Neutral sterols of sawflies (symphyta): Their relationship to other hymenoptera

To investigate sterol utilization in sawflies, the neutral sterols of four species of sawflies were determined by gas-liquid chromatography and mass spectrometry, and compared to the respective dietary plant material. Cholesterol was the predominant (55–76%) sterol in all species and stages of sawflies examined. Host plants, however, contained primarily sitosterol (50–88%), along with other 24-alkylsterols and only 0.5–5.9% cholesterol, indicating that the sawflies examined are capable of dealkylating the C₂₈ and C₂₉ phytosterols in their diet to cholesterol. Comparative sterol metabolism in Hymenoptera is discussed.     

Early soot formation stages in low-pressure diffusional counterflow hydrocarbon flames

Early soot formation stages were investigated in low-pressure counterflow hydrocarbon flames. A mechanism is proposed for the formation of aggregates and discrete spherical soot particles. It is proposed that the formation of the physical surface is preceded by the emergence of a skeleton structure consisting of carbon molecule chains as a result of their polarizing and dipole interaction with the charged soot nuclei.Kiev. Translated from Fizika Goreniya i Vzryva, Vol. 29, No. 3, pp. 97–100, May–June, 1993.     

Solvation of ions—XX. The ferrocene—ferricinium couple and its role in the estimation of free energies of transfer of single ions

The ferrocene-ferricinium electrode (Pt/Foc, Fic⁺) was investigated in water, acetonitrile, ethanol, DMSO and DMF using single scan cyclic voltammetry and phase sensitive ac polarography. The oxidation-reduction is pseudo-reversible in all five solvents with an electrochemical rate constant of approximately 10⁻² cm/s. In all solvents a slow irreversible chemical step involving the ferricinium cation follows electron transfer, so that slow cyclic voltammetry or polarography rather than potentiometry is preferred if ferrocene is to be used as a reference electrode in non-aqueous solvents.

The Strehlow assumption, ΔG_tr(Foc) = ΔG_tr(Fic⁺ gives very different free energies of transfer of single ions from non-aqueous solvents to water when compared with the TATB assumption that ΔG_tr(Ph₄As⁺) = ΔG_tr(Ph₄B⁻). This discrepancy is likely to be because ferricinium is only a moderately large cation, so that ΔG_tr(Fic⁺) is less positive than ΔG_tr(Foc) for transfer to water. The discrepancy is not because of abnormal electrochemical behavior of the Pt/Foc, Fic⁺ electrode in water or other solvents. Values of E° vs nhe, H₂O in a variety of solvents based on the TATB assumption are presented.     

On the thermal stability of xanthan gum

The thermal stability of xanthan gum in dilute aqueous solutions at 90°C is considered. The relative viscosity as a function of ageing time is discussed, and it has been found to depend on the polymer concentration and conformation as well as on the salt content. The effectiveness of a quencher demonstrates the existence of a free-radical process in the degradation. During ageing, the molecular weight first decreases by rapid random hydrolysis of the main chain and loss of the pyruvate and acetate substituents. Later, oligomers are formed corresponding to a breakdown of both the side chain and the main chain. The identification of cellodextrins in the oligomer pool demonstrates the second effect.     

Influence of catalyst type on the curing process and network structure of alkyd coatings

Recent studies have shown that cobalt catalysts, used for curing of alkyd coatings, are potentially carcinogenic, and hence replacement by new environmental friendly catalysts is needed. The influence of different metal based catalysts on the oxidation process has been studied extensively in model systems, consisting of unsaturated oils. However, these results may not be representative for real coatings, since in these systems the oxygen diffusion is much lower than in model systems and therefore may have a large effect on the curing. In this paper, we will show how the curing of an alkyd coating depends on the type of catalyst (cobalt or manganese based). The curing process is studied using a high spatial resolution nuclear magnetic resonance (NMR) setup. The final network structure and cross-link density are found to be correlated with the catalyst used, i.e. a cobalt based catalyst and two manganese based catalysts. The difference in final network structure is investigated by NMR T₂ relaxation analysis and the glass transition temperature T_g measured using a differential scanning calorimeter (DSC). In case of the cobalt based catalyst a cross-linking front was observed and a high cross-link density was found, compared to the manganese based catalysts, in which case no sharp cross-linking front was observed. To interpret the observed NMR profiles in more detail, simulations based on a reaction-diffusion model were performed. From the results of these simulations estimates were obtained for the reaction constants and the diffusion of oxygen for the different catalysts.     

Iron species incorporated over different silica supports for the heterogeneous photo-Fenton oxidation of phenol

Iron-containing catalysts have been prepared following different synthesis routes and silica supports (amorphous, zeolitic and mesostructured materials). Activity and stability of these materials were assessed on the photo-Fenton degradation of phenolic aqueous solutions using near UV irradiation (higher than 313 nm) at room temperature and initial neutral pH. Their catalytic performance was monitored in terms of phenol and total organic carbon (TOC) conversions. Aromatic compounds and carboxylic acids as by-products coming from incomplete mineralization of phenol as well as the efficiency of each catalytic system in the use of the oxidant were also studied. Stability of the materials throughout the photo-Fenton reaction was evaluated in terms of metal leachibility. Activity and stability depend on the environment of iron species and features of silica support. The evolution of pH with the reaction time and their relationship with TOC degradation and leaching degree has been discussed. A nanocomposite material of crystalline iron oxides supported over mesostructured SBA-15 material is shown the most successful catalyst for degradation of phenolic aqueous solutions by photo-Fenton processes, achieving an outstanding overall catalytic performance accompanied with a noteworthy stability.     

Mechanosynthesis of complex oxides and preparation of mixed conducting nanocomposites for catalytic membrane reactors

Nanopowders of LaGaO₃- and LaMnO₃-based complex perovskites (P) and ceria-based fluorites (F) were prepared by mechanosynthesis. Compatible nanocomposites F + P and P + P with mixed ion and electron conducting (MIEC) properties were prepared and sintered at moderate temperatures up to dense ceramics. The obtained materials were studied by means of XRD, SEM, TEM, electrical conductivity measurements, temperature programmed (TP) reduction/oxidation and preliminary estimations of permeability were obtained. A new strategy based on the advantages of the mechanochemical ceramic approach is proposed to design multilayer ceramic membranes for CMR. Casting technology and one-step sintering were used for the production of thin film membranes with MIEC properties on porous substrates. The coarse fraction of as-milled powders from agglomerates with density 70% was used for the porous substrate, and fine fractions of aggregates with sizes <1 μm were used in preparation of composites for thin dense films. Ceria-based composites prepared by the Pechini route and/or mechanochemical method are proposed as materials for protecting thin films.     

Terpolymers. II. Mechanical properties and transition temperatures of terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Vinyl stearate was studied as a major internal plasticizer in terpolymers containing vinyl acetate and vinyl chloride. The terpolymers were prepared by systematically replacing vinyl acetate by close increments of vinyl stearate starting with combinations of vinyl acetate and vinyl chloride, in increments, over all compositions. For comparison of properties, a complete range of copolymers of vinyl stearate and vinyl chloride, as well as mixtures of poly(vinyl chloride) and di-2-ethylhexyl phthalate (DOP) were also made. The external plasticizer was more efficient in reducing the glass temperature than was vinyl stearate. The decline in T_g with weight fraction of plasticizer was linear for the copolymers and terpolymers but concave downward with the liquid diluent. The linear decline was shown to involve mere additivity of the free volume contributed by each side-chain methylene (or methyl) group in both vinyl esters to reducing T_g. The mechanism of the diluent system was more complex. However, the magnitude of the reduction of tensile modulus at a given weight fraction of DOP could be equaled or exceeded by the same amount of vinyl stearate, by increasing the vinyl acetate content of the base copolymer to 40 mole-% or more. Unfortunately, the ultimate strengths and elongations of internally plasticized systems were reduced more than those of the mixtures at comparable compositions. Vinyl stearate was found to markedly retard photolytic degradation compared to both vinyl acetate and the external plasticizer in unstabilized samples having nearly the same thermal treatment. The effect was greater than could be ascribed to dilution by the long alkyl group. The production of a stearoyl radical more stable than the radicals initiating dehydrochlorination is suggested as a possible mechanism.