Organic-inorganic Hybrid Sol-gel Research Articles

Amino-Alcohol Organic-Inorganic Hybrid Sol-Gel Materials Based on an Epoxy Bicyclic Silane: Synthesis and Characterization.

Organic-inorganic hybrids (OIHs) are a type of material that can be obtained using the sol-gel process and has the advantages of organic and inorganic moieties in a single material. Polyetheramines have been widely used in the preparation of this type of material, particularly in combination with epoxy-based alkoxysilanes. Nevertheless, epoxyciclohexylethyltrimethoxysilane (ECHETMS) is a promising alkoxysilane with an epoxy terminal group that is quite unexplored. In this work, four novel OIH materials were synthesized using the sol-gel method. The OIHs were based on Jeffamines® of different molecular weights (D-230, D-400, ED-600, and ED-900), together with ECHETMS. The materials were characterized using multinuclear solid state NMR, FTIR, BET, UV/Vis spectroscopy, EIS, and TGA. The influence of the Jeffamine molecular weight and the suitability of these materials to act as a supporting matrix for heteroaromatic probes were assessed and discussed. The materials show interesting properties in order to be applied in a wide range of sensing applications.

The Antimicrobial Activity of Micron-Thin Sol-Gel Films Loaded with Linezolid and Cefoxitin for Local Prevention of Orthopedic Prosthesis-Related Infections.

Orthopedic prosthesis-related infections (OPRI) are an essential health concern. OPRI prevention is a priority and a preferred option over dealing with poor prognosis and high-cost treatments. Micron-thin sol-gel films have been noted for a continuous and effective local delivery system. This study aimed to perform a comprehensive in vitro evaluation of a novel hybrid organic-inorganic sol-gel coating developed from a mixture of organopolysiloxanes and organophosphite and loaded with different concentrations of linezolid and/or cefoxitin. The kinetics of degradation and antibiotics release from the coatings were measured. The inhibition of biofilm formation of the coatings against Staphylococcus aureus, S. epidermidis, and Escherichia coli strains was studied, as well as the cell viability and proliferation of MC3T3-E1 osteoblasts. The microbiological assays demonstrated that sol-gel coatings inhibited the biofilm formation of the evaluated Staphylococcus species; however, no inhibition of the E. coli strain was achieved. A synergistic effect of the coating loaded with both antibiotics was observed against S. aureus. The cell studies showed that the sol-gels did not compromise cell viability and proliferation. In conclusion, these coatings represent an innovative therapeutic strategy with potential clinical use to prevent staphylococcal OPRI.

Development and characterisation of strontium-doped sol-gel coatings to optimise the initial bone regeneration processes

Strontium plays an important role in bone regeneration; it promotes the differentiation and maturation of osteoblasts and inhibits the activity of osteoclasts. Our principal objective in this study was to formulate new organic-inorganic hybrid sol-gel coatings applied to titanium discs. These coatings were functionalised with different amounts of SrCl 2 and examined using in vitro tests and proteomics. The chemical and morphological characteristics of obtained coatings were scrutinised. The in vitro evaluation using the MC3T3-E1 osteoblasts and RAW264.7 macrophages showed the osteogenic and anti-inflammatory effects of strontium doping. The proteomic assay identified 111 different proteins adhering to the coatings. Six of these proteins reduced their adhesion affinity as a result of Sr-doping, whereas 40 showed increased affinity. Moreover, the proteomic analysis revealed osteogenic and anti-inflammatory properties of these biomaterials. The analysis also showed increased adhesion of proteins related to the coagulation system. We can conclude that proteomic methods are invaluable in developing new biomaterials and represent an important tool for predicting the biocompatibility of dental implants. • A new sol-gel coating doped with SrCl 2 was developed and characterized. • New Sr-enriched coatings with osteogenic, coagulatory and anti-inflammatory properties. • Protein adsorption patterns on Sr-coatings correlates with their in vitro results.

Organic-inorganic hybrid sol–gel membranes for pH sensing in highly alkaline environment

This work reports the synthesis of organic–inorganic hybrid (OIH) membranes for potential optical fibre sensors (OFS) functionalisation for pH monitoring of concrete and reinforced concrete structures (RCS). As precursors, 3-glycidyloxypropyltrimethoxysilane and Jeffamine® THF-170 were used. The OIH sol–gel materials were doped with phenolphthalein (phph) for pH sensing proposes and cetyl trimethyl ammonium bromide as surfactant.OIH membranes with pH sensing ability properties were successfully obtained. The dielectric properties of the resultant membranes were determined by electrochemical impedance spectroscopy. The logarithm of resistance obtained was 10.19 Ω cm2 for the undoped matrix and, 7.06 Ω cm2 for the doped one with phph. The results obtained in simulated concrete pore solutions, for the OIH produced, showed to be promising for application in fresh concrete. The transmittance of the synthesized OIH materials decreased after the doping with phph. The matrix showed intrinsic fluorescence and doping it only led to small deviations in the wavelength of the peak of maximum emission. Regarding thermal analysis, no significant changes were obtained on the thermal profile of the doped and undoped OIH membranes. The pH variation was detected by the OIH membrane colour change. Stability studies regarding the release of phph from the OIH matrix led to a mean dissolution time equal to 75.4 (±0.02) hours, indicating that the proposed system reveals long-term stability.

Polyaniline-based room temperature ammonia gas sensor employing hybrid organic-inorganic substrate

Air pollution poses a serious threat to public health, and gas sensors for detection of the pollution has gained great attention over the past decades. In this work, a novel idea based on the substrate material integrated by structure and function was built to prepare NH3 sensor with an improving sensing properties. Hybrid organic–inorganic sol gel with methacryloxy and epoxy groups was first synthesized. A hybrid organic–inorganic substrate was then prepared based on continuous condensation, radical polymerization and anionic polymerization. The thermal stability and microstructural of the hybrid substrate were studied and the results indicated that the hybrid has excellent thermal and structural stability. Then, polyaniline (PANI) was directly loaded on the hybrid substrate due to hydrogen bonding though a facile in-situ polymerization method to fabricate a PANI/hybrid nanocomposite for NH3 sensing. The hydroxyl groups generated from the epoxide ring-open reaction and silane hydrolysis condensation contribute to improve the sensing properties. This sensor showed superior selectivity and reproducibility to 50 ppm NH3 at room temperature. The low detection limit towards NH3 at room temperature can reach 1 ppm. This strategy may provide a promising and straightforward method in gas sensing electronics at room temperature.

Sol-Gel Coating Membranes for Optical Fiber Sensors for Concrete Structures Monitoring

The use of advanced sensing devices for concrete and reinforced concrete structures (RCS) is considered a rational approach for the assessment of repair options and scheduling of inspection and maintenance strategies. The immediate benefits are cost reduction and a reliable prevention of unpredictable events. The use of optical fiber sensors (OFS) for such purposes has increased considerably in the last few years due to their intrinsic advantages. In most of the OFS, the chemical transducer consists of immobilized chemical reagents placed in the sensing region of the optical sensor by direct deposition or by encapsulation in a polymeric matrix. The choice of the support matrix impacts directly on the performance of the OFS. In the last two decades, the development of OFS functionalized with organic–inorganic hybrid (OIH) sol–gel membranes have been reported. Sol–gel route is considered a simple method that offers several advantages when compared to traditional synthesis processes, allowing to obtain versatile materials with unique chemical and physical properties, and is particularly valuable in the design of OIH materials. This review will provide an update of the current state-of-the-art of the OFS based on OIH sol-gel materials for concrete and RCS since 2016 until mid-2021. The main achievements in the synthesis of OIH membranes for deposition on OFS will be discussed. The challenges and future directions in this field will also be considered, as well as the main limitations of OFS for RCS monitoring.

Fabric Phase Sorptive Extraction: A Paradigm Shift Approach in Analytical and Bioanalytical Sample Preparation.

Fabric phase sorptive extraction (FPSE) is an evolutionary sample preparation approach which was introduced in 2014, meeting all green analytical chemistry (GAC) requirements by implementing a natural or synthetic permeable and flexible fabric substrate to host a chemically coated sol–gel organic–inorganic hybrid sorbent in the form of an ultra-thin coating. This construction results in a versatile, fast, and sensitive micro-extraction device. The user-friendly FPSE membrane allows direct extraction of analytes with no sample modification, thus eliminating/minimizing the sample pre-treatment steps, which are not only time consuming, but are also considered the primary source of major analyte loss. Sol–gel sorbent-coated FPSE membranes possess high chemical, solvent, and thermal stability due to the strong covalent bonding between the fabric substrate and the sol–gel sorbent coating. Subsequent to the extraction on FPSE membrane, a wide range of organic solvents can be used in a small volume to exhaustively back-extract the analytes after FPSE process, leading to a high preconcentration factor. In most cases, no solvent evaporation and sample reconstitution are necessary. In addition to the extensive simplification of the sample preparation workflow, FPSE has also innovatively combined the extraction principle of two major, yet competing sample preparation techniques: solid phase extraction (SPE) with its characteristic exhaustive extraction, and solid phase microextraction (SPME) with its characteristic equilibrium driven extraction mechanism. Furthermore, FPSE has offered the most comprehensive cache of sorbent chemistry by successfully combining almost all of the sorbents traditionally used exclusively in either SPE or in SPME. FPSE is the first sample preparation technique to exploit the substrate surface chemistry that complements the overall selectivity and the extraction efficiency of the device. As such, FPSE indeed represents a paradigm shift approach in analytical/bioanalytical sample preparation. Furthermore, an FPSE membrane can be used as an SPME fiber or as an SPE disk for sample preparation, owing to its special geometric advantage. So far, FPSE has overwhelmingly attracted the interest of the separation scientist community, and many analytical scientists have been developing new methodologies by implementing this cutting-edge technique for the extraction and determination of many analytes at their trace and ultra-trace level concentrations in environmental samples as well as in food, pharmaceutical, and biological samples. FPSE offers a total sample preparation solution by providing neutral, cation exchanger, anion exchanger, mixed mode cation exchanger, mixed mode anion exchanger, zwitterionic, and mixed mode zwitterionic sorbents to deal with any analyte regardless of its polarity, ionic state, or the sample matrix where it resides. Herein we present the theoretical background, synthesis, mechanisms of extraction and desorption, the types of sorbents, and the main applications of FPSE so far according to different sample categories, and to briefly show the progress, advantages, and the main principles of the proposed technique.

Organic-inorganic hybrid sol-gel materials doped with a fluorescent triarylimidazole derivative.

The development of sensors for pH monitoring is of extreme importance in the monitoring of concrete and reinforced concrete structures. Imidazole derivatives are promising probes for pH sensing due to the amphoteric nature of their heterocyclic ring, which can be protonated/deprotonated upon pH changes. In this work, a triarylimidazole was synthesised and used as a dopant in an organic–inorganic hybrid (OIH) sol–gel matrix to obtain a pH-sensitive membrane for further application in optical fibre sensors (OFS). The triarylimidazole probe shows fluorimetric response in pH between 9 and 13, which is the desired range for monitoring carbonation of concrete. This degradation process lowers the highly alkaline pH of concrete (12.5–13) to values below 9, which creates favourable conditions for corrosion of concrete reinforcement. The OIH membranes used were based on Jeffamine THF170 and 3-glycidoxypropytrimethoxysilane precursors, which had already been shown to be suitable and resistant in contact with cement-based materials. The OIHs were doped with three different contents of the triarylimidazole and the structural, dielectric, thermal and optical properties of the pure and doped OIH materials were evaluated. The structural analysis showed that the presence of the triarylimidazole did not change the structural properties of the OIH material. Electrochemical impedance spectroscopy showed that in the doped samples the conductivity increased with the imidazole concentration. The εr obtained for the doped samples ranged approximately from 11 to 19 and for the pure matrices was 8. Thermal analysis showed that these materials are stable up to 350 °C and that the presence of the probe did not change that feature. The optical properties showed that the prepared OIH materials have promising properties to be used as pH sensitive fluorimetric probes.

Synthesis, Optical and Electrical Characterization of Amino-alcohol Based Sol-gel Hybrid Materials.

This manuscript describes the synthesis and characterization of five new organic–inorganic hybrid (OIH) sol-gel materials that were obtained from a functionalized siloxane 3-glycidoxypropyltrimethoxysilane (GPTMS) by the reaction with the new Jeffamine®, namely three different diamines, i.e., EDR-148, RFD-270, and THF-170, a secondary diamine, i.e., SD-2001, and a triamine, i.e., T-403. The OIH sol-gel materials were characterized by UV-visible absorption spectrophotometry, steady-state photoluminescence spectroscopy, and electrochemical impedance spectroscopy. The reported OIH sol-gel materials showed that, with the exception of the samples prepared with Jeffamine® SD-2001, the transmittance values ranged between 61% and 79%. Regarding the capacitance data, the values reported changed between 0.008 and 0.013 nF cm−2. Due to their optical and electrical properties these new OIH materials show promising properties for applications as support films in an optical sensor area such as fiber sensor devices. Studies to assess the chemical stability of the OIH materials in contact with cement pastes after 7, 14, and 28 days were also performed. The samples prepared with THF–170 and GPTMS, when compared to the samples prepared with RFD-270 and T-403, exhibited improved behavior in the cement paste (alkaline environment), showing promising properties for application as support film in optical fiber sensors in the civil engineering field.

Effect of lanthanum 4-hydroxy cinnamate on the polymerisation, condensation and thermal stability of hybrid sol–gel formulations

Hybrid organic–inorganic sol–gel based coatings are of increasing interest nowadays as conversion coating replacements due to their promising performance. They provide good barrier properties; however, they lack active corrosion protection. Lanthanum 4-hydroxy cinnamate [La(4-OHCin)3] was incorporated into a known sol–gel formulation with the aim of improving the overall corrosion resistance of the derived coating. Since the final properties of these sol–gel coatings are dependent on the hydrolysis and condensation reactions of the alkoxide precursors, as well as the polymerisation processes that occur in the organic component, the effect of adding an inhibiting agent, such as La(4-OHCin)3, on the sol–gel chemistry and the polymerisation process needs to be investigated. This study focuses on the role of La(4-OHCin)3 on the sol–gel formation when it is incorporated into two different sol–gel formulations (Si sol and Si–Ti sol). Its influence on hydrolysis and condensation reactions has been studied by 29Si NMR and the opening of the epoxide ring from one of the precursors has been monitored by 1H NMR and Fourier-transformed infrared. Differential scanning calorimetry and Thermogravimetric analysis have also been performed to investigate the effect of this compound on the thermal properties of the final materials synthesised. It has been observed that the addition of La(4-OHCin)3 plays an important catalytic role both in the organic and inorganic polymerisation of the different metal alkoxide precursors. Furthermore, this effect is enhanced when only silicon alkoxides are present in the formulation, as the titanium precursor also plays a role on this catalysis.

Enhancing the Corrosion Protection of AA2024-T3 Alloy by Surface Treatments Based on Piperazine-Modified Hybrid Sol–Gel Films

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.

Effect of Sol-Gel Film on the Corrosion Resistance of Low Carbon Steel Plate

To improve the corrosion resistance on Q235 low carbon steel, in this paper, tetraethyl orthosilicate (TEOS), N-dodecyl trimethoxysilane and γ-(2,3-epoxypropoxy) propytrimethoxysilane (KH560) were used to make organic-inorganic hybrid sol-gel film. Cross cut test adhesion method, neutral salt spray test, electrochemical test and film protective efficiency were taken to value the corrosion resistance property. The corrosion topography was studied by optical microscope. In addition, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) curves and equivalent electric circuit fitting were used to analyze the corrosion mechanism. The cross cut adhesion of sol-gel film can reach 1 class and the protection class can attain 5 class after 72 hours neutral salt spray test. According to the potentiodynamic polarization curve analysis, the corrosion potential of sol-gel film coating sample after 0.5 hours immersion was -0.46 V (vs. SCE) on the 0.1 Hz, and its corrosion current density was 4.74×10-7 A·cm-2. The corrosion potential of bare Q235 low carbon steel plate after 0.5 hours immersion was -0.78 V (vs. SCE) on the 0.1 Hz, and its corrosion current density was 4.75×10-6 A·cm-2. The impedance value on 0.1 Hz (|Z|0.1Hz) (1.27×106 Ω·cm2) of sol-gel film coating sample was more than three orders of magnitude higher than the value of the low carbon steel plate. Even dipping in 3.5 wt. % NaCl for 72 hours, the |Z|0.1Hz value of sol-gel coating sample was still one order of magnitude higher than the low carbon steel plate with 0.5 hours immersion. Sol-gel film with excellent adhesion can significantly improve the corrosion resistance of low carbon steel plate. Sol-gel film can increase the protection efficiency of low carbon steel plate by 90%.

Solution-Processed Flexible Gas Barrier Films for Organic Field-Effect Transistors

The solution-processed gas barrier film was fabricated and used for organic field-effect transistors (OFETs). Organic-inorganic hybrid sol-gel materials and cyclic transparent optical polymer (CYTOP) were used as the bottom and top layers of the barrier films, respectively, to effectively protect against gas permeation through the barrier films. The organic-inorganic hybrid material includes sol-gel precursors and amphiphilic polymers. The conventional sol-gel precursors form siloxane bonds by sol-gel reaction and form densely-packed rigid part in thin films. The alkoxysilane-functionalized amphiphilic polymer in the sol-gel precursor solutions has two hydrophobic segments and a hydrophilic segment. The amphiphilic polymer with reactive alkoxysilane groups at both ends of the hydrophobic segments can be involved in the sol-gel reaction, and they can act as surfactants to surround the conventional precursors stabilizing the nanoparticles formed by the hydrolytic condensation reaction of precursors. The amphiphilic polymer also provides flexibility for hybrid sol-gel thin films. CYTOP was used to introduce hydrophobicity on top of the organic-inorganic hybrid thin films. The barrier films containing the organic-inorganic hybrid and hydrophobic CYTOP layers were applied to OFETs and exhibited notable gas barrier properties, high transparency, and flexibility. The encapsulated OFETs with 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) as an organic semiconductor showed a slight decrease in hole mobility from 0.13 to 0.11 cm2 V-1 s-1, while the OFETs without barrier films showed a mobility decrease from 0.11 to 0.03 cm2 V-1 s-1.

Hybrid Sol-gel Coatings for Corrosion Mitigation: A Critical Review.

The corrosion process is a major source of metallic material degradation, particularly in aggressive environments, such as marine ones. Corrosion progression affects the service life of a given metallic structure, which may end in structural failure, leakage, product loss and environmental pollution linked to large financial costs. According to NACE, the annual cost of corrosion worldwide was estimated, in 2016, to be around 3%–4% of the world’s gross domestic product. Therefore, the use of methodologies for corrosion mitigation are extremely important. The approaches used can be passive or active. A passive approach is preventive and may be achieved by emplacing a barrier layer, such as a coating that hinders the contact of the metallic substrate with the aggressive environment. An active approach is generally employed when the corrosion is set in. That seeks to reduce the corrosion rate when the protective barrier is already damaged and the aggressive species (i.e., corrosive agents) are in contact with the metallic substrate. In this case, this is more a remediation methodology than a preventive action, such as the use of coatings. The sol-gel synthesis process, over the past few decades, gained remarkable importance in diverse areas of application. Sol–gel allows the combination of inorganic and organic materials in a single-phase and has led to the development of organic–inorganic hybrid (OIH) coatings for several applications, including for corrosion mitigation. This manuscript succinctly reviews the fundamentals of sol–gel concepts and the parameters that influence the processing techniques. The state-of-the-art of the OIH sol–gel coatings reported in the last few years for corrosion protection, are also assessed. Lastly, a brief perspective on the limitations, standing challenges and future perspectives of the field are critically discussed.

Optimization of Hybrid Sol-Gel Coating for Dropwise Condensation of Pure Steam.

We developed hybrid organic–inorganic sol–gel silica coatings with good durability in harsh environment (high temperatures, high vapor velocities) and with slightly hydrophobic behavior, sufficient to promote dropwise condensation (DWC) of pure steam. DWC is a very promising mechanism in new trends of thermal management and power generation systems to enhance the heat transfer during condensation as compared to film-wise condensation (FWC). The sol–gel coatings have been prepared from methyl triethoxy silane (MTES) and tetraethyl-orthosilicate (TEOS) and deposited on an aluminum substrate. The coatings were optimized in terms of precursor ratio and annealing temperature highlighting potentials and limits of such mixtures. A comprehensive surface characterization before and after saturated steam condensation tests has been performed and related to the thermal measurements for evaluating the heat transfer augmentation as compared to FWC obtained on untreated aluminum surfaces. The results showed that the developed hybrid organic-inorganic sol–gel silica coatings are promising DWC promoters.

Characterization and corrosion protection of nano-titanium dioxide doped BTSE-GPTMS sol–gel coating on cast Al–Si alloy

A hybrid organic–inorganic sol–gel coating was prepared on the surface of cast aluminum–silicon (Al–Si) alloy via dip coating method to improve the anticorrosion ability. In the present work, bis(triethoxysilyl) ethane (BTSE) and 3-glycidoxypropyl-trimethoxysilane (GPTMS) were employed as the precursors to prepare hybrid sol–gel (BG) coating. Nano titanium dioxide (nano-TiO2) was introduced to improve the corrosion resistance of the coating. The microstructures of the BG/nano-TiO2 (BG-T) coating was characterized by scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), and Fourier-transform infrared (FT-IR) spectroscopy. The results showed that there was a chemical reaction between nano-TiO2 and BG coating and a complete defect-free coating formed on the surface of Al–Si alloy. Moreover, there were a few only minor cracks appeared on the surface of BG-T coating after 15 days immersion in 3.5 wt.% NaCl solution. The corrosion resistant performances of the coatings were evaluated by the electrochemical tests. The results showed that the nano-TiO2 particles elevated the corrosion potential and depressed the corrosion current, thereby improved the corrosion resistance. The long-term immersion tests of BG and BG-T coating further showed that the BG-T coating possesses an excellent long-term stability for corrosion protection.

Improved mechanical and anticorrosion properties of metal oxide-loaded hybrid sol–gel coatings for mild steel in a saline medium

A hybrid organic–inorganic sol–gel coating was successfully prepared and subsequently functionalized individually with five different metal oxide additives. The effect of the incorporated oxides on the corrosion protection performance and scratch-resistance properties of the hybrid base coating on mild steel substrates was investigated using electrochemical techniques, namely electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PDP) as well as mechanical testing. The steel-coated specimens were immersed in 3.5 wt.% NaCl corrosive medium for two weeks and the results reveal an excellent corrosion protection performance by all coating formulations with a significant high corrosion-resistance property for the sample loaded with molybdenum oxide. Scanning electron microscopy (SEM) images proved the absence of corrosion signs, defects, micro cracks, or delamination on the surface of the coated samples. Compared with the pure hybrid coating, all the metal oxide-embedded coatings (except for the sample loaded with yttrium(III) oxide) show comparable aqueous contact angle values as well as enhanced hardness and adherence properties. No noticeable dependence was observed for the surface roughness parameters as a function of the type of incorporated metal oxide within the sol–gel matrix. Overall, the results of this study demonstrate that metal oxides can be advantageous to the desired properties of hybrid sol–gel coatings applied to steel surfaces.

Hydrophobic, organic–inorganic hybrid sol–gel coatings containing boehmite nanoparticles for metal corrosion protection

In this study, fluoro-functionalized hydrophobic/oleophobic hybrid nanocomposite coatings, which are highly resistant and transparent, long-lasting and mechanically stable, have been deposited on metal substrate surfaces by the sol–gel method. Organic–inorganic hybrid matrix was prepared using tetraethoxysilane and organically modified silicon alkoxide, namely 3-(glycidyloxypropyl) trimethoxysilane. Additionally, to increase hydrophobic behavior, a fluorinated silica-alkoxide precursor and AlO(OH) NPs were added to the hybrid matrix. Water and n-hexadecane contact angle, surface morphologies, thicknesses and surface roughness of the films were determined. Additionally, optical characterizations and mechanical properties of the films such as light transmittance, haze, clarity, gloss were investigated. A salt spray corrosion test and electrochemical corrosion measurements were also performed. Optimum properties were acquired in the hydrophobic hybrid nanocomposite coating containing 15 wt% of 3 nm AlO(OH) NPs.

Enhanced Antibacterial Capability and Corrosion Resistance of Ti6Al4V Implant Coated with ZrO2/Organosilica Nanocomposite Sol-Gel Films

Ti6Al4V is one of the most commonly used biomaterials in orthopedic applications due to its interesting mechanical properties, corrosion resistance and reasonable biocompatibility, which derive from a compact, thin, and chemically stable oxide film that spontaneously develops on these materials surface able to minimize ion release. Despite these advantages, a post-operative serious and unresolved problem leading to the failure of the implant is the appearance of implant-associated infections. For this reason, the ability to control microbial adhesion is of importance in healthcare, particularly in modern surgery where postoperative implant associated infections are still an unresolved and serious complication. As a proof of concept, we have assessed the antibacterial behaviour of Ti6Al4V surfaces modified by organic-inorganic hybrid sol-gel films with different loading of ZrO2 nanoparticles. The starting organosilica sol was prepared using a mixture of γ-methacryloxypropyltrimethoxysilane (MAPTMS) and tetramethyl orthosilicate (TMOS). Tetrabutoxyzirconium (TBZ) was used as precursor of ZrO2 nanoparticles. Sol-gel films with variable contents of TBZ (0.2—1.0 wt.%) have been tested. The thermal stability of the resulting sol-gel films was studied by using thermal analysis (TG/DTG). Structural characterization of the films was carried out using Attenuated Total Reflectance Fourier transformer Infrared spectroscopy (ATR-FTIR). Surface morphology and composition of coated samples have been analized by Optical and Scanning Electron Microscopy coupled with Energy Dispersive X-ray (OM and SEM/EDX) both before and after the corrosion tests were carried out. The evaluation of the barrier properties on the films and corrosion behaviour of the Ti6Al4V were carried out using Global and Local Electrochemical Impedance Spectroscopy (EIS/LEIS) during immersion in a simulated body fluid (SBF). Regarding bacterial adhesion, two representative strains of the vast majority of nosocomial infections related to orthopedic implants, i.e., Staphylococcus aureus and Staphylococcus epidermidis, were used. Optical and scanning electron microscopies observations have shown the formation of a uniform, homogeneous, crack free and highly adherent protective film on the Ti6Al4V substrates. The electrochemical studies and bacterial adhesion assessments have shown that the incorporation of ZrO2 in MAPTMS/TMOS matrix of the sol-gel films enhance their corrosion protection behaviour and antibacterial capability. Studies on the optimization of the sol-gel formulation to obtain the films with the best antibacterial capability without compromising their good corrosion resistance using different ZrO2 doses are in progress. Acknowledgments The authors would like to acknowledge financial support from the Ministry of Economy of Spain (MAT2015-65445-C2-1-R and MAT2015-63974-C4-3 Projects). M-ERA.NET PCIN-2016-146; Spanish “Junta de Extremadura” and FEDER for the projects IB16117, TE-0016-18 and GR15089

An improved fabric phase sorptive extraction method for the determination of five selected antidepressant drug residues in human blood serum prior to high performance liquid chromatography with diode array detection

Fabric phase sorptive extraction (FPSE), a recently introduced sorbent-based microextraction technique, was applied for the first time in order to achieve a simple and rapid simultaneous extraction of five common antidepressant drug residues (venlafaxine, paroxetine, fluoxetine, amitriptyline and clomipramine) from human blood serum. Elimination of protein precipitation step and minimized solvent consumption led to a sample preparation workflow compliant with the principles of green analytical chemistry (GAC). FPSE utilizes permeable and flexible fabric substrate chemically coated with a sol-gel organic-inorganic hybrid sorbent as the extraction device. Among all the membrane examined, sol-gel polycaprolactone-dimethylsiloxane-polycaprolactone coated polyester substrate presented optimum extraction efficiency and was found to be reusable for at least 30 times. The selected drugs were analyzed and detected by reversed phase high performance liquid chromatography method using gradient elution and a diode array detector operated at 235 nm. Limit of detection was found 0.15 ng μL−1, while good absolute recoveries (9.4–88.1%) and low relative standard deviations (≤9.2% and ≤ 11.0 for within-day and between-day precision, respectively) were obtained.