Degradation of pharmaceutical beta-blockers by electrochemical advanced oxidation processes using a flow plant with a solar compound parabolic collector

The degradation of the beta-blockers atenolol, metoprolol tartrate and propranolol hydrochloride was studied by electro-Fenton (EF) and solar photoelectro-Fenton (SPEF). Solutions of 10 L of 100 mg L⁻¹ of total organic carbon of each drug in 0.1 M Na₂SO₄ with 0.5 mM Fe²⁺ of pH 3.0 were treated in a recirculation flow plant with an electrochemical reactor coupled with a solar compound parabolic collector. Single Pt/carbon felt (CF) and boron-doped diamond (BDD)/air-diffusion electrode (ADE) cells and combined Pt/ADE-Pt/CF and BDD/ADE-Pt/CF cells were used. SPEF treatments were more potent with the latter cell, yielding 95-97% mineralization with 100% of maximum current efficiency and energy consumptions of about 0.250 kWh g TOC⁻¹. However, the Pt/ADE-Pt/CF cell gave much lower energy consumptions of about 0.080 kWh g TOC⁻¹ with slightly lower mineralization of 88-93%, then being more useful for its possible application at industrial level. The EF method led to a poorer mineralization and was more potent using the combined cells by the additional production of hydroxyl radicals (^•OH) from Fenton’s reaction from the fast Fe²⁺ regeneration at the CF cathode. Organics were also more rapidly destroyed at BDD than at Pt anode. The decay kinetics of beta-blockers always followed a pseudo first-order reaction, although in SPEF, it was accelerated by the additional production of ^•OH from the action of UV light of solar irradiation. Aromatic intermediates were also destroyed by hydroxyl radicals. Ultimate carboxylic acids like oxalic and oxamic remained in the treated solutions by EF, but their Fe(III) complexes were photolyzed by solar irradiation in SPEF, thus explaining its higher oxidation power. NO₃⁻ was the predominant inorganic ion lost in EF, whereas the SPEF process favored the production of NH₄⁺ ion and volatile N-derivatives.     

Acylation of a substituted benzofuran over an HY zeolite and its subsequent deacylation and reacylation

The acylation reaction of 2-butylbenzofuran withp-anisoyl chloride andp-anisic acid in the presence of faujasite type zeolites, in the liquid phase, is reported. A good initial selectivity to the 3-acylated derivative is obtained, but the selectivity decreases with time. This result is explained by the involvement of a deacylation-reacylation process.     

Prediction of catalyst stability in naphtha reforming

A method to predict catalyst activity (RON) and selectivity (ηc5⁺, liquid yield) of naphtha-reforming catalysts during normal operation is described. It involves performing experiments at normal operational conditions and testing accelerated deactivation. These last experiments have a severe intermediate period at lower pressure. Carbon formation is related to time and the decrease in RON and ηc5⁺ is related to carbon at normal operation. The accelerated deactivation produces a similar coke to the one at normal conditions for an equal amount of coke. Therefore for each time at normal conditions there is a corresponding pressure in the accelerated deactivation test. Power law-equations fit the data well and combining them results in the following relations: P = at^b; Δ_NRON = cP^d; Δ_Nηc5⁺ = eP^f. The coefficients a, b, c, d, e and f depend on the catalyst and are calculated from four or six experiments (half at normal conditions and half accelerated deactivation tests); b, d and f bare negative. The value of pressure for the time at which it is desired to predict catalyst activity and selectivity is calculated from the first equation. This value when applied to the second and third equations gives the activity and selectivity, respectively, that the catalyst will have after time t.     

Polymeric Microspheres/Cells/Extracellular Matrix Constructs Produced by Auto-Assembly for Bone Modular Tissue Engineering

Modular tissue engineering (MTE) is a novel “bottom-up” approach to create engineered biological tissues from microscale repeating units. Our aim was to obtain microtissue constructs, based on polymer microspheres (MSs) populated with cells, which can be further assembled into larger tissue blocks and used in bone MTE. Poly(L-lactide-co-glycolide) MS of 165 ± 47 µm in diameter were produced by oil-in-water emulsification and treated with 0.1 M NaOH. To improve cell adhesion, MSs were coated with poly-L-lysine (PLL) or human recombinant collagen type I (COL). The presence of oxygenated functionalities and PLL/COL coating on MS was confirmed by X-ray photoelectron spectroscopy (XPS). To assess the influence of medium composition on adhesion, proliferation, and osteogenic differentiation, preosteoblast MC3T3-E1 cells were cultured on MS in minimal essential medium (MEM) and osteogenic differentiation medium (OSG). Moreover, to assess the potential osteoblast–osteoclast cross-talk phenomenon and the influence of signaling molecules released by osteoclasts on osteoblast cell culture, a medium obtained from osteoclast culture (OSC) was also used. To impel the cells to adhere and grow on the MS, anti-adhesive cell culture plates were utilized. The results show that MS coated with PLL and COL significantly favor the adhesion and growth of MC3T3-E1 cells on days 1 and 7, respectively, in all experimental conditions tested. On day 7, three-dimensional MS/cell/extracellular matrix constructs were created owing to auto-assembly. The cells grown in such constructs exhibited high activity of early osteogenic differentiation marker, namely, alkaline phosphatase. Superior cell growth on PLL- and COL-coated MS on day 14 was observed in the OSG medium. Interestingly, deposition of extracellular matrix and its mineralization was particularly enhanced on COL-coated MS in OSG medium on day 14. In our study, we developed a method of spontaneous formation of organoid-like MS-based cell/ECM constructs with a few millimeters in size. Such constructs may be regarded as building blocks in bone MTE.     

Anticipation of digital patterns

A memristive device is a novel passive device, which is essentially a resistor with memory. This device can be used for novel technical applications like neuromorphic computation. In this paper, we focus on anticipation—a capability of a system to decide how to react in an environment by predicting future states. Especially, we have designed an elementary memristive circuit for the anticipation of digital patterns, where this circuit is based on the capability of an amoeba to anticipate periodically occurring unipolar pulses. The resulting circuit has been verified by digital simulations and has been realized in hardware as well. For the practical realization, we have used an Ag‐doped TiO_2?x‐based memristive device, which has been fabricated in planar capacitor structures on a silicon wafer. The functionality of the circuit is shown by simulations and measurements. Finally, the anticipation of information is demonstrated by using images, where the robustness of this anticipatory circuit against noise and faulty intermediate information is visualized.     

Growth Kinetics and Characterization of Chromia Scales Formed on Ni–30Cr Alloy in Impure Argon at 700 °C

Oxidation of Metals - The oxidation of a Ni–30Cr alloy at 700 °C in impure argon was studied in order to provide new elements of understanding on chromia scale growth in low...     

Influence of pH cycling and mechanical loading on the resin-dentin microtensile bond strength

The durability of adhesive interfaces is still a problem in adhesive restorations in dentistry. Laboratorial ageing methods have been proposed to predict the performance of materials, but they still require standardization. The objective of this study was to evaluate the resin-dentin microtensile bond strength of composite restorations subjected to pH cycling and different levels of mechanical loading. Resin blocks were built over a flat superficial dentin of bovine incisors (n = 40), using a three-step adhesive system. Half of the specimens were submitted to 10 cycles of pH cycling, followed by mechanical loading (0, 500,000; 1,000,000; 2,000,000 cycles – 98 N, 4 Hz). The other half was directly subjected to mechanical loading. After ageing, all groups were subjected to a microtensile bond test. Data were analyzed using two-way ANOVA and Tukey’s test (α = 0.05). The frequency of the early de-bonding was compared using the Chi-square test (α = 0.05). The statistical analysis revealed that the cross-product interaction ‘pH cycling’ vs. ‘number of mechanical loading cycles’ (p = 0.72) as well as the main factor ‘pH cycling’ (p = 0.49) was not statistically significant, and they were not able to reduce the resin–dentin bond strength values. Regarding the number of mechanical loading cycles, the groups subjected to 2,000,000 cycles showed lower bond strength values than the others (p = 0.003). The frequency of debonded specimens increased with mechanical loading. Therefore, it can be concluded that in this restorative model, at least 2,000,000 mechanical cycles are need to decrease the microtensile strength and simulate the ageing of the interface.     

Oxidative and photochemical processes for the removal of galaxolide and tonalide from wastewater

Synthetic musks have been reported in wastewaters at concentrations as high as tens of micrograms per litre. The two most significant polycyclic musk fragrance compounds are 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyran (HHCB, trade name galaxolide^®) and 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene (AHTN, trade name tonalide^®). We report the result of several irradiation and advanced oxidation processes carried out on samples of the effluent of a wastewater treatment plant located in Alcalá de Henares, Madrid. Wastewater samples were pre-ozonated and spiked with 500 ng/L of tonalide or galaxolide in order to obtain final concentrations in the same order as the raw effluent. The treatments assayed were ozonation with and without the addition of hydrogen peroxide (O₃, O₃/H₂O₂), ultraviolet (254 nm low pressure mercury lamp) and xenon-arc visible light irradiation alone and in combination with ozone (UV, O₃/UV, Xe, O₃/Xe) and visible light photocatalytic oxidation using a Ce-doped titanium dioxide photocatalyst performed under continuous oxygen or ozone gas bubbling (O₂/Xe/Ce-TiO₂, O₃/Xe/Ce-TiO₂). In all cases, samples taken at different contact times up to 15 min were analyzed. An analytical method based on stir bar sorptive extraction (SBSE), followed by comprehensive two-dimensional gas chromatography (SBSE-GC × GC-TOF-MS), was used for the automatic searching and evaluation of the synthetic musks and other nonpolar or semipolar contaminants in the wastewater samples. In all cases tonalide was more easily removed than galaxolide. The best results for the latter (more than 75% removal after 5 min on stream) were obtained from ozonation (O₃) and visible light photocatalytic ozonation (O₃/Xe/Ce-TiO₂). A significant removal of both pollutants (∼60% after 15 min) was also obtained during visible light photocatalysis (O₂/Xe/Ce-TiO₂). UV radiation was able to deplete tonalide (+90%) after 15 min but only reduced the concentration of galaxolide to about half of its initial concentration. The toxicity of treated samples decreased for O₃/UV and O₃/Ce-TiO₂, but increased during irradiation processes UV, Xe and Xe/Ce-TiO₂. Ozone treatments tend to decrease toxicity up to a certain dosage, from which point the presence of toxic transformation products has adverse effects on aquatic microorganisms.