from aqueous solutions. The effect of synthesis conditions on the structural and sorption parameters of TiSi xerogels was planned to determine in order to obtain a highly efficient sorption material. The ability of the obtained TiSis to retain Cs+, Sr2+ and other potentially toxic metal cations from the synthetic and real aqueous solutions was intended to assess. To our expectations, abovementioned studies will illustrate the efficiency and profitability of the chosen synthesis approach, synthesis conditions and the obtained materials. X-ray diffraction, low temperature adsorption/desorption surface area analysis, X-ray photoelectron spectroscopy, infrared spectroscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy was used for xerogels characterization. The sorption capability of the synthesized TiSi gels was studied as a function of pH, adsorbent mass, initial concentration of target ion, contact time, temperature, composition and concentration of the background solution. It was found that the applied sol-gel approach yielded materials with a poorly crystalline sodium titanosilicate structure under relatively mild synthesis conditions. The temperature of HTT has the strongest influence on the structure of the materials and consequently was concluded to be the control factor for the preparation of gels with the desired properties. The obtained materials proved to be effective and selective for both Sr2+ and Cs+ decontamination from synthetic and real aqueous solutions like drinking, ground, sea and mine waters, blood plasma and liquid radioactive wastes.

Mechanical properties of thin sol-gel films

This thesis presents a study of the mechanical properties of thin films. The main aim was to determine the properties of sol-gel derived coatings. These films are used in a range of different applications and are known to be quite porous. Very little work has been carried out in this area and in order to study the mechanical properties of sol-gel films, some of the work was carried out on magnetron sputtered metal coatings in order to validate the techniques developed in this work. The main part of the work has concentrated on the development of various bending techniques to study the elastic modulus of the thin films, including both a small scale three-point bending, as well as a novel bi-axial bending technique based on a disk resting on three supporting balls. The bending techniques involve a load being applied to the sample being tested and the bending response to this force being recorded. These experiments were carried out using an ultra micro indentation system with very sensitive force and depth recording capabilities. By analysing the result of these forces and deflections using existing theories of elasticity, the elastic modulus may be determined. In addition to the bi-axial bending study, a finite element analysis of the stress distribution in a disk during bending was carried out. The results from the bi-axial bending tests of the magnetron sputtered films was confirmed by ultra micro indentation tests, giving information of the hardness and elastic modulus of the films. It was found that while the three point bending method gave acceptable results for uncoated steel substrates, it was very susceptible to slight deformations of the substrate. Improvements were made by more careful preparation of the substrates in order to avoid deformation. However the technique still failed to give reasonable results for coated specimens. In contrast, biaxial bending gave very reliable results even for very thin films and this technique was also found to be useful for determination of the properties of sol-gel coatings. In addition, an ultra micro indentation study of the hardness and elastic modulus of sol-gel films was conducted. This study included conventionally fired films as well as films ion implanted in a range of doses. The indentation tests showed that for implantation of H⁺ ions at doses exceeding 3x10¹⁶ ions/cm², the mechanical properties closely resembled those of films that were conventionally fired to 450°C.

Mathematical modelling of the drying of sol gel microspheres

This thesis presents a mathematical model of the evaporation of colloidal sol droplets suspended within an atmosphere consisting of water vapour and air. The main purpose of this work is to investigate the causes of the morphologies arising within the powder collected from a spray dryer into which the precursor sol for Synroc™ is sprayed. The morphology is of significant importance for the application to storage of High Level Liquid Nuclear Waste. We begin by developing a model describing the evaporation of pure liquid droplets in order to establish a framework. This model is developed through the use of continuum mechanics and thermodynamic theory, and we focus on the specific case of pure water droplets. We establish a model considering a pure water vapour atmosphere, and then expand this model to account for the presence of an atmospheric gas such as air. We model colloidal particle-particle interactions and interactions between colloid and electrolyte using DLVO Theory and reaction kinetics, then incorporate these interactions into an expression for net interaction energy of a single particle with all other particles within the droplet. We account for the flow of material due to diffusion, advection, and interaction between species, and expand the pure liquid droplet models to account for the presence of these species. In addition, the process of colloidal agglomeration is modelled. To obtain solutions for our models, we develop a numerical algorithm based on the Control Volume method. To promote numerical stability, we formulate a new method of convergence acceleration. The results of a MATLAB™ code developed from this algorithm are compared with experimental data collected for the purposes of validation, and further analysis is done on the sensitivity of the solution to various controlling parameters.

Sol-gel synthesis and characterization of cubic bismuth zinc niobium oxide nanopowders

Bismuth zinc niobium oxide (BZN) was successfully synthesized by a diol-based sol-gel reaction utilizing metal acetate and alkoxide precursors. Thermal analysis of a liquid suspension of precursors suggests that the majority of organic precursors decompose at temperatures up to 150°C, and organic free powders form above 350°C. The experimental results indicate that a homogeneous gel is obtained at about 200°C and then converts to a mixture of intermediate oxides at 350–400°C. Finally, single-phased BZN powders are obtained between 500 and 900°C. The degree of chemical homogeneity as determined by X-ray diffraction and EDS mapping is consistent throughout the samples. Elemental analysis indicates that the atomic ratio of metals closely matches a Bi1.5ZnNb1.5O7 composition. Crystallite sizes of the BZN powders calculated from the Scherrer equation are about 33–98 nm for the samples prepared at 500–700°C, respectively. The particle and crystallite sizes increase with increased sintering temperature. The estimated band gap of the BZN nanopowders from optical analysis is about 2.60–2.75 eV at 500-600°C. The observed phase formations and measured results in this study were compared with those of previous reports.

Structural and lithium ion transport studies in sol-gel-prepared lithium silicophosphate glasses

Lithium silicophosphate glasses have been prepared by a sol-gel route over a wide range of compositions. Their structural and electrical properties have been investigated. Infrared spectroscopic studies show the presence of hydroxyl groups attached to Si and P. MAS NMR investigations provide evidence for the presence of different phosphatic units in the structure. The variations of de conductivities at 423 K and activation energies have been studied as a function of composition, and both exhibit an increasing trend with the ratio of nonbridging oxygen to bridging oxygen in the structure. Ac conductivity behavior shows that the power law exponent, s, is temperature dependent and exhibits a minimum. Relaxation behavior has been examined in detail using an electrical modulus formalism, and modulus data were fitted to Kohlraush-William-Watts stretched exponential function. A structural model has been proposed and the unusual properties exhibited by this unique system of glasses have been rationalized using this model. Ion transport in these glasses appears to be confined to unidimensional conduits defined by modified phosphate chains and interspersed with unmodified silica units.

Assembly of sol-gel-grown $Li _{(x)} CoO_{2}$ nanocrystals through electromagnetic irradiation

We report the fabrication of assembled nanostructures from the pre-synthesized nanocrystals building blocks through optical means of exciton formation and dissociation. We demonstrate that Li (x) CoO2 nanocrystals assemble to an acicular architecture, upon prolonged exposure to ultraviolet-visible radiation emitted from a 125 W mercury vapor lamp, through intermediate excitation of excitons. The results obtained in the present study clearly show how nanocrystals of various materials with band gaps appropriate for excitations of excitons at given optical wavelengths can be assembled to unusual nanoarchitectures through illumination with incoherent light sources. The disappearance of exciton bands due to Li (x) CoO2 phase in the optical spectrum of the irradiated film comprising acicular structure is consistent with the proposed mechanism of exciton dissociation in the observed light-induced assembly process. The assembly process occurs through attractive Coulomb interactions between charged dots created upon exciton dissociation. Our work presents a new type of nanocrystal assembly process that is driven by light and exciton directed.