Search Results (13)

This work assesses the dietary use of two insect meals of Tenebrio molitor (TM) larvae reared in conventional (TM-10) or MAP-enriched substrates (MAP-TM-10) as fish meal replacements (10%) in the diets of gilthead seabream (Sparus aurata). Fish (n = 4500; 207.19 ± 1.47 g) were divided into three groups with triplicates: control (fed conventional diet), TM-10, and MAP-TM-10 groups. The fish were reared in floating cages for 12 weeks and the dietary effects on white blood cell activation, heat shock proteins, MAPKs, and apoptosis of the fish were evaluated. The MAP-TM-10 group exhibited the highest eosinophilic induction. Phosphorylated levels of p38 MAPK, p44/42 MAPK, HSP70, and HSP90 increased in the TM-10 and MAP-TM-10 groups. In terms of apoptosis, Bax levels were lower in the TM groups compared to the control, and the MAP-TM-10 group showed even lower levels than the TM-10 group. Bcl-2 levels increased in the TM-10 group compared to the control, and further increased in the MAP-TM-10 group. The Bax/Bcl-2 ratio, an apoptosis indicator, decreased in the TM groups, with the MAP-TM-10 group showing a further decrease compared to TM-10. These findings suggest that insects’ breeding substrate being enriched with MAPs modulated the effect of TM on cellular stress and apoptosis. Full article

Sol–gel coatings can provide anti-fouling and erosion resistance while being safe to use in the marine environment. MAPTMS/ZPO multilayer coatings deposited on the AA2024-T3 aluminium surface using the dip-coating method at three different thicknesses (2, 4, and 6 µm) are investigated in this work. The coatings are characterised in terms of physical and mechanical properties, and these properties are investigated in comparison to previously obtained cavitation erosion resistance levels of the coatings. Additionally, the efficiency of the coatings against biofouling was assessed using Phaeodactylum tricornutum, a marine diatom. The influence of the formation of organic–inorganic hybrid materials (OIHMs) from the prepared sols on the physical and mechanical properties of the coatings were analysed. A variety of techniques, including attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR), water contact angle (WCA) measurements, pencil hardness testing, cross-cut adhesion testing, a roughness profilometer, and nano-indentation, were performed on the bare and coated substrates. The results indicated that the thickness, hydrophobicity, and adherence of the coatings are strongly affected by the roughness. The elastic strain failure (H/E) and resistance to plastic deformation (H³/E²) coefficients were higher than those of the bare substrate before and after the cavitation erosion test, indicating that the coating had a higher ability to withstand deformation in comparison to the substrate alone. Furthermore, the microscopic analysis of a marine diatom, Phaeodactylum tricornutum, revealed that coated surfaces exhibited a decreased rate of bacterial adhesion and biofilm formation. The data show that sol–gel formed coatings outperform uncoated AA2024-T3 in terms of hardness, elastic strain, plastic deformation, and biofouling resistance. These characteristics are attributed to the coatings’ mechanical and adhesive capabilities, as well as their tribological behaviour. Full article

The application of sol–gel on plasma electrolytic oxidation (PEO) coatings can increase wear resistance by sealing the surface defects such as pores and cracks in the outer layer of the PEO layer and strengthen the coating. Four different sol–gel formulations based on precursors—(3-glycidyloxypropyl)trimethoxysilane (GPTMS), methyltriethoxysilane (MTES), methacryloxypropyltrimethoxysilane (MAPTMS), (3-aminopropyl)triethoxysilane (APTES), and zirconium(IV) propoxide (ZTP) along with tetraethoxysilane (TEOS)—were used to seal PEO pores, and the samples were tested tribologically. A sliding reciprocating tribometer was used to carry out a wear test with an alumina ball as the counter body in two different conditions: (a) 2.5 N load for 20 min, and (b) 3 N load for 40 min. The coefficient of friction and wear rate as volume loss per unit sliding length were obtained for all sol–gel-sealed specimens and unsealed PEO-coated and bare AA2024 substrate. 3D mechanical profilometer surface scans were used to compare the depth of wear traces. The elemental color mapping using SEM and EDS revealed that silicon remains present in the wear tracks of PEO coatings sealed with sol–gel layers containing GPTMS (PSG) and ZTP (PSG-ZT). GPTMS (PSG) was able to fill the pores of the PEO layer efficiently due to its cross-linked network. Moreover, sol–gel containing ZTP (PSG-ZT) was deposited as a thick layer on top of the PEO layer which provided good lubrication and resistance to wear. However, other sol–gel formulations (PSG-MT and PSG-AP) were worn out during tests at a higher load (3 N). The most stable friction coefficient (COF) and specific wear rates were observed with sol–gels with GPTMS and ZTP. Full article

AA2024-T3 are widely used in various applications because of their exceptional physical properties. However, they are susceptible to corrosion and cavitation erosion in aggressive environments due to high concentration of copper. Sol-gel coatings in the field of corrosion prevention are emerging. Improved thickness of coatings significantly improves the barrier effect of the coatings, thereby improving their operational-life in industrial applications. To date, a limited amount of work has been carried out in determining the effect of hybrid sol-gel coatings on abrasion and cavitation erosion of AA2024-T3. The present study investigates the effect of thickness of the coatings on morphology, corrosion, abrasion and cavitation erosion properties of the prepared hybrid sol-gel coatings deposited on AA2024-T3 surfaces. The hybrid sol-gels have been synthesized from 3-trimethoxysilylpropylmethacrylate (MAPTMS), and a zirconium complex prepared from the chelation of zirconium n-propoxide (ZPO), and methacrylic acid (MAAH). AA-2024 T3 were coated using single-dip, double-dip and triple-dip. Abrasion and cavitation erosion tests were performed according to the relevant standards. Structural damage caused by corrosion, abrasion and cavitation erosion was studied by Optical Microscope and Scanning Electron Microscope (SEM). Corrosion protection performance of the coatings was tested using Open Circuit Potential (OCP) and Potentiodynamic polarization (PDS). Results indicated that the multilayer coated samples improved the corrosion, cavitation erosion and abrasion resistance of AA2024-T3. Hence, the prepared silica-based coatings can be proposed as a potential choice for marine renewable energy applications. Full article

Infection is one of the most common causes that leads to joint prosthesis failure. In the present work, biodegradable sol-gel coatings were investigated as a promising controlled release of antibiotics for the local prevention of infection in joint prostheses. Accordingly, a sol-gel formulation was designed to be tested as a carrier for 8 different individually loaded antimicrobials. Sols were prepared from a mixture of MAPTMS and TMOS silanes, tris(tri-methylsilyl)phosphite, and the corresponding antimicrobial. In order to study the cross-linking and surface of the coatings, a battery of examinations (Fourier-transform infrared spectroscopy, solid-state ²⁹Si-NMR spectroscopy, thermogravimetric analysis, SEM, EDS, AFM, and water contact angle, thickness, and roughness measurements) were conducted on the formulations loaded with Cefoxitin and Linezolid. A formulation loaded with both antibiotics was also explored. Results showed that the coatings had a microscale roughness attributed to the accumulation of antibiotics and organophosphites in the surface protrusions and that the existence of chemical bonds between antibiotics and the siloxane network was not evidenced. Full article

Across all ages, individuals with Down syndrome (DS) experience high rates of sleep problems as well as cognitive impairments. This study sought to investigate whether circadian rhythm disruption was also experienced by people with DS and whether this kind of sleep disorder may be correlated with cognitive performance. A cross-sectional study of 101 participants (58 with DS, 43 with typical development) included individuals in middle childhood (6–10 years old), adolescence (11–18 years old), and young adulthood (19–26 years old). Sleep and markers of circadian timing and robustness were calculated using actigraphy. Cognitive and behavioral data were gathered via a novel touchscreen battery (A-MAP^TM, Arizona Memory Assessment for Preschoolers and Special Populations) and parent questionnaire. Results indicated that children and adolescents with DS slept the same amount as peers with typical development, but significant group differences were seen in phase timing. The circadian robustness markers, interdaily stability and intradaily variability of sleep-wake rhythms, were healthiest for children regardless of diagnostic group and worst for adults with DS. Amplitude of the 24-h activity profile was elevated for all individuals with DS. In analyses of the correlations between sleep quality, rhythms, and cognition in people with DS, interdaily stability was positively correlated with reaction time and negatively correlated with verbal and scene recall, a finding that indicates increased stability may paradoxically correlate with poorer cognitive outcomes. Further, we found no relations with sleep efficiency previously found in preschool and adult samples. Therefore, the current findings suggest that a thorough examination of sleep disorders in DS must take into account age as well as circadian robustness to better understand sleep-cognitive correlations in this group. Full article

Zr-based oxoclusters M_xO_y(OR)_w(OOR’)_z are promising catalysts for the activation of hydrogen peroxide. However, they need to be integrated into suitable matrices to increase their hydrolytic stability and allow for their recovery after use. Polymeric materials can be successfully employed for this aim, since they modify the properties of the resulting hybrid materials, in terms of polarity and chemical affinity for the substrates, improving the catalytic activity. Herein, we report the synthesis of different acrylic polymers based on various co-monomers (methyl methacrylate (MMA), 2,2,2-trifluoroethylmethacrylate (TFMA) and 3-methacryloxypropyltrimethoxylsilane (MAPTMS)) covalently cross-linked by a Zr₄-based oxocluster, whose composition was tuned to optimise the catalytic oxidation of methyl p-tolyl sulphide. To assess their properties and stability, the materials were characterised via Fourier Transform Infrared (FT-IR) and Raman spectroscopies, Thermogravimetric Analysis (TGA), Solid-State NMR (SS-NMR) and X-Ray Absorption Spectroscopies XAS, before and after catalytic turnover. Full article

The aim of this study was to develop new chrome-free surface pretreatments for AA2024-T3 aluminum alloy. These pretreatments were based on hybrid organic–inorganic sol–gel thin films prepared from mixtures of γ-methacryloxypropyltrimethoxysilane (MAPTMS) and tetramethylorthosilicate (TMOS). Different MAPTMS/TMOS molar ratios were used for optimizing the physical–chemical characteristics of the sol–gel films. The formulation of a set of these sols was modified by incorporating piperazine (1,4-diazacyclohexane) as a corrosion inhibitor. The resulting sol–gel films were characterized by using Fourier transform infrared spectroscopy (FTIR), liquid-state ²⁹Si nuclear magnetic resonance spectroscopy (²⁹Si-NMR) and viscosity measurements. The corrosion performance of the sol–gel films was analyzed by using electrochemical impedance spectroscopy (EIS) and local electrochemical impedance mapping (LEIM). The characterization techniques indicated that piperazine behaved as a catalyst for the condensation reaction during the formation of the MAPTMS/TMOS organopolysiloxane network and produces an increase of the crosslinking degree of the sol–gel films. EIS and LEIM results showed that piperazine is an effective corrosion inhibitor, which can be used to enhance the active corrosion protection performance of sol–gel films. Full article

Pre-hydrolysed/condensed tetraethyl orthosilicate (TEOS) was added to a solution of methyl methacrylate (MMA) and 3-methacryloxypropyltrimethoxysilane (MAPTMS), and then copolymerised for various times to study the influence of the latter on the structure of hybrid sol-gel coatings as corrosion protection of aluminium alloy 7075-T6. The reactions taking place during preparation were characterised using real-time Fourier transform infrared spectroscopy, dynamic light scattering and gel permeation chromatography. The solution characteristics were evaluated, using viscosimetry, followed by measurements of thermal stability determined by thermogravimetric analysis. The optimal temperature for the condensation reaction was determined with the help of high-pressure differential scanning calorimetry. Once deposited on 7075-T6 substrates, the coatings were evaluated using a field emission scanning electron microscope coupled to an energy dispersive spectrometer to determine surface morphology, topography, composition and coating thickness. Corrosion properties were tested in dilute Harrison’s solution (3.5 g/L (NH₄)₂SO₄ and 0.5 g/L NaCl) using electrochemical impedance spectroscopy. The copolymerization of MMA and MAPTMS over 4 h was optimal for obtaining 1.4 µm thick coating with superior barrier protection against corrosion attack (|Z_{10 mHz}| ~ 1 GΩ cm²) during three months of exposure to the corrosive medium. Full article

This study investigated polysiloxane hybrid sol-gel coatings synthesized from tetraethyl orthosilicate (TEOS), 3-(trimethoxysilyl)propyl methacrylate (MAPTMS) and two different precursors, i.e., methyl- or ethyl- methacrylate (MMA or EMA), as corrosion protection of aluminium alloy 7075-T6. The hypothesis was that the additional alkyl group might affect the chemical properties and, consequently, the corrosion properties. Synthesis of the sols proceeded in two steps, each involving either MMA or EMA in the same molar ratio. The resulting sols, siloxane-(poly(methyl methacrylate-co-MAPTMS)) or siloxane-(poly(ethyl methacrylate-co-MAPTMS)), were applied on aluminium alloy followed by characterization in terms of chemical structure and composition, topography, wettability, adhesion and corrosion resistance in 0.1 M sodium chloride solution. The chemical properties of sols, monoliths and coatings were investigated using Fourier transform infrared spectrometry, solid state nuclear magnetic resonance spectrometry, X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry. Coatings were similar in terms of surface topography, while the wettability of the coating with EMA showed 6° greater water contact angle compared to the coating with MMA. Both coatings were shown, by electrochemical impedance spectroscopy in 0.1 M NaCl solution, to act as barriers to protect the underlying substrate in which coating with EMA exhibits better protection properties after 2 months of immersion. Adhesion tests confirmed the highest grade of adhesion to the substrate for both coatings. Testing in a salt-spray chamber demonstrated excellent corrosion protection, where coatings remaining intact after more than 600 h of exposure. Full article

The functional properties displayed by graphene oxide (GO)-polymer nanocomposites are strongly affected by the dispersion ability of GO sheets in the polymeric matrix, which can be largely improved by functionalization with organosilanes. The grafting to GO of organosilanes with the general formula RSi(OCH₃)₃ is generally explained by the condensation reactions of silanols with GO reactive groups. In this study, the influence of the organic group on the RSi(OCH₃)₃ grafting ability was analyzed in depth, taking into account the interactions of the R end chain group with GO oxidized groups. Model systems composed of commercial graphene oxide reacted with 3-aminopropyltrimethoxysilane (APTMS), 3-mercaptopropyltrimethoxysilane (MPTMS), and 3-methacryloxypropyltrimethoxysilane, (MaPTMS), respectively, were characterized by natural abundance ¹³C, ¹⁵N and ²⁹Si solid state nuclear magnetic resonance (NMR), x-ray diffraction (XRD), and electron spin resonance (ESR). The silane organic tail significantly impacts the grafting, both in terms of the degree of functionalization and direct interaction with GO reactive sites. Both the NMR and XRD proved that this is particularly relevant for APTMS and to a lower extent for MPTMS. Moreover, the epoxy functional groups on the GO sheets appeared to be the preferential anchoring sites for the silane condensation reaction. The characterization approach was applied to the GO samples prepared by the nitric acid etching of graphene and functionalized with the same organosilanes, which were used as a filler in acrylic coatings obtained by cataphoresis, making it possible to correlate the structural properties and the corrosion protection ability of the layers. Full article

This study aimed at the adsorption of 18β-glycyrrhetinic acid (18β-GA), a pentacyclic triterpenoid derivative of oleanane type, onto functionalized mesoporous SBA-15 silica and non-porous silica (Aerosil^®) as the reference adsorbent. Although 18β-GA possesses various beneficial pharmacological properties including antitumor, anti-inflammatory, and antioxidant activity, it occurs is small amounts in plant materials. Thus, the efficient methods of this bioactive compound enrichment from vegetable raw materials are currently studied. Siliceous adsorbents were functionalized while using various alkoxysilane derivatives, such as (3-aminopropyl)trimethoxysilane (APTMS), [3-(methylamino)propyl]trimethoxysilane (MAPTMS), (N,N-dimethylaminopropyl)trimethoxysilane (DMAPTMS), and [3-(2-aminothylamino)propyl] trimethoxysilane (AEAPTMS). The effect of silica surface modification with agents differing in the structure and the order of amine groups on the adsorption capacity of the adsorbent and adsorption efficiency were thoroughly examined. The equilibrium adsorption data were analyzed while using the Langmuir, Freundlich, Redlich-Peterson, Temkin, Dubinin-Radushkevich, and Dubinin-Astakhov isotherms. Both linear regression and nonlinear fitting analysis were employed in order to find the best-fitted model. The adsorption isotherms of 18β-GA onto silicas functionalized with APTMS, MAPTMS, and AEAPTMS indicate the Langmuir-type adsorption, whereas sorbents modified with DMAPTMS show the constant distribution of the adsorbate between the adsorbent and the solution regardless of silica type. The Dubinin-Astakhov, Dubinin-Radushkevich, and Redlich-Peterson equations described the best the process of 18β-GA adsorption onto SBA-15 and Aerosil^® silicas that were functionalized with APTMS, MAPTMS, and AEAPTMS, regardless of the method that was used for the estimation of isotherm parameters. Based on nonlinear fitting analysis (Dubinin-Astakhov model), it can be concluded that SBA-15 sorbent that was modified with APTMS, MAPTMS, and AEAPTMS is characterized by twice the adsorption capacity (202.8–237.3 mg/g) as compared to functionalized non-porous silica (118.2–144.2 mg/g). Full article

Different characterization techniques were used to study the hydrolysis and condensation reaction kinetics of 3-methacryloxypropyltrimethoxysilane (MAPTMS) to obtain open cage silsesquioxane oligomers. The formation of hydrogen bonds, which condition the chemical structures of the resulting products, was identified. Improved thermal and fire resistant behavior of unsaturated polyester (UP) composites prepared with aluminium trihydroxide (ATH) and the synthesized oligomer were registered. Opened silsesquioxane structures also showed an improvement in the mechanical properties of the char formed after firing. Full article