Search Results (15)

The paper deals with the joining of dissimilar steels by adhesive bonding. The base materials for the experimental work were deep-drawn low-carbon steel DC04, and hot-dip galvanized HSLA steel HX340LAD+Z. Adhesive bonding was performed using rubber-based and epoxy-based adhesives. The research aimed to verify the importance of surface preparation of steel substrates using a formulation with organically modified silica nanoparticles and epoxy organic functional groups, where one end of the functional group can be incorporated into the organic binder of the coating material and the other end can be firmly bonded to substances of an inorganic nature (metals). Since the binder base of adhesives is very similar to that of coatings, verifying the performance of this surface preparation when interacting with the adhesive is necessary. The load-bearing tensile shear capacity of single-lapped joints and the resistance of the joints against corrosion-induced disbanding in a climate chamber were tested. The energy dissipated by the joints up to fracture was calculated from the load-displacement curves. Bonded joints with organosilane were compared with joints without surface preparation and joints prepared by chroman-free zirconate passivation treatment. Exposure of the joints in the climatic chamber did not cause a relevant reduction in the characteristics of the joints. Organosilicate formulation was proved effective when bonding ungalvanized steels with a rubber-based structural adhesive, where it improves the bond quality between the adhesive and the substrate. Full article

Quaternary ammonium (QA) compounds have been widely studied as potential disinfectants in dental restorative materials. The present work investigates whether the gradual displacement of nanosilica by QA-clay nanoparticles may have an impact on the physicochemical and mechanical properties of dental nanocomposite resins. For this purpose, Bis-GMA/TEGDMA-based composite resins were initially synthesized by incorporating 3-(trimethoxysilyl)propyl methacrylate (γ-MPS)-modified nanosilica/QA-clay nanoparticles at 60/0, 55/5, 50/10, 40/20, and 30/30 wt% filler loadings. Their structural characterization was performed by means of scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). The degree of double bond conversion (DC) over time and the polymerization shrinkage were determined with Fourier transform infrared spectroscopy (FTIR) and a linear variable displacement transducer (LVDT), respectively. Mechanical properties as well as water sorption and solubility parameters were also evaluated after storage of nanocomposites in water for 7 days at 37 °C. Spectral data revealed intercalated clay configurations along with areas characterized by silica-clay clusters for clay loadings up to 30 wt%. Furthermore, the insertion of 10 wt% QA-clay enhanced the auto-acceleration effect also sustaining the ultimate (DC), reduced the setting contraction and solubility, and, finally, yielded flexural modulus and strength very close to those of the control nanocomposite resin. The acquired results could herald the advanced design of dental restorative materials appropriate for contemporary clinical applications. Full article

Cultural heritage metallic artifacts are often subjected to environmental factors that promote degradation through corrosion processes. Anticorrosion protection is needed both for the long-term preservation of outdoor monuments and the short-term conservation of archaeological artifacts. In this work, functional nanocoatings based on ZnO nanoparticles (NPs) in a silica matrix are prepared as a replacement for a commercial Incralac lacquer. Facile sol–gel synthesis is employed for obtaining silica filmogenic materials, using tetraethoxysilane (TEOS) and 3-glycidyloxypropyl trimethoxysilane (GPTMS). Silica-based nanocomposite coatings, with and without ZnO NPs and benzotriazole (BTA) as anticorrosion agents, applied on copper coupons by brushing are characterized by using VIS and FTIR spectroscopy, SEM and AFM and compared to Incralac lacquer as reference materials. The optical and morphological properties of the proposed silica coatings are similar to the Incralac specimens. The protective effect against corrosion is investigated on the copper coupons as model metallic objects subjected to a corrosion test by using potentiodynamic polarization in a 3.5% NaCl solution at ambient temperature. The influence of the presence of BTA and ZnO NPs in both silica and Incralac coatings is studied, and the variations in the anticorrosive, morphological and optical properties with the concentration of ZnO NPs are evidenced. The presence of moderate concentrations of ZnO in both nanomaterials leads to changes in the color parameters slightly above the limit accepted in the field of cultural heritage (ΔE* 5.09 and 6.13), while a high ZnO concentration of 3% leads to higher values (ΔE* > 10). Regarding the anticorrosive effect, the silica-based coatings with ZnO and BTA present similar efficiencies to that of the Incralac reference material (corrosion rates in the range of 0.044–0.067 mm/year for silica coatings compared to 0.055 mm/year for Incralac). Full article

Intracellular bacteria are inaccessible and highly tolerant to antibiotics, hence are a major contributor to the global challenge of antibiotic resistance and recalcitrant clinical infections. This, in tandem with stagnant antibacterial discovery, highlights an unmet need for new delivery technologies to treat intracellular infections more effectively. Here, we compare the uptake, delivery, and efficacy of rifampicin (Rif)-loaded mesoporous silica nanoparticles (MSN) and organo-modified (ethylene-bridged) MSN (MON) as an antibiotic treatment against small colony variants (SCV) Staphylococcus aureus (SA) in murine macrophages (RAW 264.7). Macrophage uptake of MON was five-fold that of equivalent sized MSN and without significant cytotoxicity on human embryonic kidney cells (HEK 293T) or RAW 264.7 cells. MON also facilitated increased Rif loading with sustained release, and seven-fold increased Rif delivery to infected macrophages. The combined effects of increased uptake and intracellular delivery of Rif by MON reduced the colony forming units of intracellular SCV-SA 28 times and 65 times compared to MSN-Rif and non-encapsulated Rif, respectively (at a dose of 5 µg/mL). Conclusively, the organic framework of MON offers significant advantages and opportunities over MSN for the treatment of intracellular infections. Full article

In this research, bio-based electrospun multilayered films for food packaging applications with good barrier properties and close to superhydrophobic behavior were developed. For this purpose, two different biopolymers, a low-melting point and fully bio-based synthetic aliphatic copolyamide 1010/1014 (PA1010/1014) and the microbially synthesized poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and food-contact-complying organomodified silica (SiO₂) nanostructured microparticles, were processed by electrospinning. The production of the multilayer structure was finally obtained by means of a thermal post-treatment, with the aim to laminate all of the components by virtue of the so-called interfiber coalescence process. The so developed fully electrospun films were characterized according to their morphology, their permeance to water vapor and oxygen, the mechanical properties, and their water contact angle properties. Interestingly, the annealed electrospun copolyamide did not show the expected improved barrier behavior as a monolayer. However, when it was built into a multilayer form, the whole assembly exhibited a good barrier, an improved mechanical performance compared to pure PHBV, an apparent water contact angle of ca. 146°, and a sliding angle of 8°. Consequently, these new biopolymer-based multilayer films could be a bio-based alternative to be potentially considered in more environmentally friendly food packaging strategies. Full article

Dental nanocomposite resins have been proposed as potential restorative materials that are inevitably challenged with dynamic oral conditions. This investigation focused on the contribution of miscellaneous silane blends, used as coupling agents, to the ultimate performance of dental nanocomposite dimethacrylate resins. Herein, silica nanoparticles were initially silanized with functional/functional or functional/non-fuctional silane mixtures (50/50 wt/wt). Fourier transforms infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA) verified the modification of nanosilica. The organomodified nanoparticles were then inserted into Bis-GMA/TEGDMA based resins by hand spatulation process. Scanning electron microscopy (SEM) findings revealed a broad distribution of fillers in the polymer network when reactive silanes and their corresponding blends were used. Furthermore, optical profilometry results showed that the presence of functional/non-functional mixtures can produce relatively smooth composite surfaces. Polymerization shrinkage was found to be limited upon the decrease of the degree of conversion regarding all the tested silane mixtures. The functional/functional silane blend assured the highest flexural properties and the lowest solubility after the storage of the nanocomposite in water for 1 week at 37 °C. The above experimental data could contribute to the proper designing of dental nanocomposite resins which may fit the modern clinical applications. Full article

A simple method to fabricate organo-modified silane coatings for water-repellent surface modification was proposed, by using a microwave sol-gel synthesis of hybrid materials. Low-cost fluorine-free tetraethoxysilane (TEOS) and dodecyltriethoxysilane (DDTES) were used as silane derivatives. The organo-modified silica coatings were prepared by the drop-casting method and were characterized by UV-VIS, FTIR spectroscopy, and AFM and SEM microscopy. The morphology of the film show the existence of submicrometer scale roughness due to the aggregation of modified silica nanoparticles. Contact angles of water and diiodomethane on surfaces modified with as prepared nanostructured film were determined in order to assess the hydrophobic and oleophobic properties. The TEOS/DDTES ratio was proved to be a crucial factor in tuning the wettability properties. The results suggest that significant increase of hydrophobicity could be achieved by using non-fluorinated cost-effective silica nanomaterials produced with a rapid ecofriendly method. Full article

Modern approaches to the production of new materials require the improvement of synthesis techniques towards simplifying the processes of their preparation and reducing the number of stages. Thus, in this study, one-stage synthesis of organomodified silica materials is developed using a special surfactant—dodecyldimethylamin N-oxide (DDAO). The peculiarity of this approach is that there is no need for heat treatment of the material, since DDAO is removed by washing in alcohol. Amino-, mercapto-, methyl-, and phenyl-modified silicas were synthesized using this method. The SEM images showed the morphology of all the obtained materials is close, all particles are spherical, and the diameter of individual particles is about 500 nm. Palladium particles were precipitated on these supports, then the experiments were carried out to study the catalytic activity of these materials in a model reaction of nitroaniline reduction. The phenyl modified matrix-based materials showed very low activity. This is due to the fact that the support and the substrate contain aromatic fragments, thus, hydrophobic interactions arise between them, which complicates the diffusion of the products. The leader is a matrix with an amino fragment, which is associated with its electron-donor effect. The XPS method revealed the amount of fixed palladium, as well as the binding energy shifts, which are 0.68 eV for 5% Pd/SiO₂–C₆H₅; 0.56 eV for 5% Pd/SiO₂–C₃H₆–NH₂; 0.26 eV for 5% Pd/SiO₂–CH₃; and 0.13 eV for 5% Pd/SiO₂. Full article

This study presents the facile sol-gel synthesis of nanostructured coatings for use in water-repellent treatment of travertine stone. The synthesized materials combine surface roughness characteristics with particular chemical compositions to give different hydrophobicity results. The influence of the silica particle coating precursor on the hydrophobicity of the polymeric film was investigated, and the octyl-modified silane was selected for further fabrication of the hybrid coatings. The water repellent properties, together with composition and structural properties of the silane-based hybrid material were measured on model glass surface. The coating with the best characteristics was subsequently deposited onto the travertine stone. The potential applicability of the nanostructured material was evaluated considering both the properties of the coating film and those of the travertine stone subjected to the treatment. The surface texture of the film, water repellent properties and uniformity were determined using scanning electron microscopy, atomic force microscopy, dynamic light scattering and contact angle measurements. The coating’s potential for use in stone conservation was evaluated by assessing its impact on the stone’s visual aspect. All the results obtained from the different types of analyses showed that the octyl-modified silica nanostructured material was highly hydrophobic and compatible both with the travertine stone and with the requirements for use on cultural heritage monuments. Full article

The design of cargo carriers with high biocompatibility, unique morphological characteristics, and capability of strong bonding of fluorescent dye is highly important for the development of a platform for smart imaging and diagnostics. In this paper, BODIPY-doped silica nanoparticles were prepared through a “one-pot” soft-template method using a sol-gel process. Several sol-gel precursors have been used in sol-gel synthesis in the presence of soft-template to obtain the silica-based materials with the most appropriate morphological features for the immobilization of BODIPY molecules. Obtained silica particles have been shown to be non-cytotoxic and can be effectively internalized into the cervical cancer cell line (HeLa). The described method of synthesis allows us to obtain silica-based carriers with an immobilized fluorescent dye that provide the possibility for real-time imaging and detection of these carriers. Full article

Powerful antioxidant α-lipoic acid (LA) is easily degraded under light and heating. This creates difficulties in its manufacture, storage and reduces efficiency and safety of the drug. The purpose of this work was to synthesize novel silica-based composites of LA and evaluate their ability to increase photo and thermal stability of the drug. It was assumed that the drug stabilization can be achieved due to LA-silica interactions. Therefore, the composites of LA with unmodified and organomodified silica matrixes were synthesized by sol-gel method at the synthesis pH below or above the pKa of the drug. The effects of silica matrix modification and the synthesis pH on the LA-silica interactions and kinetics of photo and thermal degradation of LA in the composites were studied. The nature of the interactions was revealed by FTIR spectroscopy. It was found that the rate of thermal degradation of the drug in the composites was significantly lower compared to free LA and mainly determined by the LA-silica interactions. However, photodegradation of LA in the composites under UV irradiation was either close to that for free drug or significantly more rapid. It was shown that kinetics of photodegradation was independent of the interactions and likely determined by physical properties of surface of the composite particles (porosity and reflectivity). The most promising composites for further development of novel silica-based formulations were identified. Full article

A novel nanoarchitecture-reinforced poly(lactic acid) (PLA) nanocomposite was prepared using multi-walled carbon nanotube (MWCNT)-grafted silica nanohybrids as reinforcements. MWCNT-grafted silica nanohybrids were synthesized by the generation of silica nanoparticles on the MWCNT surface through the sol-gel technique. This synthetic method involves organo-modified MWCNTs that are dispersed in tetrahydrofuran, which incorporates tetraethoxysilane that undergoes an ultrasonic sol-gel process. Gelation yielded highly dispersed silica on the organo-modified MWCNTs. The structure and properties of the nanohybrids were established using ²⁹Si nuclear magnetic resonance, Raman spectroscopy, wide-angle X-ray diffraction, thermogravimetric analysis, and transmission electron microscopy. The resulting MWCNT nanoarchitectures were covalently assembled into silica nanoparticles, which exhibited specific and controllable morphologies and were used to reinforce biodegradable PLA. The tensile strength and the heat deflection temperature (HDT) of the PLA/MWCNT-grafted silica nanocomposites increased when the MWCNT-grafted silica was applied to the PLA matrix; by contrast, the surface resistivity of the PLA/MWCNT-grafted silica nanocomposites appeared to decline as the amount of MWCNT-grafted silica in the PLA matrix increased. Overall, the reinforcement of PLA using MWCNT-grafted silica nanoarchitectures was efficient and improved its mechanical properties, heat resistance, and electrical resistivity. Full article

Chlorophyll is a pyrrolic pigment with important optical properties, which is the reason it has been studied for many years. Recently, interest has been rising with respect to this molecule because of its outstanding physicochemical properties, particularly applicable to the design and development of luminescent materials, hybrid sensor systems, and photodynamic therapy devices for the treatment of cancer cells and bacteria. More recently, our research group has been finding evidence for the possibility of preserving these important properties of substrates containing chlorophyll covalently incorporated within solid pore matrices, such as SiO₂, TiO₂ or ZrO₂ synthesized through the sol-gel process. In this work, we study the optical properties of silica xerogels organo-modified on their surface with allyl and phenyl groups and containing different concentrations of chlorophyll bonded to the pore walls, in order to optimize the fluorescence that these macrocyclic species displays in solution. The intention of this investigation was to determine the maximum chlorophyll a concentration at which this molecule can be trapped inside the pores of a given xerogel and to ascertain if this pigment remains trapped as a monomer, a dimer, or aggregate. Allyl and phenyl groups were deposited on the surface of xerogels in view of their important effects on the stability of the molecule, as well as over the fluorescence emission of chlorophyll; however, these organic groups allow the trapping of either chlorophyll a monomers or dimers. The determination of the above parameters allows finding the most adequate systems for subsequent in vitro or in vivo studies. The characterization of the obtained xerogels was performed through spectroscopic absorption, emission and excitation spectra. These hybrid systems can be employed as mimics of natural systems; the entrapment of chlorophyll inside pore matrices indicates that it is possible to exploit some of the most physicochemical properties of trapped chlorophyll for diverse technological applications. The data herein collected suggest the possibility of applying the developed methodology to other active, captive molecules in order to synthesize new hybrid materials with optimized properties, suitable to be applied in diverse technological fields. Full article

A sol-gel methodology has been duly developed in order to perform a controlled covalent coupling of tetrapyrrole macrocycles (e.g., porphyrins, phthalocyanines, naphthalocyanines, chlorophyll, etc.) to the pores of metal oxide networks. The resulting absorption and emission spectra intensities in the UV-VIS-NIR range have been found to depend on the polarity existing inside the pores of the network; in turn, this polarization can be tuned through the attachment of organic substituents to the tetrapyrrrole macrocycles before bonding them to the pore network. The paper shows clear evidence of the real possibility of maximizing fluorescence emissions from metal-free bases of substituted tetraphenylporphyrins, especially when these molecules are bonded to the walls of functionalized silica surfaces via the attachment of alkyl or aryl groups arising from the addition of organo-modified alkoxides. Full article

The crossed and linked histories of tetrapyrrolic macrocycles, interwoven with new research discoveries, suggest that Nature has found in these structures a way to ensure the continuity of life. For diverse applications porphyrins or phthalocyanines must be trapped inside solid networks, but due to their nature, these compounds cannot be introduced by thermal diffusion; the sol-gel method makes possible this insertion through a soft chemical process. The methodologies for trapping or bonding macrocycles inside pristine or organo-modified silica or inside ZrO₂ xerogels were developed by using phthalocyanines and porphyrins as molecular probes. The sizes of the pores formed depend on the structure, the cation nature, and the identities and positions of peripheral substituents of the macrocycle. The interactions of the macrocyclic molecule and surface Si-OH groups inhibit the efficient displaying of the macrocycle properties and to avoid this undesirable event, strategies such as situating the macrocycle far from the pore walls or to exchange the Si-OH species by alkyl or aryl groups have been proposed. Spectroscopic properties are better preserved when long unions are established between the macrocycle and the pore walls, or when oligomeric macrocyclic species are trapped inside each pore. When macrocycles are trapped inside organo-modified silica, their properties result similar to those displayed in solution and their intensities depend on the length of the alkyl chain attached to the matrix. These results support the prospect of tuning up the pore size, surface area, and polarity inside the pore cavities in order to prepare efficient catalytic, optical, sensoring, and medical systems. The most important feature is that research would confirm again that tetrapyrrolic macrocycles can help in the development of the authentic pore engineering in materials science. Full article