Development of catalysts for hydrogen generation from hydride compounds

Catalytic hydrolysis of NaBH₄ and NH₃BH₃ has been studied. It was shown that the nature of the support and the active component of the catalyst affect the H₂ generation rate. Despite similar sizes of rhodium particles formed on the surface of different supports (γ-Al₂O₃, TiO₂, carbon), their reactivity is different. Rh/TiO₂ with low rhodium concentration (1 wt.%) is the most active catalyst both in the hydrolysis of NaBH₄ and NH₃BH₃. The obtained results show that the rhodium chloride interaction with titania determines the reactivity of rhodium particles formed under action of NaBH₄ medium. TEM, DRS UV–vis and XPS were used to characterize the catalysts.     

To treat or not to treat: comparison of different criteria used to determine whether weight loss is to be recommended

Background  

Excess body fat is a major risk factor for disease primarily due to its endocrine activity. In recent years several criteria have been introduced to evaluate this factor. Nevertheless, treatment need is currently assessed only on the basis of an individual's Body Mass Index (BMI), calculated as body weight (in kg) divided by height in m². The aim of our study was to determine whether application of the BMI, compared to adiposity-based criteria, results in underestimation of the number of subjects needing lifestyle intervention.     

The flame retardant mechanism of polyolefins modified with chalk and silicone elastomer

This paper presents the current understanding of the flame retardant mechanism of Casico?. The study includes the flame retardant effect of each individual component: ethylene–acrylate copolymer, chalk and silicone elastomer, as well as the formation of an intumescent structure during heating. The flame retardant properties were investigated by cone calorimetry and oxygen index tests. To obtain insight into the flame retardant mechanism, heat treatment under different conditions has also been performed. The results indicate that the flame retardant mechanism of Casico is complex and is related to a number of reactions, e.g. ester pyrolysis of acrylate groups, formation of carbon dioxide by reaction between carboxylic acid and chalk, ionomer formation and formation of an intumescent structure stabilized by a protecting char. Special emphasis is given to the formation of the intumescent structure and its molecular structure as evaluated from ¹³C MAS‐NMR and ²⁹Si MAS‐NMR, ESCA and XRD analysis. After treatment at 500°C the intumescent structure consists mainly of silicon oxides and calcium carbonate and after treatment at 1000°C the intumescent structure consists of calcium silicate, calcium oxide and calcium hydroxide. Copyright © 2003 John Wiley & Sons, Ltd.     

Laser irradiation of oligosiloxane copolymer thin films functionalized with side chain bulky carbosilane moieties

Linear oligosiloxanes functionalized with bulky side chain tris(trimethylsilyl)hexyl (TTSH) substituents were transformed into cross-linked materials by UV 193 nm excimer pulsed laser ablation. The process occurred without any catalyst, by reactions of radicals formed in UV laser induced photolysis of side tris(trimethylsilyl)hexyl groups. Chemical changes were monitored by FTIR, LC/UV, GC/MS and solubility tests.     

On-Line LC-GC for the Analysis of the Minor Components in Edible Oils and Fats – The Direct Method Involving Silylation

The previous on-line LC-GC method for the direct analysis of the minor components in oils and fats (without cleavage of esters) was modified: The free alcohols/sterols were silylated instead of acylated, and the LC fraction transferred to GC is widened to range from the beginning of the LC chromatogram up to the sterol esters. Silylation eliminated the problem that acylation may esterify some free alcohols with free fatty acids from the oil if the oil or fat is of high acidity. Widening of the LC fraction to include squalene and the tocopherols added information to that previously obtained.     

Analysis of a homologous series of non-reducing oligosaccharides from Arnica montana L. Roots

The oligosaccharide component compositions of a series of non-reducing oligosaccharides extracted from the roots of Arnica montana L. has been determined by gel permeation chromatography (g.p.c.). The range of oligosaccharides present was found to extend beyond the octasaccharide previously reported. with 16% to 19% of the oligosaccharides having a degree of polymerisation of between 11 and 19 and almost 3% having a degree of polymerisation greater than 20. The chromatographic behaviour of this series of oligosaccharides is compared with that observed for series of D-gluco-oligosaccharides.     

The content and composition of sterols and sterol esters in low erucic acid rapeseed (Brassica napus)

The low temperature crystallization technique for the enrichment of “minor” components, such as sterols and sterol esters, from vegetable oils was applied to low erucic acid rapeseed oils. The recovery of free sterols and sterol esters was estimated by use of¹⁴C-cholesterol and¹⁴C-cholesterol oleate. 80% of the free sterols and 45% of the sterol esters were recovered in the liquid fraction, while in two studies total recoveries were 95% and 99%, respectively. This technique showed some selectivity toward the sterol bound fatty acids when compared to direct preparative thin layer chromatography (TLC) of the crude oil. Gas liquid chromatography (GLC) analysis of the free and esterified sterols as TMS-derivatives showed very little selectivity in the enrichment procedure. The fatty acid patterns of the sterol esters demonstrated, however, a preference in the liquid fraction for those sterol esters which have a high linoleic and linolenic acid content. The content of free sterols was 0.3–0.4% and that of sterol esters 0.7–1.2% of the rapeseed oils in both winter and summer types of low erucic acid rapeseed (Brassica napus) when the lipid classes were isolated by direct preparative TLC of the oils. The free sterols in the seven cultivars or breeding lines analyzed were composed of 44–55% sitosterol, 27–36% campesterol, 17–21% brassicasterol, and a trace of cholesterol. The esterified sterols were 47–57% sitosterol, 36–44% campesterol, 6–9% brassicasterol, and traces of cholesterol and Δ5-avenasterol. The fatty acid patterns of these esters were characterized by ca. 30% oleic acid and ca. 50% linoleic acid, whereas these acids constitute 60% and 20%, respectively, of the total fatty acids in the oil. Little or no variation in sterol and sterol ester patterns with locality within Sweden was observed for the one cultivar of summer rapeseed investigated by the low temperature crystallization technique.     

The removal of dichloromethane from atmospheric pressure air streams using plasma-assisted catalysis

Plasma-assisted catalysis was used for the destruction of 500 ppm of dichloromethane, CH₂Cl₂ (DCM), in gas streams of air using a non-thermal, atmospheric pressure plasma utilising a dielectric packed bed. The combination of plasma and catalyst gave improved destruction of DCM. Eight catalysts which including alumina, TiO₂ and various zeolites were investigated with the finding that alumina in a one-stage reactor configuration and TiO₂ and HZSM-5 in two-stage configurations gave the best DCM destructions. The sodium zeolites are capable of reducing by 50% the unwanted NO_x by-products, formed by plasma processing in air. The nature of the catalyst is important in terms of the destruction efficiency, end-product selectivity and NO_x reduction.     

Engineering of functional supramacromolecular complexes of proteins (enzymes) using reversed micelles as matrix microreactors

The size of the inner water cavity of reversed micelles formedin a triple system ‘water-surfactant-organic solvent’can be widely varied by changing the degree of surfactant hydration.This gives grounds to use reversed micelles as matrix microreactorsfor the design of supramolecular complexes of proteins. Usingultracentrifugation analysis, it has been demonstrated thatthe oligomeric composition of various enzymes (ketoglutaratedehydrogenase, alkaline phosphatase, lactic dehydrogenase, glyceraldehyde-3-phosphatedehydrogenase) solubilized in reversed micelles of Aerosol OT[sodium bis(2-ethylehexyl)sulfosuccinate] in octane changesupon variation of the degree of hydration. An oligomeric complexforms under conditions when the radius of the micelle innercavity is big enough to incorporate this complex as a whole.At lower degrees of hydration the micelles ‘uncouple’such complexes to their components. The catalytic propertiesof various oligomeric complexes have been studied. Possibilitiesof using reversed micelles for the separation of subunits ofoligomeric enzymes under non-denaturating conditions have beendemonstrated. In particular, the isolated subunits of alkalinephosphatase, lactic dehydrogenase and glyceralde-hyde-3-phosphatedehydrogenase have been found to be active in Aerosol OT reversedmicelles. The dependences of the catalytic activity of oligomericenzymes represent saw-like curves. The maxima of the catalyticactivity observed at these curves relate to the functioningof various oligomeric forms of an enzyme. The radii of the micelleinner cavity under conditions when these maxima are observedcorrelate with the linear dimensions of the enzyme oligomericforms. Correlation of the position of a maximum with the shapeof an oligomeric complex is discussed.