Natural rubber–based composites filled with bioglasses from a CaO‐SiO2‐P2O5‐Ag2O system. Effect of Ag2O concentration in the filler on composite properties

Bioactive glass was first synthesized by L. Hench in 1971. There are many studies on the properties of several metals and metal ions dopants used in the SiO₂‐CaO‐P₂O₅ system of bioglasses, such as Ag, Cu, Zn, and Fe. A number of authors have carried out research related to the influence of silver oxide on the properties of bioglasses . However, publications on the properties of elastomer‐based composites containing bioactive glasses are relatively scarce. We have not found in the literature studies discussing how silver oxide concentration in bioglasses of the CaO‐SiO₂‐P₂O₅‐Ag₂O system affects the significant properties of a natural rubber biocomposite. In this regard, the purpose of the present work is to investigate the aforementioned influence on the properties of this type of composites, namely, vulcanization, physicomechanical, thermal, dynamic, dielectric, electric, and thermoconductive characteristics. We have established those parameters of the composites to be impacted considerably by both degree of filling with bioglass and the silver oxide content in the latter. The improvement in the composites thermostability and some of their physicomechanical performance is the most significant. The volume resistance decreases, and the thermal conductivity coefficients increase. Results from scanning electron microscopy and energy‐dispersive X‐ray (EDX) analyses have confirmed the influence of silver oxide initially on the phase composition of the bioglass, hence on the properties of the biocomposites through changes in the bioglass used as filler. The dielectric characteristics of some of the biocomposites suggest that they can be used as substrates and insulating layers in flexible antennas for short‐range wireless communications.     

X‐ray microanalysis in STEM of short‐term physicochemical reactions at bioactive glass particle/biological fluid interface. Determination of O/Si atomic ratios

Short‐term physicochemical reactions at the interface between bioactive glass particles and biological fluids are studied and we focus our attention on the measurements of O/Si atomic ratio. The studied bioactive glass is in the SiO₂? Na₂O? CaO? P₂O₅? K₂O? Al₂O₃? MgO system. The elemental analysis is performed at the submicrometre scale by scanning transmission electron microscopy associated with energy‐dispersive x‐ray spectroscopy (EDXS) and electron energy‐loss spectroscopy (EELS). We previously developed an EDXS quantification method based on the ratio method and taking into account local absorption corrections. In this way, we use EELS data to determine, by an iterative process, the local mass thickness, which is an essential parameter for correcting absorption in EDXS spectra. After different immersion times of bioactive glass particles in a simulated biological solution, results show the formation of different surface layers at the bioactive glass periphery. Before 1 day of immersion, we observe the presence of an already shown (Si,O,Al)‐rich layer at the periphery. In this paper, we demonstrate that a thin ‘electron dense’ (Si,O)‐layer is formed on top of the (Si,O,Al)‐layer. In this (Si,O)‐layer, depleted in aluminium, we point out an increase of oxygen weight concentration that can be interpreted by the presence of Si(OH)₄ groups, which permit the formation of a (Ca,P)‐layer. Aluminium plays a role in the glass solubility and may inhibit apatite nucleation. After the beginning of the (Ca,P)‐layer formation, the size of the ‘electron dense’ (Si,O)‐layer decreases and tends to disappear. After 2 days of immersion, the (Ca,P)‐layer grows in thickness and leads to apatite precipitation. Copyright © 2004 John Wiley & Sons, Ltd.     

Fe3O4@SiO2@Im‐bisethylFc [HC2O4] as a novel recyclable heterogeneous nanocatalyst for synthesis of bis‐coumarin derivatives

Nanomagnetic bisethylferrocene‐containing ionic liquid supported on silica‐coated iron oxide (Fe₃O₄@SiO₂@Im‐bisethylFc [HC₂O₄]) as a novel catalyst was designed and synthesized. The described catalyst was recycled and used without change in the time and efficiency of the condensation reaction. The Fourier transform‐infrared spectroscopy (FT‐IR), scanning electron microscopy images, X‐ray diffraction patterns, energy‐dispersive X‐ray spectroscopy, transmission electron microscope and vibrating‐sample magnetometer results confirmed the formation of Fe₃O₄@SiO₂@Im‐bisethylFc [HC₂O₄] magnetic nanoparticle. The novel bis‐coumarin derivatives were identified by ¹H‐NMR, ¹³C‐NMR, FT‐IR and CHNS analysis.     

Synthesis of polyethylene‐octene elastomer/SiO2‐TiO2 nanocomposites via in situ polymerization: Properties and characterization of the hybrid

In this study, a silicic acid and tetra isopropyl ortho titanate ceramic precursor and a metallocene polyethylene‐octene elastomer (POE) or acrylic acid grafted metallocene polyethylene‐octene elastomer (POE‐g‐AA) were used in the preparation of hybrids (POE/SiO₂? TiO₂ and POE‐g‐AA/SiO₂? TiO₂) using an in situ sol‐gel process, with a view to identifying a hybrid with improved thermal and mechanical properties. Hybrids were characterized using Fourier transform infrared spectroscopy, ²⁹Si solid‐state nuclear magnetic resonance (NMR), X‐ray diffraction, differential scanning calorimetry, thermogravimetry analysis, dynamic mechanical thermal analysis, and Instron mechanical testing. Properties of the POE‐g‐AA/SiO₂? TiO₂ hybrid were superior to those of the POE/SiO₂? TiO₂ hybrid. This was because the carboxylic acid groups of acrylic acid acted as coordination sites for the silica‐titania phase to allow the formation of stronger chemical bonds. ²⁹Si solid‐state NMR showed that Si atoms coordinated around SiO₄ units were predominantly Q₃ and Q₄. The 10 wt % SiO₂? TiO₂ hybrids gave the maximum values of tensile strength and glass transition temperature in both POE/SiO₂? TiO₂ and POE‐g‐AA/SiO₂? TiO₂. It is proposed that above this wt %, excess SiO₂? TiO₂ particles caused separation between the organic and inorganic phases. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1690–1701, 2005     

Magnetized inorganic–bioorganic nanohybrid [nano Fe3O4‐SiO2@Glu‐Cu (II)]: A novel nanostructure for the efficient solvent‐free synthesis of thiazolidin‐2‐imines

In this research, a solvent‐free four‐component one‐pot reaction of phenyl isothiocyanate, phenylacetylene, various kinds of aldehydes, and amines was interpreted to obtain the desired five‐membered heterocycles named thiazolidin‐2‐imines. The promotor of this transformation is a novel magnetite‐based multilayered inorganic–bioorganic nanohybrid prepared via embedding glutamic acid on the magnetized silica followed by anchoring Cu (II) [nano Fe₃O₄‐SiO₂@Glu‐Cu (II)]. The newly synthesized nanostructure is characterized through Fourier‐transform infrared (FT‐IR), field‐emission scanning electron microscopy (FESEM), energy dispersive X‐ray analysis (EDAX), transmission electron microscopy (TEM), X‐ray fluorescence (XRF), thermogravimetric analysis or derivative thermogravimetric (TGA/DTG), vibrating sample magnetometer (VSM), X‐ray photoelectron spectroscopy (XPS), and Brunauer–Emmett–Teller (BET) techniques. This protocol is a straightforward one‐step procedure to obtain thiazolidin‐2‐imines without requirement to propargylamines or imines as substrates. In addition, easy work‐up procedure, high yields of products, absence of organic solvents in the reaction media, recovery and reusability of nano Fe₃O₄‐SiO₂@Glu‐Cu ( II) to promote the reaction at least for three runs without activity lost, simple separation of the catalyst from reaction mixture via an external magnet, and regioselectivity of the method are some highlighted aspects of the approach.     

Preparation of ZSM‐5 Coated on Monolithic Interconnected Macroporous Al2O3 Using Cheap n‐Butylamine as Template

Using cheap n‐butylamine as template, ZSM‐5 zeolites have been successfully synthesized and coated on monolithic interconnected macroporous Al₂O₃ by the secondary growth method. The use of cheap n‐butylamine could significantly reduce the synthesis cost. Hierarchical monolithic ZSM‐5 zeolites were prepared from synthetic mixtures with different H₂O/Na₂O or SiO₂/Al₂O₃ ratio. The synthesized samples were characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR) and N₂ adsorption‐desorption. The results show that the hierarchical monolithic zeolites were obtained with cheap n‐butylamine template as template. During the hydrothermal reaction process, the morphology of the micrometer‐sized support was well maintained. The irregular crystals were formed in a wide range of the H₂O/Na₂O or SiO₂/Al₂O₃ ratio of synthetic mixtures and coated on monolithic Al₂O₃. The relative crystallinity of the zeolites was highest at H₂O/Na₂O=250 or SiO₂/Al₂O₃=160. This type of composites exhibited hierarchical porous structures and relatively high specific surface areas.     

In vitro bioactivity and crystallization behavior of bioactive glass in the system SiO2-CaO-Al2O3-P2O5-Na2O-MgO-CaF2

In this study, bioactivity of glass in the system SiO₂-CaO-Al₂O₃-P₂O₅-Na₂O-MgO-CaF₂ was investigated. For this purpose, a glass sample was prepared by the traditional melting method. Crystallization behavior of bioactive glass was also investigated using differential thermal analyses. The Avrami constant of bioactive glass sample calculated according to the Ozawa equation was 3.72 ± 0.4, which indicates bulk crystallization. Using the Matusita-Sakka and the Kissinger equations, activation energy of crystal growth was determined as (394 ± 17) kJ mol⁻¹ and (373 ± 12) kJ mol⁻¹, respectively. These results indicate that the crystallization activation energy data of bioactive glass obtained in this study are accurate and reliable. Bioactivity of the resultant glass sample was analyzed by immersion in simulated body fluid. Scanning electron microscopy, thin film X-ray diffraction, ultraviolet spectroscopy and inductively coupled plasma techniques were used to monitor changes in the glass surface and the simulated body fluid composition. The results revealed that a hydroxyapatite layer was formed on the glass surface after 21 days of immersion in SBF. Formation of the hydroxyapatite layer confirmed the bioactivity of the glass in the system SiO₂-CaO-Al₂O₃-P₂O₅-Na₂O-MgO-CaF₂. In addition, physical and mechanical properties of the sample were measured to determine changes in the properties with the immersion time. The results show that bioactive glass maintained its strength during the immersion in a simulated body fluid solution.     

Solvent‐free synthesis of propargylamines catalyzed by an efficient recyclable ZnO‐supported CuO/Al2O3 nanocatalyst

An efficient nanocatalyst of ZnO‐supported CuO/Al₂O₃ (CuO/ZnO/Al₂O₃ nanocatalyst) was prepared by the co‐precipitation method and characterized by scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray powder diffraction and Brunauer–Emmett–Teller surface area analysis. CuO/ZnO/Al₂O₃ nanocatalyst proved to be a very efficient catalyst on the synthesis of propargylamines under solvent‐free conditions in high yields. Moreover, the catalyst can be recyclable without reducing catalytic activity up to five times.     

Fe3O4@SiO2@l‐arginine@Pd(0): a new magnetically retrievable heterogeneous nanocatalyst with high efficiency for C–C bond formation

The surface of Fe₃O₄@SiO₂ nanoparticles was modified using l ‐arginine as a green and available amino acid to trap palladium nanoparticles through a strong interaction between the metal nanoparticles and functional groups of the amino acid. The proposed green synthetic method takes advantage of nontoxic reagents through a simple procedure. Characterization of Fe₃O₄@SiO₂@l ‐arginine@Pd(0) was done using Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray diffraction, vibrating sample magnetometry and inductively coupled plasma analysis. The catalytic activity of Fe₃O₄@SiO₂@l ‐arginine@Pd(0) as a new nanocatalyst was investigated in C – C coupling reactions. Waste‐free, use of green medium, efficient synthesis leading to high yield of products, eco‐friendly and economic catalyst, excellent reusability of the nanocatalyst and short reaction time are the main advantages of the method presented. Copyright © 2016 John Wiley & Sons, Ltd.     

Efficient Noble‐Metal‐Free γ‐Fe2O3@NiO Core–Shell Nanostructured Photocatalysts for Water Oxidation

Flowerlike noble‐metal‐free γ‐Fe₂O₃@NiO core–shell hierarchical nanostructures have been fabricated and examined as a catalyst in the photocatalytic oxidation of water with [Ru(bpy)₃](ClO₄)₂ as a photosensitizer and Na₂S₂O₈ as a sacrificial electron acceptor. An apparent TOF of 0.29 μmols^?1 m^?2 and oxygen yield of 51 % were obtained with γ‐Fe₂O₃@NiO. The γ‐Fe₂O₃@NiO core–shell hierarchical nanostructures could be easily separated from the reaction solution whilst maintaining excellent water‐oxidation activity in the fourth and fifth runs. The surface conditions of γ‐Fe₂O₃@NiO also remained unchanged after the photocatalytic reaction, as confirmed by X‐ray photoelectron spectroscopy (XPS).     

Preparation and enhanced properties of poly(propylene)/ silica‐grafted‐hyperbranched polyester nanocomposites

A series of poly(propylene) silica‐grafted‐hyperbranched polyester nanocomposites by grafting the modified hyperbranched polyester (Boltorn? H20), possessing theoretically 50% end carboxylic groups and 50% end hydroxyl groups, which endcapped with octadecyl isocyanate (C19), onto the surface of SiO₂ particles (30 nm) through 3‐glycidoxy‐propyltrimethoxysilane (GPTS) was prepared. The effect of silica‐grafted‐modified Boltorn? H20 on the mechanical properties of polypropylene (PP) was investigated by tensile and impact tests. The morphological structure of impact fracture surface and thermal behavior of the composites were determined by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC), respectively. The melt viscosity of composites was investigated by melt flow index (MFI). The obtained results showed that: (1) the modified Boltorn? H20 was successfully grafted onto the SiO₂ surface confirmed by FT‐IR and X‐ray photoelectron spectroscopy (XPS) analysis; (2) the incorporation of silica‐grafted‐modified Boltorn? H20 (3–5 wt% SiO₂) greatly enhanced the notched impact strength as well the tensile strength of the composites; (3) the incorporation of silica‐grafted‐modified Boltorn? H20 had no influence on the melting temperature and crystallinity of PP phase; (4) the MFI of PP composites increased when the silica‐grafted‐modified Boltorn? H20 particles were added compared with PP/SiO₂ or PP/SiO₂‐GPTS composites. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis,characterization and application of alumina/ vanadium pentoxide nanocomposit by sol–gel method

In this work, we report the preparation of Al₂O₃/V₂O₅ nanocomposit using vanadium and aluminum nitrate by sol–gel method. Characterization of nanocomposit was carried out by powder X‐ray diffractometry (XRD), Fourier transform infrared (FT‐IR), scanning electron microscopy (SEM), Energy‐Dispersive X‐ray (EDX) and UV spectroscopy. Then, applicability of the synthesized nanocomposit was tested as a nanocatalyst for the synthesis of diindolyl oxindole derivatives, an important class of potentially bioactive compounds. The products were obtained in good to high yields from one‐pot three‐component condensation of isatin with indole. Also, this nanocatalyst has been reused several times, without observable loss of activity.     

Ni@Pd core–shell nanoparticles immobilized on yolk–shell Fe3O4@polyaniline composites as a highly efficient,magnetically separable and atom‐economical catalyst for reduction of nitrobenzenes

The preparation of Ni@Pd core–shell nanoparticles immobilized on yolk–shell Fe₃O₄@polyaniline composites is reported. Fe₃O₄ nanoclusters were first synthesized through the solvothermal method and then the SiO₂ shell was coated on the Fe₃O₄ surface via a sol–gel process. To prepare Fe₃O₄@SiO₂@polyaniline composites, polyvinylpyrrolidone was first grafted on to the surface of Fe₃O₄@SiO₂ composites and subsequently polymerization of aniline was carried out via an ultrasound‐assisted in situ surface polymerization method. Selective etching of the middle SiO₂ layer was then accomplished to obtain the yolk–shell Fe₃O₄@polyaniline composites. The approach uses polyaniline (PANI) conductive polymer as a template for the synthesis of Ni@Pd core–shell nanoparticles. The catalytic activity of the synthesized yolk–shell Fe₃O₄@PANI/Ni@Pd composite was investigated in the reduction of o‐nitroaniline to benzenediamine by NaBH₄, which exhibited conversion of 99% in 3 min with a very low content of the catalyst. Transmission electron microscopy, X‐ray photoelectron spectroscopy, TGA, X‐ray diffraction, UV–visible, scanning electron microscopy, X‐ray energy dispersion spectroscopy and FT‐IR were employed to characterize the synthesized nanocatalyst. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and Crystal Structure of a Rare Tetra‐Yttrium‐Supported Krebs‐Type Tungstoantimonate

A rare tetra‐yttrium‐supported Krebs‐type tungstoantimonate was prepared in an acidic solution at pH 2.2 and characterized by elemental analysis and IR spectroscopy. Single‐crystal X‐ray analysis was carried out on Na₂[{Y(H₂O)₇}₄Sb₂W₂₂O₇₆]·14H₂O ( 1 ), which comprises a Krebs‐type [Sb₂W₂₂O₇₆]^14– unit supported by four yttrium ions.     

An Enzyme‐free H2O2 Sensor Based on Poly(2‐Aminophenylbenzimidazole)/Gold Nanoparticles Coated Pencil Graphite Electrode

A poly(2‐aminophenylbenzimidazole)/gold nanoparticles (P2AB/AuNPs) coated disposable pencil graphite electrode (PGE) was fabricated as an enzyme‐free sensor for the H₂O₂ determination. P2AB/AuNPs and P2AB were successfully synthesized electrochemically on PGE in acetonitrile for the first time. The coatings were characterized by scanning electron microscopy, X‐ray diffraction spectroscopy, Energy‐dispersive X‐ray spectroscopy, Surface‐enhanced Raman spectroscopy, and UV‐Vis spectroscopy. AuNPs interacted with P2AB as carrier enhances the electrocatalytic activity towards reduction of H₂O₂. The analytical performance was evaluated in a 100 mM phosphate buffer solution at pH 6.5 by amperometry. The steady state current vs. H₂O₂ concentration is linear in the range of 0.06 to 100 mM (R²=0.992) with a limit of detection 3.67×10^?5 M at ?0.8 V vs. SCE and no interference is caused by ascorbic acid, dopamine, uric acid, and glucose. The examination for the sensitive determination of H₂O₂ was conducted in commercially available hair oxidant solution. The results demonstrate that P2AB/AuNPs/PGE has potential applications as a sensing material for quantitative determination of H₂O₂.     

Novel Flower‐Like Ag‐SiO2‐MgO‐Al2O3 Material: Preparation,Characterization and Catalytic Application in Methanol Dehydrogenation

Catalytic direct dehydrogenation of methanol to formaldehyde was carried out over Ag‐SiO₂‐MgO‐Al₂O₃ catalysts prepared by sol‐gel method. The optimal preparation mass fractions were determined as 8.3% MgO, 16.5% Al₂O₃ and 20% silver loading. Using this optimum catalyst, excellent activity and selectivity were obtained. The conversion of methanol and the selectivity to formaldehyde both reached 100%, which were much higher than other previously reported silver supported catalysts. Based on combined characterizations, such as X‐ray diffraction (XRD), scanning electronic microscopy (SEM), diffuse reflectance ultraviolet‐visible spectroscopy (UV‐Vis, DRS), nitrogen adsorption at low temperature, temperature programmed desorption of ammonia (NH₃‐TPD), desorption of CO₂ (CO₂‐TPD), etc., the correlation of the catalytic performance to the structural properties of the Ag‐SiO₂‐ MgO‐Al₂O₃ catalyst was discussed in detail. This perfect catalytic performance in the direct dehydrogenation of methanol to formaldehyde without any side‐products is attributed to its unique flower‐like structure with a surface area less than 1 m²/g, and the strong interactions between neutralized support and the nano‐sized Ag particles as active centers.     

Dye degradation studies of Mo‐doped TiO2 thin films developed by reactive sputtering

TiO₂ thin films with various Mo concentrations have been deposited on glass and n‐type silicon (100) substrates by this radio‐frequency (RF) reactive magnetron sputtering at 400°C substrate temperature. The crystal structure, surface morphology, composition, and elemental oxidation states of the films have been analyzed by using X‐ray diffraction, field emission scanning electron microscopy, atomic force microscopy, and X‐ray photoelectron spectroscopy, respectively. Ultraviolet‐visible spectroscopy has been used to investigate the degradation, transmittance, and absorption properties of doped and undoped TiO₂ films. The photocatalytic degradation activity of the films was evaluated by using methylene blue under a light intensity of 100 mW cm⁻². The X‐ray diffraction patterns show the presence of anatase phase of TiO₂ in the developed films. X‐ray photoelectron spectroscopy studies have confirmed that Mo is present only as Mo⁶⁺ ions in all films. The Mo/TiO₂ band gap decreases from ~3.3 to 3.1 eV with increasing Mo dopant concentrations. Dye degradation of ~60% is observed in Mo/TiO₂ samples, which is much higher than that of pure TiO₂.     

Synthesis of W‐doped TiO2 by low‐temperature hydrolysis: Effects of annealing temperature and doping content on the surface microstructure and photocatalytic activity

A series of tungsten‐doped Titania photocatalysts were synthesized using a low‐temperature method. The effects of dopant concentration and annealing temperature on the phase transitions, crystallinity, electronic, optical, and photocatalytic properties of the resulting material were studied. The X‐ray patterns revealed that the doping delays the transition of anatase to rutile to a high temperature. A new phase W_yTi_1‐yO₂ appeared for 5.00 wt% W‐TiO₂ annealed at 900 °C. Raman and diffuse reflectance UV–Vis spectroscopy showed that band gap values decreased slightly up to 700 °C. X‐ray photoelectron spectroscopy showed that surface species viz. Ti³⁺, Ti⁴⁺, O^2?, oxygen‐vacancies, and adsorbed OH groups vary depending on the preparation conditions. The photocatalytic activity was evaluated via the degradation of methylene blue using LED white light. The degradation rate was affected by the percentage of dopants. The best photocatalytic activity was achieved with the sample labeled 5.00 wt% W‐TiO₂ annealed at 700 °C.     

Enhanced epoxidation of soybean oil by novel Al2O3–ZrO2–TiO2 solid acid catalyst

This study aims to develop highly efficient, recyclable solid catalysts for the epoxidation of vegetable oils. An Al₂O₃–ZrO₂–TiO₂ solid acid catalyst was prepared by a co‐precipitation/impregnation method and characterised through scanning electron microscopy, energy‐dispersive spectroscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, Fourier‐transform infrared and nitrogen adsorption–desorption analyses. The solid acid catalyst with a high surface area and typical slit pore adsorption was successfully synthesised. Al₂O₃–ZrO₂–TiO₂ also exhibits high stability and improved catalytic efficiency in the epoxidation of soybean oil. An oil conversion rate of 86.6%, which is higher than that of conventional catalysts, was obtained with a catalyst loading of 0.8 wt% and was maintained at 76.6% even after recycling the catalyst three times. The performance of the solid catalyst was slightly superior to that of H₂SO₄. Therefore, this novel catalyst may potentially be applicable in catalysing soybean oil epoxidation.     

Synthesis of Fe3O4@SiO2@DOPisatin‐Ni(II) and Cu(II) nanoparticles: Highly efficient catalyst for the synthesis of sulfoxides and disulfides

The catalytic activity of two magnetic catalysts Fe₃O₄@SiO₂@DOPisatin‐M(II) (M = Ni, Cu) was investigated in the environmentally green H₂O₂ oxidant‐based oxidation of sulfides to sulfoxides and oxidative coupling of thiols to disulfides. By using these catalysts, various substrates were successfully converted into their corresponding product. These catalysts could also be reused multiple time without significant loss of activity. The physical and chemical properties of the catalysts were determined using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), thermogravimetric analysis (TGA), vibrating sample magnetometer (VSM), energy dispersive X‐ray spectroscopy (EDX) and atomic absorption spectroscopy (AAS).