Effect of calcination temperature on the characteristics of SO<Emphasis Type="Italic">sk</Emphasis>4/2-/TiO<Subscript>2</Subscript> catalysts for the reduction of NO by NH<Subscript>3</Subscript>

The catalytic activity of sulfated titania (ST) calcined at a variety of temperatures has been investigated for selective catalytic reduction (SCR) of NO by NH₃. The NO removal activity of ST catalyst mainly depends on its sulfur content, indicating critical role of sulfur species on the surface of TiO₂. The role of sulfur is mainly the formation of acid sites on the catalyst surface. The presence of both BrØnsted and Lewis acid sites on the surface of sulfated titania has been identified by IR study with the adsorption of NH₃ and pyridine on ST. The reduction of the intensity of IR bands representing BrØsted acid sites is more pronounced than that revealing Lewis acid sites as the calcination temperature increases. It has been further clarified by IR study of ST500 catalyst evacuated at a variety of temperatures. The NO removal activity also decreases with the increase of the catalyst calcination temperature. It simply reveals that BrØnsted acid sites induced by sulfate on the catalyst surface are primarily responsible for the enhancement of catalytic activity of ST catalyst containing sulfur for NO reduction by NH₃.     

Thermodynamics of ionic-association in aqueous solutions of Ca and Mg organic salts using ion-selective electrode technique—II. benzoate, o-toloate, o-chlorobenzoate and salycylate

The stoichiometric association constants, K, the thermodynamic association constant, K_A, and the other thermodynamic parameters such as ΔS°, ΔH° and ΔG° for the association between each of the Ca and Mg ions with benzoate, o-toloate, o-chlorobenzoate and salycylate have been determined at 25°C, 35°C and 45°C in aqueous media. Ion-selective electrode technique has been used in the measurements of Ca and Mg ion activitiesThe trend of association behavior of both Ca and Mg aromatic salts could not be explained on the basis of pK_a of the mother organic acids but could be explained based on the trend of Hammet function σ of these salts themselves relative to the corresponding benzoate salt.     

Anodic behaviour of zinc in methanol solutions of lithium perchlorate

Anodic dissolution of poly- and single-crystals of zinc was performed in methanol solution of lithium perchlorate by means of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The mechanism of anodic dissolution of zinc in organic solvents occurs in two oxidation steps. It is the first step that surface anodic product is created. Stability of the surface product is much better in anhydrous organic environments than in aqueous media; because the product is stable, a barrier layer composed of is formed at low anodic overvoltage. The formation of the layer is much stronger on the low index than on the high-index plane (0 0 0 1), where the adsorption of anodic product is more difficult.     

Observations on the estimation of scavenging activity of phenolic compounds using rapid 1,1-diphenyl-2-picrylhydrazyl (DPPH<Superscript>•</Superscript>) tests

Rapid 1,1-diphenyl-2-picrylhydrazyl (DPPH^•) tests are often applied to classify the scavenging activity of phenolic compounds (AH). Published analytical protocols differ in more than one experimental condition, and results for the relative order or magnitude of activity are often contradictory. In this work, parameters such as duration of test, [AH]/[DPPH^•] molar ratio, and solvent effects were examined and discussed. The test duration and the value of the [AH]/[DPPH^•] ratio did not influence the order of activity among tested antioxidants. Ethanol, commonly used as solvent in such tests, was compared with acetonitrile and tert-butyl alcohol. Solvent properties such as the ability to form hydrogen bonds with the AH seem to influence the level of the relative activity (%RSA). Higher %RSA values were observed in ethanol. The activity of the most polar compounds was affected the most, and in some cases (caffeic, dihydrocaffeic, and rosmarinic acids) the order of activity was changed owing to different kinetics. Standardization of the analytical protocol should include a 20-min reaction period and a molar ratio that permits attainment of a 60–80% RSA value for the most potent antioxidant. Solvent choice is critical for classifying activity. Safe classification can be based only on results from kinetic studies.     

Volatile compounds of original African black and white shea butter from Tchad and Cameroon

Shea butter is used as an edible vegetable fat in many African countries. It can be utilized as a substitute or complete replacement for cocoa butter in various applications and plays an important role in traditional African medicinal practice. Although detection of volatile compounds by solid‐phase micro‐extraction gas‐chromatography mass‐spectroscopy (SPME‐GC‐MS) is a very reliable and reproducible technique, which can be used as an important part of authenticity checking, production monitoring and contamination detection, no published data about volatile compounds of shea butter are available so far. In this investigation, the characteristic volatiles in the headspace of original African shea butter samples were identified by using SPME‐capillary‐GC coupled to a mass selective detector. Almost 100 different volatile components were identified, e.g. fatty acids, saturated and unsaturated aldehydes and ketones, terpenes, and typical Maillard reaction products such as methylfuranes and pyrazines. Furthermore, the samples have been olfactorily evaluated by a panel of professional flavorists and trained analytical chemists. It can be stated that variations in processing conditions of shea butter result in considerable differences in the composition of headspace volatiles, detected by SPME‐GC‐MS and human olfaction.     

Hyperbranched Polymers Containing Cyclopentadienyliron Complexes

A number of hyperbranched polymers containing cyclopentadienyliron moieties were prepared using the A₂+B₃ method. The A₂ compounds used were common diols, dithiols or dichloroarenecomplexes. B₃ compounds included either prepared star-shaped molecules or a purchased triol. The effect of the reaction conditions on the properties of the products was probed. Analysis of the prepared polymers was conducted using ¹H and ¹³C NMR, viscometry, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Viscometry values were generally found to be low, in the range of 0.175–0.300 dl/g. TGA showed losses starting at approximately 230°C and ending at 280°C, corresponding to the decomposition of the cyclopentadienyliron moiety. Degradation of the polyether backbone was found to occur starting at 390–567°C. Glass transition temperatures were found to be between 60 and 134°C, whereas melting temperatures ranged from 155 to 190°C.     

Thermal and flow properties of oils from salmon heads

Thermal and flow properties of unrefined oils from the heads of red or pink salmon were evaluated. Major thermal degradation of the salmon oils occurred between 200 and 450°C. Red and pink salmon oils were completely decomposed at 533 and 668°C, respectively. The phase transition of salmon oils occurred over a wide range of temperatures. The melting points of −69.6 to −0.36°C and −64.7 to 20.8°C were observed for red and pink salmon oils, respectively. The enthalpy was 40 j/g for red salmon oil and 39 j/g for pink salmon oil. Specific heat capacity ranges of 0.8 to 1.6 and 1.3 to 2.3 j/g/°C were observed for red and pink salmon oils, respectively. Both salmon oils exhibited Newtonian flow behavior. Red salmon oil required higher magnitudes of energy (kj·mol⁻¹) to flow than pink salmon oil. The viscosity of salmon oils was temperature-dependent and could be predicted by the Arrhenius equation.     

The effect of supercooling on crystallization of cocoa butter-vegetable oil blends

The solid fat content (SFC), Avrami index (n), crystallization rate (z), fractal dimension (D), and the pre-exponential term [log(γ)] were determined in blends of cocoa butter (CB) with canola oil or soybean oil crystallized at temperatures (T _Cr) between 9.5 and 13.5°C. The relationship of these parameters with the elasticity (G′) and yield stress (σ^*) values of the crystallized blends was investigated, considering the equilibrium melting temperature (T _M ^o) and the supercooling (i.e., T _Cr ^o−T _M ^o) present in the blends. In general, supercooling was higher in the CB/soybean oil blend [T _M ^o=65.8°C (±3.0°C)] than in the CB/canola oil blend [T _M ^o=33.7°C (±4.9°C)]. Therefore, under similar T _Cr values, higher SFC and z values (P<0.05) were obtained with the CB/soybean oil blend. However, independent of T _Cr TAG followed a spherulitic crystal growth mechanism in both blends. Supercooling calculated with melting temperatures from DSC thermograms explained the SFC and z behavior just within each blend. However, supercooling calculated with T _M ^o explained both the SFC and z behavior within each blend and between the blends. Thus, independent of the blend used, SFC described the behavior of G′_eq and σ^* and pointed out the presence of two supercooling regions. In the lower supercooling region, G′_eq and σ^* decreased as SFC increased between 20 and 23%. In this region, the crystal network structures were formed by a mixture of small β′ crystals and large β crystals. In contrast, in the higher supercooling region (24 to 27% SFC), G′_eq and σ^* had a direct relationship with SFC, and the crystal network structure was formed mainly by small β′ crystals. However, we could not find a particular relationship that described the overall behavior of G′_eq and σ^* as a function of D and independent of the system investigated.     

A biomarker of n−3 compliance in patients taking fish oil for rheumatoid arthritis

Dietary fish oil supplements have been shown to have benefits in rheumatoid arthritis (RA), other inflammatory diseases, and in cardiovascular disease. As with any medical advice, variability will exist with regard to adherence and consequent biochemical or pharmacophysiologic effects. The aim was to explore the utility of plasma phospholipid EPA as a measure of n−3 PUFA intake and response to standardized therapeutic advice given in an outpatient or office practice setting, to increase dietary n−3 PUFA, including a fish oil supplement. Patients with early RA were given verbal and written advice to alter their dietary n−3 PUFA intake, including ingestion of 20 mL of bottled fish oil on juice daily. The advice included instructions to increase n−3 PUFA and to avoid foods rich in n−6 PUFA. Every 3 mon, blood samples were obtained for analysis of plasma phospholipid FA. Plasma phospholipid EPA was used as the primary index of n−3 PUFA intake. A diverse response was seen, with about one-third of patients achieving a substantial elevation of plasma phospholipid EPA over the 12-mon study period. A third had little change, with the remainder achieving intermediate levels. Data obtained longitudinally from individual patients indicated that substantial elevations of EPA (>5% total plasma phospholipid FA) could be maintained for more than 3 yr. Plasma phospholipid EPA is a convenient measure of adherence to advice to take a dietary n−3 PUFA-rich fish oil supplement. This measure may prove a useful adjunct to intention to treat analyses in determining the effect of dietary fish oil supplements on long-term outcomes in arthritis and other chronic inflammatory diseases. It may also provide a guide to the effectiveness of therapeutic and preventive messages designed to increase n−3 PUFA intake.     

Transformations of sulphur compounds in high-sulphur coals during reduction in the potassium/liquid ammonia system

The two types of high-sulphur coals Mequinenza and Illinois No. 6, in the initial form and subjected to potassium/liquid ammonia reduction, were analysed by atmospheric pressure-temperature programmed reduction (AP-TPR) method. It has been shown that preliminary demineralisation was beneficial for AP-TPR measurements because of the removal of calcium compounds. The reduction of sulphides and disulphides in the potassium/liquid ammonia system was found to lead to formation of aromatic and aliphatic thiols. The presence of the latter is better manifested in the AP-TPR kinetograms when the measurements are performed in the presence of a special reducing mixture. It has been shown that the coal reduction in the potassium/liquid ammonia system apart from transformations of non-thiophene sulphur groups also leads to breaking up of the C-S bonds in some thiophene systems.