Search Results (12)

Warm asphalt mixtures can suffer from decreased short-term high-temperature performance; therefore, introducing additional modifiers can mitigate this risk. This study investigates the effects of a liquid organosilane warm mix additive (WMAd) and grade-bumping polyethylene-based additive added simultaneously to asphalt binders on their chemical composition and its relationship with performance characteristics. Previous studies found relationships between the formation of certain chemical species during bitumen ageing and the increase in their viscosity, stiffness and other performance characteristics—the present work intended to verify these relationships when the two mentioned additives are used. Two asphalt binders were investigated—a paving-grade 50/70 binder and a 45/80-55 polymer-modified bitumen. The chemical analysis was performed using Fourier-transform infrared (FTIR) spectroscopy in attenuated total reflectance mode and focused on the quantification of carbonyl, sulfoxide, polybutadiene and polystyrene structures in the asphalt binders subjected to laboratory short- and long-term ageing. Additionally, the relationships between asphalt binder performance and selected FTIR indices were evaluated using a dynamic shear rheometer. It was found that the investigated additives significantly affected the apparent contents of all evaluated chemical structures in the asphalt binders; however, these changes were not reflected in their performance evaluation. Full article

A source of Brønsted acid centers, generated on the surface of two mesoporous silica supports of different structures (SBA-15 and MCF), was 3-(trihydroxysilyl)-1-propanesufonic acid (TPS). The materials obtained were characterized and applied as catalysts for the oxidative desulfurization of dibenzothiophene (DBT) with hydrogen peroxide as a model ODS (oxidative desulfurization) process. The properties of the materials were examined via nitrogen physisorption, XRD (X-ray Diffraction) and elemental analysis showing the preservation of the support structure after modification with organosilane species. Due to the aggregation of catalyst particles in the reaction mixture, the SBA-15 based catalyst was not very effective in DBT oxidation. Contrary, TPS/MCF catalyst exhibited a very good activity (almost total conversion of DBT after 1 h in optimized reaction conditions) and stability in dibenzothiophene oxidation in mild reaction conditions. Full article

In this work, impermeable and ultrathin surface nanomodifications for joint applications based on graphene oxide (GO) are assembled on CoCr surfaces via covalent immobilization between GO nanosheets and silane monolayers. Two silane curing temperatures, 45 °C for 24 h and 75 °C for 30 min, on CoCr surfaces and two incubation times for GO suspension, 12 h and 24 h, on silanized CoCr surfaces are prepared. Electrochemical characterization is performed using electrochemical impedance spectroscopy (EIS) in a 3 g/L hyaluronic acid solution. Results show that GO nanosheets immobilized with silane covalent bonding confer impermeability of sp2 networks on GO and strong interfacial adhesion of GO sheets anchored to silanized CoCr via organosilane chemistry, which prevents the permeation of oxidant species at the metal interface. At short GO incubation times (12 h), the Rs values decrease with the immersion time, indicating that small species, such as metal ions, are able to diffuse through the interlayer gaps of nanolayers. Longer GO incubation times (24 h) favor the formation of bonds between the GO and the silane, thus slowing downdiffusion and metal ion release into the medium. EIS data confirm the impermeability of GO nanocoatings with lengthening GO incubation time for medical application of metallic implants. Full article

This review focuses on techniques for modifying the surface of carbon that is produced from sustainable resources, such as pyrolytic carbon. Many of these materials display high specific surface area and fine particle distribution. Functionalization of a surface is a commonly used approach in designing desired surface properties of the treated material while retaining its bulk properties. Usually, oxidation is a primary step in carbon functionalization. It can be performed as wet oxidation, which is a type of chemical surface modification. Wet oxidation is usually performed using nitric acid and hydrogen peroxide, as well as using hydrothermal and solvothermal oxidation. On the other side, dry oxidation is representative of physical surface modification. This method is based on corona discharge and plasma oxidation which are promising methods that are in line with green chemistry approaches. Whilst the oxidation of the carbon surface is a well-known method, other chemical modification techniques, including cycloadditions and various radical reactions on graphene layers, are presented as an alternative approach. Regarding secondary functionalization, coupling organosilanes to activated carbon is a common technique. Organosilanes bearing reactive groups present a bridge between inorganic species and polymer systems, e.g., epoxy and polyurethane resins, and facilitate the use of carbonaceous materials as reinforcing components for polymers and thermosetting resins. Along with the presented functionalization methods, this review also provides an overview of new applications of modified (i.e., functionalized) carbon materials, e.g., for the building industry, wastewater treatment, semiconducting materials and many more. Full article

The current study evaluates the role of reactive oxygen species (ROS) in bioeffects of magnetite nanoparticles (MNPs), such as bare (Fe₃O₄), humic acids (Fe₃O₄-HA), and 3-aminopropyltriethoxysilane (Fe₃O₄-APTES) modified MNPs. Mössbauer spectroscopy was used to identify the local surrounding for Fe atom/ions and the depth of modification for MNPs. It was found that the Fe₃O₄-HA MNPs contain the smallest, whereas the Fe₃O₄-APTES MNPs contain the largest amount of Fe²⁺ ions. Bioluminescent cellular and enzymatic assays were applied to monitor the toxicity and anti-(pro-)oxidant activity of MNPs. The contents of ROS were determined by a chemiluminescence luminol assay evaluating the correlations with toxicity/anti-(pro-)oxidant coefficients. Toxic effects of modified MNPs were found at higher concentrations (>10⁻² g/L); they were related to ROS storage in bacterial suspensions. MNPs stimulated ROS production by the bacteria in a wide concentration range (10⁻¹⁵–1 g/L). Under the conditions of model oxidative stress and higher concentrations of MNPs (>10⁻⁴ g/L), the bacterial bioassay revealed prooxidant activity of all three MNP types, with corresponding decay of ROS content. Bioluminescence enzymatic assay did not show any sensitivity to MNPs, with negligible change in ROS content. The results clearly indicate that cell-membrane processes are responsible for the bioeffects and bacterial ROS generation, confirming the ferroptosis phenomenon based on iron-initiated cell-membrane lipid peroxidation. Full article

The demand for exterior wood siding is stagnating in North America due in part to perceptions of low durability and the need for frequent maintenance. One way to address these concerns is to modify the wood to improve its physical properties, while maintaining its appearance. In this study, white spruce was treated with organosilanes and a combination of aluminum treatments followed by a thermal treatment to improve the dimensional stability and the wood durability. Anti-swelling efficiency (ASE), leaching and decay tests were performed on the treated Canadian wood species. The quantity of hydroxyls available after treatment was evaluated by water vapor sorption. The results showed that the treatment improved the dimensional stability up to 50%. Available hydroxyls decreased by as much as 37%. The organosilanes treatment was resistant to leaching, while the aluminum was observed to leach. Organosilanes in combination with aluminum showed brown rot resistance. The addition of aluminum to the organosilanes treatment did not have effect on dimensional stability but it had a great impact on the brown rot resistance. Full article

In this work, an electrode modified with an amino-functionalized clay mineral was used for the electrochemical analysis and quantification of quercetin (QCT). The resulting amine laponite (LaNH₂) was used as modifier for a glassy carbon electrode (GCE). The organic–inorganic hybrid material was structurally characterized using X-ray diffraction, Fourier transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and CHN elemental analysis. The covalent grafting of the organosilane to the clay backbone was confirmed. The charge on the aminated laponite, both without and with the protonation of NH₂ groups, was evaluated via cyclic voltammetry. On the protonated amine (LaNH₃⁺)-modified GCE, the cyclic voltammograms for QCT showed two oxidation peaks and one reduction peak in the range of −0.2 V to 1.2 V in a phosphate buffer–ethanol mixture at pH 3. By using the differential pulse voltammetry (DPV), the modification showed an increase in the electrode performance and a strong pH dependence. The experimental conditions were optimized, with the results showing that the peak current intensity of the DPV increased linearly with the QCT concentration in the range from 2 × 10⁻⁷ M to 2 × 10⁻⁶ M, leading to a detection limit of 2.63 × 10⁻⁸ M (S/N 3). The sensor selectivity was also evaluated in the presence of interfering species. Finally, the proposed aminated organoclay-modified electrode was successfully applied for the detection of QCT in human urine. The accuracy of the results achieved with the sensor was evaluated by comparing the results obtained using UV–visible spectrometry. Full article

Clays are very important from an economic and application point of view, as they are suitable hosts for organic compounds. In order to diversify the fields of application, they are structurally modified by physical or chemical methods with cationic species, and/or different bifunctional compounds, such as organosilanes. In this study, palygorskite was modified with (3-Aminopropyl) triethoxysilane, which was subsequently modified at the amino group by grafting an acetate residue. By using this strategy, two types of host hybrid materials were obtained on which curcumin derivatives were deposited. The composites obtained were structurally characterized and their photophysical properties were investigated in relation to the structure of the host matrices and interactions with curcumin-type visiting species. The hybrid composites have different colors (orange, yellow, pink), depending on the polarity of the inorganic matrices modulated by different organic groups grafted at the surface. Fluorescence emission in the visible range is characterized by the presence of two emission maxima, one belonging to the chromophore and the other influenced by the physical interactions between auxochromes and host matrices. These hybrid materials, compared to other composite structures, are obtained by a simple adsorption process. They are temperature stable in aggressive environments (acid/base) and render the fluorescent properties of dyes redundant, with improved luminescent performance compared to them. Full article

Wood of black pine and poplar species were subjected to thermal modification under variant conditions, while subsequently, a number of the thermally-modified black pine specimens were subjected to surface modification with organosilane solutions, and the biological resistances of the different materials were examined using laboratory agar block tests against the action of basidiomycetes and microfungi. Thermally-modified pine specimens were exposed to the brown rot fungi Coniophora puteana and Oligoporus placenta, whereas poplar wood was exposed to the white rot fungus Trametes versicolor and O. placenta. Regarding the biological durability of thermally-chemically-treated pine wood with organosilanes, it was tested against the action of C. puteana. Additionally, both of the thermally-treated wood species, as well as thermally-chemically-treated pine wood were exposed to a microfungi mixture, so that the wood treatments efficacy would be evaluated through a visual assessment of fungal growth on the specimen’s surface The thermal treatments seem to increase the biological resistance of black pine against C. puteana by 9.65–36.73% compared to unmodified wood. The most significant increase in biological durability among all the thermally-treated wood categories was recorded by O. placenta, with 28.75–68.46% lower mass losses in treated pine specimens and 31.98–64.72% in thermally-treated poplar, respectively, compared to unmodified wood. The resistance of treated poplar against T. versicolor was also found increased (13.25–46.08%), compared to control. Thermal modification affected positively the biological resistance of both species, though it did not manage to protect effectively pine and poplar wood from the microfungi action. The combination of thermal and organosilanes treatment revealed a significant improvement of the durability of pine wood compared to? control (45.68–87.83% lower mass losses against C. puteana), as well as against the microfungi action, with the presence of benzin to have a positive effect on the silanes solutions performance and protective action. Full article

Recalcitrant sulfur compounds are common impurities in crude oil. During combustion they produce SO_x derivatives that are able to affect the atmospheric ozone layer, increasing the formation of acid rains, and reducing the life of the engine due to corrosion. In the last twenty years, many efforts have been devoted to develop conventional hydrodesulfurization (HDS) procedures, as well as alternative methods, such as selective adsorption, bio-desulfurization, oxidative desulfurization (ODS) under extractive conditions (ECODS), and others. Among them, the oxidative procedures have been usually accomplished by the use of toxic stoichiometric oxidants, namely potassium permanganate, sodium bromate and carboxylic and sulfonic peracids. As an alternative, increasing interest is devoted to selective and economical procedures based upon catalytic methods. Heterogeneous catalysis is of relevance in industrial ODS processes, since it reduces the leaching of active species and favors the recovery and reuse of the catalyst for successive transformations. The heterogenization of different types of high-valent metal transition-based organometallic complexes, able to promote the activation of stoichiometric benign oxidants like peroxides, can be achieved using various solid supports. Many successful cases have been frequently associated with the use of mesoporous silicas that have the advantage of easy surface modification by reaction with organosilanes, facilitating the immobilization of homogeneous catalysts. In this manuscript the application of SBA-15 as efficient support for different active metal species, able to promote the catalytic ODS of either model or real fuels is reviewed, highlighting its beneficial properties such as high surface area, narrow pore size distribution and tunable pore diameter dimensions. Related to this topic, the most relevant advances recently published, will be discussed and critically described. Full article

The effect of physisorbed and chemisorbed species on the time-dependent self-assembly mechanism of organosilane films has been investigated on aluminium oxide using X-ray Photoelectron Spectroscopy. The role of physisorbed species was determined through their removal using a simple rinsing procedure while monitoring film substrate coverage. Removing physisorbed species from Propyldimethylmethoxysilane films, shown to follow a Langmuir-type adsorption profile, reduces the substrate coverage initially but quickly results in coverages equivalent to films that did not undergo a rinsing procedure. This indicates that all Propyldimethylmethoxysilane molecules are covalently bound to the substrate following 15 s of film growth. Removing physisorbed species from films, which have been shown to follow an oscillatory adsorption profile, Propyltrimethoxysilane and Propylmethyldimethoxysilane, reveal the persistence of these oscillations despite a reduction in silane substrate coverage. These results not only confirm the presence of two thermodynamically favourable phases in the condensation equilibrium reaction as physisorbed and chemisorbed species, but also indicate that the desorption of species during film growth involves both states of chemical binding. Full article

Nanoporous SnO₂ thin films were elaborated to serve as sensing electrodes for label-free DNA detection using electrochemical impedance spectroscopy (EIS). Films were deposited by an electrodeposition process (EDP). Then the non-Faradic EIS behaviour was thoroughly investigated during some different steps of functionalization up to DNA hybridization. The results have shown a systematic decrease of the impedance upon DNA hybridization. The impedance decrease is attributed to an enhanced penetration of ionic species within the film volume. Besides, the comparison of impedance variations upon DNA hybridization between the liquid and vapour phase processes for organosilane (APTES) grafting on the nanoporous SnO₂ films showed that vapour-phase method is more efficient. This is due to the fact that the vapour is more effective than the solution in penetrating the nanopores of the films. As a result, the DNA sensors built from vapour-treated silane layer exhibit a higher sensitivity than those produced from liquid-treated silane, in the range of tested target DNA concentration going to 10 nM. Finally, the impedance and fluorescence response signals strongly depend on the types of target DNA molecules, demonstrating a high selectivity of the process on nanoporous SnO₂ films. Full article