IrO2–SnO2 mixtures as electrocatalysts for the oxygen reduction reaction in alkaline media

In this work, SnO₂ + IrO₂ mixed oxides are studied as electrocatalysts for the oxygen reduction reaction (ORR) in alkaline media by means of voltammetric techniques under controlled mass transfer conditions thanks to the use of rotating (ring) disk electrodes (RDE/RRDE). The oxides, prepared by sol–gel methodology, are supported on the disk electrodes using a thin layer of anionic exchange polymer as gluing agent. The amount of deposited polymer was optimized to avoid any limitation due to the diffusion of reactant/products across the film thickness. The mixed oxides were prepared at the following mole fractions of IrO₂: $ x_{{{\text{IrO}}_{ 2} }} $  = 0.15, 0.31, 0.55, 0.73, and 1. The role of composition was studied in terms of the reaction pathways and the relevant fraction of H₂O₂ production, together with the potentials of the onset of ORR. The fraction of sites able to give proton/hydroxyl and electron transfers is also determined and discussed. The results point to the best performance of low-Ir containing mixtures and to their low sensitivity to the presence of methanol, a key feature in the case of crossover in alkaline direct alcohol fuel cells.     

ENGINEERING ASPECTS OF PENICILLIN G TRANSFER AND CONVERSION TO 6-AMINOPENICILLANIC ACID IN A BIOREACTOR WITH A MOBILE BED OF IMMOBILIZED PENICILLIN AMIDASE

This article presents studies on the external and internal mass transfers of penicillin G for 6-aminopenicillanic acid enzymatic production using a bioreactor with a stirred bed of immobilized penicillin amidase. By means of the substrate mass balance for a single particle of biocatalyst and considering the kinetic model adapted for competitive and noncompetitive inhibitions, specific mathematical models were developed for describing the profiles of penicillin G concentration in the outer and inner regions of biocatalyst and for estimating its mass flows in the liquid boundary layer surrounding the particle and inside the particle. The values of the mass flows are significantly influenced by the internal diffusion velocity and rate of the enzymatic conversion of substrate. These cumulated influences led to the appearance of an enzymatic inactive region near the particle center, its magnitude varying from 0 to 9.2% of the overall volume of particles.     

Influence of post-curing temperature on the structure,properties, and adhesion of vinyl ester adhesive

Vinyl ester (VE) resins are widely used as thermoset adhesives in structural joints and composites, but complete curing under environmental conditions is not produced. The existing literature dealing with the effect of post-curing on the structure, viscoelastic, mechanical, and adhesion properties of VE resin is scarce. Therefore, in this study, VE resin was subjected to different post-curing temperatures (50–140 °C) for one hour, and the changes in structure and properties were assessed. The degree of cross-linking of the VE resin depended on the post-curing temperature and cure started to be completed above 100 °C, a temperature close to the glass transition temperature (115 °C) of the completely cross-linked polymer. Furthermore, gel formation in VE resin was evidenced for post-curing temperature below 100 °C. In order to fully cross-link the VE resin, post-curing at 140 °C for one hour was necessary, and it was evidenced by an increase in the glass transition temperature and in the mechanical properties; an increase in adhesion to cold rolled steel was obtained although the shear strength was lower than in the joint produced with the non-post-cured VE resin.     

Influence of chlorhexidine in cavities prepared with ultrasonic or diamond tips on microtensile bond strength

This study evaluated the effect of chlorhexidine (CLX) in cavities prepared with either ultrasound-mounted CVDentUS diamond tips or conventional diamond burs on dentin bond strength after 24 h and 180 days. Forty-eight dentin surfaces from sound third molars were flattened and divided into four groups (n = 12), according to the type of cavity preparation (CVDentUS ultrasound tip or conventional diamond) and with or without 2% CLX (Consepsis) treatment. After application of the adhesive system (Clearfil SE Bond), microhybrid composite resin blocks (Charisma) were made on the dentin surface in increments. After 24 h, the specimens were sectioned into stick-shaped samples with an adhesive interface of approximately 1 mm². From each tooth, half of the sticks were evaluated after 24 h of storage in distilled water and the other half after 180 days, using a universal testing machine. Three-way analysis of variance showed no significant triple interactions (p = 0.722) or double interactions between factors. Higher bond strength values were observed with the use of ultrasonic tips (p = 0.019), irrespective of whether or not CLX was applied in either time period. No difference in bond strength values was observed in terms of CLX application (p = 0.581). No significant difference in bond strength values was shown after storage for 24 h or 180 days (p = 0.302). In conclusion, the ultrasonic tips promoted greater bond strength to dentin, irrespective of whether or not CLX was applied, and storage time.     

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.     

Endodontic irrigants effect on long-term intraradicular adhesion of resin cements

The aim of this study was to evaluate over time the bond strength of dual-cure and self-adhesive resin cements used for bonding fiberglass posts following irrigation with different solutions. Ninety roots from single-rooted premolars were selected and divided into 6 groups (n = 15) according to the resin cement, dual-cure or self-adhesive (RelyX ARC and RelyX U100) or the endodontic irrigant used (2% chlorhexidine digluconate - CH, 1% sodium hypochlorite - SH and deionized distilled water – control). Following post cementation, the roots were cross-sectioned in order to obtain two slices from each root third (cervical, mid and apical). The specimens were stored for 7 or 180 days in water and the push-out bond strength test applied. The data was analyzed using three-way ANOVA and Tukey Kramer. The interaction endodontic irrigants-resin cement vs. storage time was significant (p = 0.008), where 7 days of storage induced no difference between the groups, however, after 180 days, the groups for which CH or SH combined with RelyX U100 were used showed higher bond strength values than RelyX ARC, regardless of the irrigant solution. There was no difference between the use of RelyX ARC after 7 and 180 days of storage. For Rely X U100 180 days of storage increased the push-out bond strength when either CH or SH was used. The dual-cure and self-adhesive resin cements associated with CH or SH demonstrated similar immediate bond strength performance. The self-adhesive cement, however, showed improved bond strength over time when either irrigant was used.     

Interaction of silicon-based quantum dots with gibel carp liver: oxidative and structural modifications

Quantum dots (QDs) interaction with living organisms is of central interest due to their various biological and medical applications. One of the most important mechanisms proposed for various silicon nanoparticle-mediated toxicity is oxidative stress. We investigated the basic processes of cellular damage by oxidative stress and tissue injury following QD accumulation in the gibel carp liver after intraperitoneal injection of a single dose of 2 mg/kg body weight Si/SiO₂ QDs after 1, 3, and 7 days from their administration.QDs gradual accumulation was highlighted by fluorescence microscopy, and subsequent histological changes in the hepatic tissue were noted. After 1 and 3 days, QD-treated fish showed an increased number of macrophage clusters and fibrosis, while hepatocyte basophilia and isolated hepatolytic microlesions were observed only after substantial QDs accumulation in the liver parenchyma, at 7 days after IP injection.Induction of oxidative stress in fish liver was revealed by the formation of malondialdehyde and advanced oxidation protein products, as well as a decrease in protein thiol groups and reduced glutathione levels. The liver enzymatic antioxidant defense was modulated to maintain the redox status in response to the changes initiated by Si/SiO₂ QDs. So, catalase and glutathione peroxidase activities were upregulated starting from the first day after injection, while the activity of superoxide dismutase increased only after 7 days. The oxidative damage that still occurred may impair the activity of more sensitive enzymes. A significant inhibition in glucose-6-phosphate dehydrogenase and glutathione-S-transferase activity was noted, while glutathione reductase remained unaltered.Taking into account that the reduced glutathione level had a deep decline and the level of lipid peroxidation products remained highly increased in the time interval we studied, it appears that the liver antioxidant defense of Carassius gibelio does not counteract the oxidative stress induced 7 days after silicon-based QDs exposure in an efficient manner.     

Microwave assisted combustion synthesis in the system Ti–Si–C for the joining of SiC: Experimental and numerical simulation results

Microwaves at 2.45 GHz have been applied to ignite the combustion synthesis of compacted Ti–Si–C powders mixtures, having 1:1:1 atomic ratio, in order to join SiC-based components. A mixture of different refractory phases such as TiC and TiSi₂ were obtained. Depending on the synthesis conditions, no residual silicon in the joint was detected, suggesting the suitability of the here proposed experimental joining approach for nuclear plants and high temperature applications. A simplified model was developed with the aim of obtaining a deeper understanding of the here proposed rapid, almost pressure-less and localized heating joining method. Experimental and numerical simulation results demonstrate that joining of SiC can be rapidly obtained with minimization of heat affected zones in the SiC substrates. Maximum apparent shear strength values of the joints ranged from 9.9 to 45.1 MPa, depending on the process conditions.     

Effect of the mimic structure on the molecular recognition properties of molecularly imprinted polymers for ochratoxin A prepared by a fragmental approach

In this work the fragmental approach was used to prepare several molecularly imprinted ethylene dimethacrylate-co-methacrylic acid polymers with molecular recognition towards the mycotoxin ochratoxin A, with the aim of searching for simpler mimic templates than the well-known N-(4-chloro-1-hydroxy-2-naphthoylamido)-(l)-phenylalanine. The screening for binding of two different kinds of ochratoxin-related molecules was performed by HPLC analysis. Ochratoxin A and the mimic templates were eluted in acetonitrile–acetic acid (0.1% v/v) and the imprinting factor was measured for all the ligands on all the columns packed with the imprinted polymers. The experimental results show that changes to the amino acidic sub-structure or the presence/absence of a chlorine atom in position 4 on the naphthalene ring system does not affect the molecular recognition of ochratoxin A by the resulting imprinted polymer. On the contrary, the presence of the bulky naphthalene ring system in the mimic template seems to be necessary to preserve the molecular recognition of ochratoxin. This binding behavior was found to be compatible with in silico simulations of the complexation between some of the mimic templates and molecules of methacrylic acid. The use of the mimic template N-(1-hydroxy-2-naphthoylamido)-(L)-phenylalanine seems to represent a synthetically simple approach to the preparation of imprinted polymers with molecular recognition properties towards ochratoxin A.     

Degradation of an Azo Dye (Ponceau 4R) and Treatment of Wastewater from a Food Industry by Ozonation

Experiments for degradation of the extensively marketed Ponceau 4R dye in aqueous solution and for oxidation of raw wastewater from a confectionary industry have been carried out by using ozone. All the experiments were performed in a cylindrical semi-batch reactor at approximately 20 ^oC for 7200 s. A mass flow rate of 1.158?×?10^?6 kg s^?1 of ozone was continuously fed in the reactor. The pH of the azo dye aqueous solution (distilled water + Ponceau 4R) was always kept at approximately 5.8, while in the case of the raw wastewater the same factor was changed from 4.7 to 9.4 in two different experimental runs. Absorbance measurements at 508 nm show that the investigated azo dye found in the azo dye aqueous solution was completely degraded after only 600 s. At this initial period a substantial fall of TOC (Total Organic Carbon) (up to 45%) was noticed, but the rate was exponentially decreased at longer reaction times up to a TOC removal no higher than 60%. The ozonation was also responsible for reducing the apparent color of the raw wastewater to almost 10% of its initial value at the optimum pH (9.4 ± 1.5). The effect of pH was important on apparent color, but it had absolutely no influence on the kinetics results of COD (Chemical Oxygen Demand), which were kept constant over the entire period of reaction.