N-methyl-2-hydroxyethylammonium oleate ionic liquid performance as corrosion inhibitor for mild steel in hydrochloric acid medium

The aim of the present study is to evaluate the performance of N-methyl-2-hydroxyethylammonium oleate ([m-2HEA][Ol]) as a corrosion inhibitor for mild steel in a 0.1-mol/L hydrochloric acid solution and also investigate the role of chloride in the inhibition mechanism. This protic ionic liquid (PIL) has formerly shown a high efficiency as a corrosion inhibitor in a neutral chloride medium. Electrochemical and weight loss measurements, surface contact angle determination, scanning electron microscopy, and Raman spectroscopy were used to understand the factors that influence the response of the studied inhibitor. Results revealed that [m-2HEA][Ol] behaves as a mixed-type adsorption inhibitor, by blocking cathodic sites and by modifying the activation energy of the anodic reaction, and it can reach up to 94–97% of inhibition efficiency. PIL adsorption was enhanced by the excess of positive charge of the mild steel. The effect of inhibitor molecule has been discussed to propose a mechanism that explains the inhibitory action of the corrosion inhibitor, pointing out the role of chloride in the inhibition mechanism.     

Electrochemical promotion of Rh catalyst in gas-phase reduction of NO by propylene

The concept of non-faradaic electrochemical modification of catalytic activity (NEMCA) has been applied for the in situ control of catalytic activity of a rhodium film deposited on YSZ (yttria stabilized zirconia) solid electrolyte towards reduction of 1000 ppm NO by 1000 ppm C₃H₆ in presence of excess (5000 ppm) O₂ at 300 °C. A temporary heating at this feed composition results in a long-lasting deactivation of the catalyst under open circuit conditions due to partial oxidation of the rhodium surface. Positive current application (5 A) over both the active and the deactivated catalysts gives rise to an enhancement of N₂ and CO₂ production, the latter exceeding several hundred times the faradaic rate. While active rhodium exhibits a reversible behaviour, electrochemical promotion on the deactivated catalyst is composed of a reversible and an irreversible part. The reversible promotion results from the steady-state accumulation of current-generated active species at the gas exposed catalyst surface whereas the irreversible effect is due to the progressive reduction of the catalyst resulting in an increased recovery rate of lost catalytic activity. The results are encouraging with respect to application of rhodium for the catalytic removal of NO from auto-exhaust gases under lean-burn conditions.     

Catalytic behavior of vanadium-containing mesoporous silicas in the oxidative dehydrogenation of propane

Three series of vanadium-containing silica catalysts (2–7.6 wt% V) have been prepared by varying the synthesis method. In all cases, conversion values in the oxidative dehydrogenation of propane increase with the temperature, vanadium loading and reducibility. For impregnated and anchored catalysts, a relationship between the selectivity towards propene and the effective acidity, as determined in the dehydration of 2-propanol, can be established. This revised version was published online in July 2006 with corrections to the Cover Date.     

Protective effect of olive oil and its phenolic compounds against low density lipoprotein oxidation

The protective effect of phenolic compounds from an olive oil extract, and of olive oils with (extra-virgin) and without (refined) phenolic components, on low density lipoprotein (LDL) oxidation was investigated. When added to isolated LDL, phenolics [0.025–0.3 mg/L caffeic acid equivalents (CAE)] increased the lag time of conjugated diene formation after copper-mediated LDL oxidation in a concentration-dependent manner. Concentrations of phenolics greater than 20 mg/L inhibited formation of thiobarbituric-acid reactive substances after AAPH-initiated LDL oxidation. LDL isolated from plasma after preincubation with phenolics (25–160 mg/L CAE) showed a concentration-dependent increase in the lag time of conjugated diene formation after copper-mediated LDL oxidation. Refined olive oil (0 mg/L CAE) and extra-virgin olive oil (0.1 and 0.3 mg/L CAE) added to isolated LDL caused an increase in the lag time of conjugated diene formation after copper-mediated LDL oxidation that was related to olive oil phenolic content. Multiple regression analysis showed that phenolics were significantly associated with the increase in lag time after adjustment for effects of other antioxidants; α-tocopherol also achieved a statistically significant effect. These results indicate that olive oil phenolic compounds protect LDL against peroxyl radical-dependent and metal-induced oxidation in vitro and could associate with LDL after their incubation with plasma. Both types of olive oil protect LDL from oxidation. Olive oil containing phenolics, however, shows more antioxidant effect on LDL oxidation than refined olive oil.     

Radiation grafting of N,N-dimethylaminoethylmethacrylate onto poly(ethylene terephthalate)

Summary Radiation-induced graft polymerization of N,N-dimethylaminoethylmethacrylate (DMAEMA) from 50% solution in chloroform onto poly(ethylene terephthalate) (PET) was carried out by means of mutual γ-irradiation of polymer in presence of liquid or vapor phase monomer solutions (direct method), or by grafting of monomer from this liquid solution onto polymer preirradiated in air. It has been shown higher effectiveness of grafting by the direct method from vapor phase of monomer or by the preirradiation method as compared with direct grafting from liquid monomer solution. Grafting did not affect crystallinity, transparency and durability of the starting PET. Received: 18 November 1999/Revised version: 7 February 2000/Accepted: 8 February 2000     

Ternary Copper(II) Complexes in Solution Formed With 8-Aza Derivatives of the Antiviral Nucleotide Analogue 9-[2-(Phosphonomethoxy)Ethyl]Adenine (PMEA)

The stability constants of the mixed-ligand complexes formed between Cu(Arm)(2+), where Arm= 2,2'-bipyridine (Bpy) or 1,10-phenanthroline (Phen), and the dianions of 9-[2-(phosphonomethoxy)ethyl]-8-azaadenine (9,8aPMEA) and 8-[2-(phosphonomethoxy)ethyl]-8-azaadenine (8,8aPMEA) (both also abbreviated as PA(2-)) were determined by potentiometric pH titrations in aqueous solution (25 ( degrees )C; I = 0.1 M, NaNO(3)). All four ternary Cu(Arm)(PA) complexes are considerably more stable than corresponding Cu(Arm)(R-PO(3)) species, where R-PO(3) (2-) represents a phosph(on)ate ligand with a group R that is unable to participate in any kind of interaction within the complexes. The increased stability is attributed to intramolecular stack formation in the Cu(Arm)(PA) complexes and also to the formation of 5-membered chelates involving the ether oxygen present in the -CH(2)-O-CH(2)-PO(3) (2-) residue of the azaPMEAs. A quantitative analysis of the intramolecular equilibria involving three structurally different Cu(Arm)(PA) species is carried out. For example, about 5% of the Cu(Bpy)(8,8aPMEA) system exist with the metal ion solely coordinated to the phosphonate group, 14% as a 5-membered chelate involving the -CH(2)-O-CH(2)-PO(3) (2-)residue, and 81% with an intramolecular stack between the 8-azapurine moiety and the aromatic rings of Bpy. The results for the other systems are similar though with Phen a formation degree of about 90% for the intramolecular stack is reached. The existence of the stacked species is also proven by spectrophotometric measurements. In addition, the Cu(Arm)(PA) complexes may be protonated, leading to Cu(Arm)(H;PA)(+) species for which it is concluded that the proton is located at the phosphonate group and that the complexes are mainly formed by a stacking adduct between Cu(Arm)(2+) and H(PA)(-). Conclusions regarding the biological properties of these azaPMEAs are shortly indicated.     

Changes in serum lipids in rats treated with oral cooper

Disturbances in lipid metabolism during copper deficiency in rats are well recognized. Copper deficiency is associated with the spontaneous retention of hepatic iron. Previous studies have reported that hypercholesterolemia and hypertriglyceridemia are associated with elevated hepatic iron concentrations in copper deficient rats. There was a direct relationship between the magnitude of blood lipids and the concentration of hepatic iron. Based on these data, it has been hypothesized that iron was responsible for the development of lipemia of copper deficiency. In this study was determined the effect of increasing doses of Cu(10, 20 and 50 ppm) in the diet, on the serum total lipids, total cholesterol, triglycerides (triacylglicerols), phospholipids, non-esterified fatty acids (NEFA) and liver iron and zinc concentrations in normal rats. The results were compared with normal rats that received a balanced diet containing 0.6 and 6 ppm of Cu, respectively. The results show that Cu-supplement diminished the cholesterol and triglyceride serum levels, increased the level of phospholipids, NEFA and concomitantly decreased the hepatic concentrations of Fe and Zn. There was a statistically significant (p < 0.05) simple correlation between triglycerides and liver Fe (r = 0.917; R2 = 64.03%), cholesterol and liver Zn (r = 0.872; R2 = 76.07%), cholesterol and liver Fe (r = 0.995; R2 = 99.10%), liver Fe and liver Cu (r = -0.612), liver Fe and liver Zn (r = 0.837), liver Cu and liver Zn (r = -0.612), and serum triglycerides and liver Zn (r = 0.967). The mechanism(s) by which Fe and Zn determine these changes is not known; none of the enzymes that act in cholesterol and triglyceride metabolism and biosynthesis require Fe and/or Zn. The increase of NEFA is due to changes in the process of lipolysis and re-esterification of the fatty acids in blood. However, additional studies are needed for the precise mechanisms of this interrelationships to be clarified.     

Enzymatic modification of the functional, nutritional and sensorial properties of soybeans for special feeding

Production of new protein-based products for special nutrition such as hypoallergenic infant formulas, fortified beverages and nutraceutics, require ideal ingredients. Protein ingredients were developed by enzymatic hydrolysis and methionine synthesis of soy protein. Hydrolysis was done at 4% (w/v) using porcine pancreatic enzymes (4% w/w), 50 degrees C, 6 h and pH 8. After drying powder was resuspended (20% w/v) and incubated with 7.6% (w/w) methionine methyl-ester, 1% (w/w) chymotrypsin and 3 M glycerol, 37 degrees C, 3 h and pH 7. Hydrolysates were fractionated by ultrafiltration (UF) before and after enrichment (E): FI > 10, 10 > FII > 3 and 3 > FIII > 1 kDa. Functional properties, amino acid content, anti-physiological factor activities and antigenicity were assayed for all the UF fractions and the soybean meal. Protein quality bioassay and sensorial test of an non-enriched fraction and an enriched fraction were performed. Functional properties were positively modified by hydrolysis and synthesis by using a minimum time and methionine added for the last reaction. After UF all the fractions under 10 kDa showed 100% solubility (pH 4 and 7), good clarity, acceptable foam capacity and negligible antigenicity and antiphysiological activities. Additionally, methionine enrichment enhanced their nutritional value, upgrading sulfur amino acid requirements for infants and adults. Because functionality and nutritional value FIII-E could be used for hypoallergenic infant formulas, FII-E for fortified soluble formulas and nutraceutics and FI-E for a semi-solid baby food.     

Influence of low molecular weight ABS species on properties of PC/ABS systems

Differential scanning calorimetry (DSC), scanning electron microscopy (SEM) rheological, mechanical and impact tests were performed on alloys consisting of polycarbonate (PC) and diverse acrylonitrile‐butadiene‐styrene copolymers (ABS), from which different amounts of low molecular (M) weight (W) species had been previously extracted in a Soxhlet apparatus by methanol. The influence on properties of the alloy composition and of the low MW species amount was investigated. The glass transition temperature (Tg) was found to be a useful probe for monitoring the migration trends of low MW ABS species towards the PC domains for the different alloys. In a morphological analysis it was found that the higher the ABS extraction extent the less the penetration of the etching agent into the surfaces of smoothed specimens. The blend rheological behavior showed that the capability of improving the PC processability, characteristic of commercial ABS's, was strongly lowered by the ABS extracted ones. The alloy modulus was higher when the ABS extraction extent was larger. The yield stress of alloys showed higher values than that of the PC one, particularly at low ABS content. The alloy composition, for which the impact resilience was at its maximum value, strongly depended on the extraction extent. All the above findings seem to suggest an increased adhesion between PC and ABS domains with enhanced extraction amounts of low MW species from the ABS component.     

Macro and microstructural characterisation of high Si cast steels – Study of microsegregation patterns

In this study the as-cast macro and microstructures of medium C – high Si cast steels of three different levels of alloying are characterised. The application of a colour-etching reagent sensitive to Si segregation effectively revealed the solidification macrostructure, showing that the patterns of macrostructure and microsegregation are governed by the initial precipitation of δ-ferrite dendrites. A study of microsegregation carried out using advanced EDS techniques showed that, for the studied chemical compositions, Si, Mn, Cr, Ni, Mo and Al tend to concentrate at the last liquid to solidify. Accordingly, effective partition coefficients of values below unity were calculated for all alloying elements tested. It was verified that the minimum local Si contents measured on the steels investigated were greater than 1.7%, value above the minimum value (1.5%) necessary to obtain carbide-free bainite after austempering.