Alejandro Ávila-Ortega

Effects of different amounts of APTES on physicochemical and structural properties of amino-functionalized MCM-41-MSNs

Mesoporous silica nanoparticles (MSNs) are frequently functionalized to be used for specific applications, including catalysis and biomedical engineering. In this research, MCM-41-MSNs were synthesized by the sol–gel method and were functionalized with different quantities of (3-aminopropyl) triethoxysilane (APTES) using a post-grafting method to determine the physicochemical and structural changes in the MSNs. The functionalized materials were assessed by different characterization techniques, namely, TGA, FTIR, BET, SEM, TEM, DLS, zeta potential, SAXS, XRD and XPS. The FTIR data confirmed the presence of amino groups on the MSN surfaces, and the results from the XPS, TGA and zeta potential demonstrated that the APTES concentration during post-grafting directly affects the quantity of amino groups bound to the MSNs. The SAXS, TEM and nitrogen adsorption–desorption analyses showed that as the amount of APTES in the MSNs increases, the mesoporous structure become more disordered.Graphical Abstract

Controlled Phase Changes of Titania Using Nitrogen Plasma

In this work, the development of a new crystallization technique is reported, using nitrogen plasma (AC) to obtain nanostructured anatase and rutile from amorphous titanium oxide (TiO2). This methodology increases throughput and minimizes thermal effects. Nanostructured amorphous TiO2 was obtained by the sol-gel method and subsequently subjected to AC treatment, at a controlled pressure, applying different powers and treatment times in order to obtain phase changes. The obtained samples were characterized using X-ray diffraction (XRD), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The results show the crystallization in parallel with anatase and rutile phases with a proportion that is directly related to the applied power in the plasma and the treatment time. This technique allows us to obtain smaller crystals in comparison with those of classic thermal methodologies. It is also demonstrated that the application of plasma represents a novel and innovative method to obtain phase polymorphic changes in titanium oxide without needing to apply prolonged heat treatments at high temperatures and can therefore be taken into consideration as a technique with low energy costs, in comparison with conventional heat treatments.

Effect of Functionalization Synthesis Type of Amino-MCM-41 Mesoporous Silica Nanoparticles on Its RB5 Adsorption Capacity and Kinetics

This study was undertaken to evaluate the adsorption of Reactive Black 5 dye (RB5), in aqueous solution, onto MCM-41 mesoporous silica nanoparticles (MSNs) functionalized with 3-aminopropyltriethoxysilane (APTES) by two methods: co-condensation and post-synthesis. The morphological and surface properties of both functionalized materials were compared by SEM, SAXS, N2 sorption and XPS characterization techniques. Sorption experiments were performed in order to determine the effect of pH, contact period and initial concentration of aqueous RB5 on the adsorption properties of bare- and both types of amino-MSNs. The results show that there exist morphological changes in the nanoparticles according to the type of functionalization synthesis, i.e. loss of hexagonal structure in co-condensation method and more density of amino groups on the surface of post-synthesis functionalized materials. The adsorption of RB5 on both type of materials is independent of the pH since they present adsorptions close to 100% in the evaluated pH range. The best fit of the data from adsorption kinetic studies is a pseudo-second-order model, being the material functionalized by the co-condensation method, which presents a higher adsorption rate because of its greater pore volume. The adsorption isotherms fitted well to the Langmuir model, with the amino-MSNs functionalized via the post-synthesis method presenting a higher capacity of adsorption, due to a greater density of amino groups on its surface, thereby facilitating their interaction with the RB5 molecules. Altogether, the results indicate that the type of functionalization synthesis affects the morphological characteristics of the nanoparticles and these, in turn, modify their adsorption properties.

Synthesis of pH-sensitive poly(β-amino ester)-coated mesoporous silica nanoparticles for the controlled release of drugs

This report describes the synthesis of a controlled drug delivery system that was obtained by coating mesoporous silica nanoparticles (MSNs) with poly(β-amino ester) (PbAE), which is a solid and stable material at physiological pH, but is dissolved at acidic pH values, such as those in tumor tissues (from 5.0 to 6.5). To synthesize the system, PbAE chains were grafted onto amino-functionalized MSNs through a reaction between the surface amino groups of MSNs and the ends of acrylate chains of a PbAE. The system was physicochemically characterized by dynamic light scattering (DLS), Fourier transform infrared spectroscopy, transmission electron microscopy, thermogravimetric analysis, X-ray photoelectron spectrometry, and X-ray diffraction analyses. In addition, the in vitro release of doxorubicin (DOX) and doxycycline (DXY) in acidic and physiological media was evaluated. It was observed that the PbAE modification did not affect the mesoporous structure of MSNs. When the amount of 3-aminopropyltriethoxysilane was increased during functionalization, the amount of PbAE binding to MSNs increased as well. With respect to drug release, the sample with the highest amount of PbAE showed better control in the delivery of DXY and DOX in acidic media, because at pH 5.5, the release of both drugs was 40% higher than that at pH 7.4. These results reveal two aspects about the presence of PbAE in MSNs: PbAE does not affect the mesoporous structure of the nanoparticles, and PbAE is the main factor controlling the delivery of drugs in acidic media.

Matrix solid-phase dispersion extraction of organophosphorus pesticide using SiO2-poly(N-vinylimidazole)

A sorbent material based on silica particles modified with poly(N-vinylimidazole) (SiO2-PVI) has been evaluated for the treatment of samples by matrix solid-phase dispersion (MSPD). The extraction of four organophosphorus pesticides was done from a spiked tomato and the extracts were analyzed by gas chromatography coupled to mass spectrometry. Six elution solvents were evaluated and acetone was selected due to better recovery of the four pesticides and low background signal in the chromatograms. A factorial design 24 was used for selection of extraction conditions. The factors were contact time, acetone volume, treatment (with or without freeze-drying) and adsorbent (SiO2 or SiO2-PVI). The best recoveries were obtained using 15 minutes of contact, 2 mL of solvent and sorbent without freeze-drying. The recoveries were between 60 and 83% for SiO2-PVI in spiked tomato with 0.2 and 0.8μg/g.