Stöber method and its nuances over the years.

Some characteristics of silica-based materials, such as the control/adjustment of their physical and chemical properties, compatibility, and friendly-use synthesis methods, have held the attention of several scientific groups over the years. This condition of prominence becomes even more evident when we seek these characteristics at the micro- and/or nanoscale. Among existing methods to obtain these micro/nanomaterials, the Stöber method is the focus of this review. This method is known to enable the production of silica micro- or nanoparticles from reagents of medium-easy manipulation under mild conditions using equipment that is common in most laboratories. However, this method has many nuances that must be considered to guarantee accurate results, either in size or distribution, and to ensure result reproducibility. Thus, in this review, we discuss the effects of the primary components used in the synthesis of these materials (i.e., TEOS, ammonia, and water), as well as those of other reaction conditions, such as solvent, temperature, and ionic strength. Therefore, we discuss studies involving the synthesis and characterization of micro- and nanoparticles over the years to establish discussions between their experimental observations and proposed models. This review provides experimental observations about the synthesis of these materials, as well as discussions according to complementary and/or contradictory evidence found over the years. This review seeks to help those who intend to work with this method and provide certain key points that, in our experience, can be important to obtain desired results.

Nanomaterials to help eco-friendly leather processing.

The leather industry converts the hide, a byproduct of slaughterhouses, into leather, a value-added product. This old industry generates wastes, causing environmental pollution. However, nanomaterials can help to decrease this problem. These tiny particles (1-100 nm) can replace chemicals in various steps of leather processing. This paper aims at giving an overview of the fundamentals of classical leather process and how nanomaterials can be applied in each step to obtain a more sustainable manufacturing. After a comprehensive literature review of journal articles, six steps were identified for potential for application of nanomaterials: unhairing, tanning, retanning, dyeing, fatliquoring, and finishing. With nano-oxides, polymers, and metals, it is feasible to reduce the amount of chemical products and also improve the properties of leather. Thus, it is possible to reach a more eco-friendly and effective process with the use of nanomaterials to turn hide/skins into finished leather.

Degradation of pharmaceuticals in wastewater matrices through solar light-driven photocatalyst prepared from petrochemical waste.

Pharmaceuticals, such as dipyrone (DIP), paracetamol (PCT), and propranolol (PPN), are widely used analgesics and beta-blockers with the greatest presence in wastewaters and, consequently, in natural waters. The present work evaluated solar light-driven photocatalyst from petrochemical industrial waste (PW) as a strategy for the degradation of three pharmaceuticals in different water matrices (distilled water-DW, simulated wastewater-SWW, and real hospital wastewater-RHWW). All experiments were carried out in a solar photo-reactor with a capacity of 1 L and the experimental condition employed was a catalyst concentration of 350 mg L-1 at pH 5.0; these conditions were selected considering the Doehlert design validation spreadsheet and the desirability function. All materials prepared were conveniently characterized by zeta potential, small-angle X-ray scattering (SAXS), diffuse reflectance ultraviolet-visible (DRUV), and infrared spectroscopy. According to the results of the characterization, significant differences have been observed between the PW and the photocatalyst such as vibrational modes, optical absorption gap, and acid-basic characteristics on the surface, which suggests the potential use of the photocatalyst in the degradation of contaminants of emerging concern. Based on pharmaceutical degradation, DIP showed the highest photosensitivity (87.5%), and therefore the highest photocatalytic degradation followed by PPN; both compounds achieved final concentrations below the limit of quantification of the chromatographic method in DW. However, PCT was the most recalcitrant pharmaceutical in all matrices. Radicals from chromophoric natural organic matter (NOM) could improve PCT degradation in the SWW matrix (56%). Nevertheless, the results in RHWW showed a matrix effect with decreased the oxidation percentages (DIP-99%; PPN-71%; PCT-17%); hence, the addition of an oxidant such as H2O2 was studied as a pharmaceutical oxidation boost in RHWW. PPN was the molecule most sensitive to this strategy of oxidation (98%). Furthermore, 20 transformation products (TPs) generated throughout the treatment were identified by LC-QTOF MS using a customized TPs database. According to quantitative structure activity relationship (Q)SAR analysis, more than 75% of the TPs identified were not biodegradable. About 35% of them have oral toxicity characteristics indicated by Cramer's rules, and the DIP TPs represent high toxicity for different trophic levels.

Antimicrobial activity of some natural extracts encapsulated within silica matrices.

Natural extracts (anthocyanins, tannin, anatto, curcuma and olive leaf extracts) were encapsulated within a silica network by acid or base-catalyzed sol-gel methods. The nominal encapsulated contents were between 2.5 and 50wt.-%. The resulting materials were characterized by Fourier transform infrared spectroscopy, diffuse reflectance in the UV region, nitrogen adsorption/desorption porosimetry and small angle X-ray scattering. Encapsulated anthocyanin and tannin afforded inhibition zones between 9-21mm towards Staphylococcus aureus, Escherichia coli, Bacillus cereus, Candida sp. and Aspergillus niger, which was comparable to the free bioactive material in which the inhibition zones were between 10 and 22mm. Anthocyanin exhibited high antioxidant activity in the free state, while tannin showed good antioxidant activity both in its free state and in its encapsulated form. Antimicrobial and antioxidant activities were shown to be dependent on the textural characteristics of the encapsulated materials.

Structural, textural and morphological characteristics of tannins from Acacia mearnsii encapsulated using sol-gel methods: Applications as antimicrobial agents.

Tannins from Acacia mearnsii were encapsulated using four different sol-gel methods acid (SGAR), basic (SGBR), silicate (SGSR) and non-hydrolytic (SGNHR) routes. The hybrid materials were analyzed using a set of techniques to characterize their structure, texture and morphology. The antimicrobial performance of the encapsulated materials was evaluated against different microorganisms (Staphylococcus aureus, Escherichia coli, Aspergillus niger and Candida sp.). The data showed that the encapsulation route significantly affects the characteristics of the resulting hybrid materials. Better functional performances were obtained using the silicate route, which produced mesoporous materials with a small surface area (0.96m2g-1) and small particle size (<1nm). These characteristics promoted the gradual release of tannins in an aqueous medium and improved their interactions with microorganisms. Furthermore, the process demonstrated the preservation of tannins after synthesis and increased antimicrobial activity (via a controlled tannin release), as demonstrated by the moderate activity against filamentous fungi and yeast.

Hybrid Thin Film Organosilica Sol-Gel Coatings To Support Neuronal Growth and Limit Astrocyte Growth.

Thin films of silica prepared by a sol-gel process are becoming a feasible coating option for surface modification of implantable neural sensors without imposing adverse effects on the devices' electrical properties. In order to advance the application of such silica-based coatings in the context of neural interfacing, the characteristics of silica sol-gel are further tailored to gain active control of interactions between cells and the coating materials. By incorporating various readily available organotrialkoxysilanes carrying distinct organic functional groups during the sol-gel process, a library of hybrid organosilica coatings is developed and investigated. In vitro neural cultures using PC12 cells and primary cortical neurons both reveal that, among these different types of hybrid organosilica, the introduction of aminopropyl groups drastically transforms the silica into robust neural permissive substrate, supporting neuron adhesion and neurite outgrowth. Moreover, when this organosilica is cultured with astrocytes, a key type of glial cells responsible for glial scar response toward neural implants, such cell growth promoting effect is not observed. These findings highlight the potential of organo-group-bearing silica sol-gel to function as advanced coating materials to selectively modulate cell response and promote neural integration with implantable sensing devices.

Photocatalytic degradation of nicotine in an aqueous solution using unconventional supported catalysts and commercial ZnO/TiO2 under ultraviolet radiation.

Nicotine, a highly toxic alkaloid, has been detected in effluents, surface and groundwater and even bottled mineral water. The present work studied the photocatalytic degradation of nicotine in aqueous solution, under ultraviolet irradiation. The experiments were carried out using commercial (ZnO, TiO2) and non-conventional catalysts, which were prepared from industrial and laboratory waste. Two experimental designs (CCD) were performed for both commercial catalysts, and initial nicotine concentration, catalyst concentration and initial solution pH effects were studied. Then, the synthesized catalysts were tested under the optimal conditions which were found through CCDs. Using commercial catalysts, about 98% of the alkaloid was degraded by ZnO, and 88% by TiO2, in 1h. Among the non-conventional catalysts, the highest photocatalytic degradation (44%) was achieved using the catalyst prepared from a petrochemical industry residue.

Tailored silica-antibiotic nanoparticles: overcoming bacterial resistance with low cytotoxicity.

New and more aggressive antibiotic resistant bacteria arise at an alarming rate and represent an ever-growing challenge to global health care systems. Consequently, the development of new antimicrobial agents is required to overcome the inefficiency of conventional antibiotics and bypass treatment limitations related to these pathologies. In this study, we present a synthesis protocol, which was able to entrap tetracycline antibiotic into silica nanospheres. Bactericidal efficacy of these structures was tested against bacteria that were susceptible and resistant to antibiotics. For nonresistant bacteria, our composite had bactericidal efficiency comparable to that of free-tetracycline. On the other hand, the synthesized composites were able to avoid bacterial growth of resistant bacteria while free-tetracycline has shown no significant bactericidal effect. Finally, we have investigated the cytotoxicity of these nanoparticles against mammalian cells to check any possible poisoning effect. It was found that these nanospheres are not apoptosis-inducers and only a reduction on the cell replication rate was seen when compared to the control without nanoparticles.

Effect of the sol-gel route on the textural characteristics of silica imprinted with Rhodamine B.

A series of silica xerogels that support Rhodamine B as a template were synthesized using distinct sol-gel routes, namely, acid-catalyzed routes, a base-catalyzed route, acid-catalyzed with base-catalyzed (two steps) hydrolytic routes, and a FeCl3 -catalyzed nonhydrolytic route. The extraction methods (thermal, Soxhlet, water washing, and ultrasound) were also evaluated. The resulting xerogels were characterized through porosimetry using nitrogen adsorption/desorption. The samples were further analyzed through small-angle X-ray scattering, Fourier transform infrared spectroscopy, and SEM. The preparation route affected the materials' textural properties. Extraction was optimized using acid and two-step routes. The acid route from Rhodamine B to Rhodamine 6G generated the highest selectivity factor (2.5). The nonhydrolytic route produced the best imprinting factor. Competitive adsorption was also used, from which the approximate imprinting factor was 2. The cavity shape generated during the production of the imprinted silica dictates the adsorption behavior, not the magnitude of the surface area.

Synthesis of zirconocene-based silica phases and evaluation in lindane and heptachlor epoxide adsorption/desorption.

Silica (350 m(2) g(-1)) was chemically modified with Cp2ZrCl2 and (nBuCp)2ZrCl2 by grafting. Hybrid silica bearing surface indene groups was synthesized by the sol-gel method, followed by metallation with ZrCl(4)2THF. The resulting phases were characterized by Rutherford backscattering spectrometry (RBS), 13C and 29Si magic angle spin nuclear magnetic resonance, X-ray photoelectron spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy. According to RBS measurements, metal content was 0.2- to 0.3-wt% Zr/SiO2 for the grafted systems and 4.5-wt% Zr/SiO2 for the phase prepared by the sol-gel method. The solid phases were evaluated for the adsorption/preconcentration of lindane and heptachlor epoxide from aqueous solution. For comparative reasons, the commercial LC-18 phase was also evaluated. Analyte concentration was monitored by gas chromatography electron capture detection. For the grafted phases, the coordination sphere around the metal center seems not to influence the adsorption/desorption properties of these phases vis-a-vis the studied analytes. In the case of the phases prepared by the sol-gel method, recovery results were comparable to those observed for LC-18. Experiments using ZrO2 and ZrO2/SiO2 phases led to lower recovery results.