Rodrigo Brambilla

Selective silica‐based sorbent materials synthesized by molecular imprinting for adsorption of pharmaceuticals in aqueous matrices

The presence of pharmaceuticals in aqueous environmental matrices often requires efficient and selective preconcentration procedures. Thus, silicas (SILs) were synthesized by a molecular imprinting technique using an acid-catalyzed sol-gel process and the following drugs as templates: fluoxetine, gentamicin, lidocaine, morphine, nifedipine, paracetamol, and tetracycline. The materials were subjected to sorbent extraction assisted by ultrasonic treatment to remove the drugs and the consequent formation of molecular imprinted cavities. The surface area of the resulting materials ranged from 290 to 960 m(2)/g. Adsorption tests were performed with the molecular imprinting phases. In terms of the potential selectivity, the SILs were subjected to the adsorption of drugs from samples such as potable and surface water. The adsorption capacity remained in the range between 55 and 65% for both matrices, while for the nonimprinted SIL it remained between 15 and 20%.

The interaction of encapsulated pharmaceutical drugs with a silica matrix.

A series of seven drugs, namely, fluoxetine, gentamicin, lidocaine, morphine, nifedipine, paracetamol and tetracycline, were encapsulated. The encapsulated systems were characterized using a series of complementary techniques: Fourier-transform infrared spectroscopy (FT-IR), diffusive reflectance spectroscopy in the UV-vis region (DRS) and X-ray photoelectron spectroscopy (XPS). According to the DRS spectra, most of the encapsulated systems showed a band shift of the maximum absorption when compared with the corresponding bare pharmaceutical. Additionally, after encapsulation, the drugs exhibited infrared band shifts toward higher wavenumbers, which in turn provided insight into potential sites for interaction with the silica framework. The amine group showed a band shift in the spectra of almost all the drugs (except nifedipine and tetracycline). This finding indicates the possibility of a hydrogen bonding interaction between the drug and the silica via electron donation from the amine group to the silica framework. XPS confirmed this interaction between the pharmaceuticals and the silica through the amine group. A correlation was observed between the textural characteristics of the solids and the spectroscopic data, suggesting that the amine groups from the pharmaceuticals were more perturbed upon encapsulation.

Silica imprinted materials containing pharmaceuticals as a template: textural aspects

Silica-based materials were prepared by the acid catalyzed sol–gel method using different pharmaceuticals as a template. The template molecules investigated were fluoxetine, gentamicin, lidocaine, morphine, nifedipine, paracetamol and tetracycline. The resulting hybrid silicas underwent ultrasound extraction in the presence of several solvents and were characterized by elemental analysis, porosimetry by adsorption/desorption of nitrogen (BET method), small-angle X-ray scattering and X-ray diffraction. Drug extraction was carried out by the combination of solvent and ultra-sound. The textural characteristics of the hybrid xerogels and resulting imprinted materials were shown to be highly dependent on the molecular weight and molecular volume of the drug template. Increasing the molecular weight of the template results in a decrease in the encapsulation content of the resulting material. In the case of paracetamol and fluoxetine, the dimensions of the surface area are not sufficient to guarantee the adsorption of the smaller molecule. Instead, the shape generated through encapsulation and extraction during the production of the imprinted silica dictates the adsorption behavior.

Combining silica-based adsorbents and SPME fibers in the extraction of the volatiles of beer: an exploratory study

AbstractA series of silica-based materials were employed as sorbents within solid-phase microextraction vials. The aim of the study was to evaluate the effect of an additional phase on the distribution of the volatile and less volatile analytes. The adsorption of six probe molecules, namely isoamyl acetate, ethyl hexanoate (ethyl caproate), phenylethyl alcohol, ethyl octanoate (ethyl caprilate), 2-phenylethyl acetate, and ethyl decanoate, was monitored by detecting the desorbed amount on a DVD–CAR–PDMS fiber from Pilsen beer. The microextraction process involved the presence of different silica-based phases produced via different methods: xerogel produced by hydrolytic and non-hydrolytic routes, aerogel, pyrogenic, and precipitated silica. The resulting data are discussed in correlation with sorbent texture properties (specific area and pore diameter). The modification of silica with alkyl groups also affects the preconcentrated amount of the target molecules in the headspace. The presence of sorbents was shown to affect the analyte signal more than the addition of NaCl or the use of ultrasound. Analyte’s equilibrium between fiber and sorbent

Effects of the sol-gel route on the structural characteristics and antibacterial activity of silica-encapsulated gentamicin

The effects of sol-gel processes, i.e., acid-catalyzed gelation, base-catalyzed gelation and base-catalyzed precipitation routes, on the encapsulation of gentamicin were investigated. The resulting xerogels were characterized using a series of complementary instrumental techniques, i.e., the adsorption/desorption of nitrogen, small-angle X-ray scattering, Fourier transform infrared spectroscopy, diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy and scanning electron microscopy. The encapsulated gentamicin samples were tested against a series of Gram-positive and Gram-negative bacterial strains. The best antimicrobial activity was observed with the encapsulated gentamicin that was prepared via the precipitation route, even in comparison with the neat antibiotic, especially in the case of the Gram-positive strain Staphylococcus aureus. The gentamicin concentration on the outermost surface and the zeta potential were identified as factors that affected the highest efficiency, as observed in the case of encapsulation via the base-catalyzed process.

Octadecylsilane-modified silicas in the adsorption of toluene

AbstractA series of octadecylsilane-modified silicas were prepared by sol-gel and grafting methods. Carbon contents and octadecyl chain conformations were shown to depend on the preparative route. Grafting engenders a low carbon content and a liquid-like chain conformation, while the sol-gel method affords a much higher carbon content and a crystalline conformation. The relationships between the toluene adsorption of the hybrid silicas and their chain conformations, their carbon contents and their textural characteristics are discussed. These sorbents, when used in combination with ultraviolet diffuse reflectance spectroscopy (UV DRS), can be employed as a rapid screening method for detection of aromatic compounds in water and air environmental matrices. FigureOctadecylsilane-modified silicas in the adsorption of toluene

Imprinted silicas for paracetamol preconcentration prepared by the sol–gel process

Paracetamol-imprinted silicas were prepared by three sol–gel routes, including two basic-catalyzed gelification and precipitation routes, and an acid-catalyzed route. The resulting materials from basic gelification were subjected to Soxhlet, ultrasound and thermal extractions, and characterized by infrared spectroscopy, elemental analysis, nitrogen porosimetry, scanning electron microscopy, and atomic force microscopy. Ultrasound was shown to be the most efficient for template extraction. The resulting materials showed surface areas between 30 m2 g−1 (for the precipitation route) and 200 m2 g−1 (for the acid-catalyzed route). After paracetamol extraction, the resulting surface area was between 30 m2 g−1 and 290 m2 g−1. The presence of paracetamol was confirmed by the presence of an infrared absorption band at 1546 cm−1, which is assigned to ν(C=O). The adsorption of paracetamol from aqueous and urine matrixes on the imprinted materials produced by the acid-catalyzed route was ca. 60% of the nominal concentration present in such matrixes. In the silica without molecular imprints, the preconcentration was ca. 20%.Graphical Abstract