Characteristics of the thiobarbituric acid reactivity of oxidized fats and oils

The thiobarbituric acid (TBA) reactivity of oxidized methyl linoleate, soybean oil, sesame oil, lard, chicken oil and sardine oil was characterized by using four different methods with 0.01% butylated hydroxytoluene (BHT). Optimal pH for the reactivity of most of the oxidized samples was 3–4, and that of some samples was above 5. Introduction of 2 mMt-butyl hydroperoxide (t-Bu00H) or 0.2 mM ferric ion in the reaction markedly enhanced the reactivity. Introduction of 0.2 mM ethylenediamine tetraacetic acid suppressed the reactivity. The characteristics of the TBA-reactivity of the samples were similar to those of alkadienals or alkenals. The most preferable method for the estimation of the TBA-reactive substances of the oxidized fats and oils was that using solvents at pH 3.5 with introduction of BHT, andt-Bu00H or ferric ion.     

Prevention of catalyst deactivation caused by coke formation in the methanation of carbon oxides

Prevention of catalyst deactivation in carbon monoxide methanation on a highly active Ni-based composite catalyst has been investigated. The composite catalyst, Ni-La₂O₃-Ru supported on silica, has greater activity than that of a Ni catalyst, but the decrease of the catalyst activity with reaction time is greater than that of the Ni catalyst, especially when the CO conversion is low. The reason for this behaviour is found in the relation between the amount of surface-carbon species and the degree of deactivation. When the CO methanation reaction is operated at above the temperature of complete CO conversion, catalyst deactivation is avoided. At such high temperatures the amount of surface-carbon species is small. The catalyst deactivation is considerably suppressed with a low concentration, e.g. 1–3 kPa, of additional CO₂ or CO₂ + H₂O. The cause of this suppression is considered to be the renewal of the covered surface with the carbon-species by the competitive adsorption of these additives.     

X-ray studies of multiple melting behavior of poly(butylene-2,6-naphthalate)

Multiple melting behavior of poly(butylene-2,6-naphthalate) (PBN) was studied with X-ray analysis and differential scanning calorimetry (DSC). Double endothermic peaks L and H attributed to the α-form crystal modification, a small peak attributed to the β-form crystal modification, and a new shoulder peak S at a lower temperature of peak H appeared in the DSC melting curves. Wide-angle X-ray diffraction patterns of the samples isothermally crystallized at 200 and 220 °C were obtained at a heating rate of 1 K min⁻¹, successively. In this heating process, change of crystal structure and increase of quantity of the β-form crystallites could not be observed up to the final melting. With increasing temperature, the diffraction intensity decreased gradually and then increased distinctly before a steep decrease due to the final melting. The X-ray analysis clearly proved the melt-recrystallization during heating. The β-form crystal modification was formed during slow heating process in the high temperature region.     

Asymmetric organocatalysis of structurally well-defined chiral quaternary ammonium fluorides

Unique organocatalysis of both naturally occurring cinchona alkaloid-derived and purely synthetic chiral quaternary ammonium fluorides in synthetically useful stereoselective bond-forming reactions is overviewed. The development of this chemistry was initiated by the in situ generation of generally hygroscopic ammonium fluorides from the corresponding easy-to-handle ammonium salts in the presence of excess metal fluorides and their direct use for subsequent enantioselective reactions. On the other hand, chiral ammonium fluorides have been prepared by using ion-exchange resins and successfully applied as catalyst to various asymmetric bond formation reactions under homogeneous conditions. In addition, utilization of chiral quaternary ammonium bifluorides as organocatalysts in asymmetric synthesis is described, featuring their characteristic reactivity and selectivity.     

Production of FAME from acid oil model using immobilized <Emphasis Type="Italic">Candida antarctica</Emphasis> lipase

Acid oil is a by-product in the neutralization step of vegetable oil refining and is an alternative source of biodiesel fuel. A model substrate of acid oil, which is composed of TAG and FFA, was used in experiments on the conversion to FAME by immobilized Candida antarctica lipase. FFA in the mixture of TAG/FFA were efficiently esterified with methanol (MeOH), but the water generated by the esterification significantly inhibited methanolysis of TAG. We thus attempted to convert a mixture of TAG/FFA to FAME by a two-step process comprising methyl esterification of FFA and methanolysis of TAG by immobilized C. antarctica lipase. The first reaction was conducted at 30°C in a mixture of TAG/FFA (1∶1, wt/wt) and 10 wt% MeOH using 0.5 wt% immobilized lipase, resulting in efficient esterification of FFA. The reaction mixture after 24 h was composed of 49.1 wt% TAG, 1.3 wt% FFA, 49.1 wt% FAME, and negligible amounts of DAG and MAG (<0.5 wt%). The reaction mixture was then dehydrated and used as a substrate for the second reaction, which was conducted at 30°C in a solution of the dehydrated mixture and 5.5 wt% MeOH using 6 wt% immobilized lipase. The activity of the lipase increased gradually when the reaction was repeated by transferring the enzyme to a fresh substrate mixture. The activity reached a maximum after 6 cycles, and the content of FAME achieved was >98.5 wt% after a 24-h reaction. The immobilized lipase was very stable in the first-and second-step reactions and could be used for >100 d without significant loss of activity.     

Phosphonitrilic chloride: 21. Synthesis of chelating polymers with cyclophosphazene thiocarbamate and the properties of chelating polymers

Chelating polymers containing copper, nickel and cobalt have been formed from cyclophosphazene thiocarbamate trimer and copper, nickel or cobalt ions. These polymers obtained from the reaction are amorphous and the values of electron conductivity are $\text{2·7 × 10}{}^{11}\text{Ω-}\text{cm}$, $\text{3·6 × 10}{}^{13}\text{Ω-}\text{cm}$ and $\text{1·5 × 10}{}^{13}\text{Ω-}\text{cm}$ for the Cu, Ni and Co polymers respectively. The Cu polymer is the most thermally stable on heating to 500°C in air.     

An application of Monte Carlo method to simulate disorders in polymer crystals

The Monte Carlo method is applied to polymer crystals of idealized linear chain molecules of 30 carbon atoms, and the unharmonic, large-amplitude, oscillations and the subsequent conformational disorders of the chains are investigated. A crystalline field that confines the chain is treated by the molecular field approximation, and assumed to be cylindrical in this work. A production type simulation is adopted taking into account rigorous statistical weights for each sample conformation. Both the rotational isomeric model and the continuous rotation model of chain conformation are considered. By averaging over 10⁴–8 × 10⁴ chains, mean-square end-to-end distance, fractions of gauche and trans states and a detailed distribution of internal rotation angle are obtained. The effects of temperature and pressure on the conformation of the chain in the crystals are also simulated.     

Alternating copolymer of bithiophene and dialkylbithiazole and its tendency to align on the surfaces

New five-membered ring π-conjugated polymers composed of 2,2′-bithiophene and 4,4′-dialkyl-2,2′-bithiazole units were prepared. The polymers were soluble in 1,2-dichlorobenzene and showed a UV-vis peak at about 490 nm above 120 °C. Cooling the solution led to the appearance of new UV-vis peaks at 550 and 600 nm, which were considered to originate from self-assembled polymer molecules. Powder XRD (X-ray diffraction) data supported a well-stacked solid structure of the polymers and a highly ordered structure of a polymer film formed on a quartz glass substrate. These data revealed a strong tendency of the new polymers to self-assemble and to form an aligned structure on the surface of the substrates.     

Synthesis of single-phase Ti3SiC2 powder

In this study, free 2Ti/2Si/3TiC powder mixture was heated at high temperatures in vacuum, in order to reveal the possibility for the synthesis of high Ti₃SiC₂ content powder. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used for the evaluation of phase identities and the morphology of the powder after different treatments. Results showed that almost single phase Ti₃SiC₂ powder (99.3 wt.%) can be synthesized by heat treatment with free 2Ti/2Si/3TiC powders in vacuum at 1210°C for about 3 h. The nucleation and growth of Ti₃SiC₂ within TiC particles was observed. The typical appearance of the formed Ti₃SiC₂ is equiaxed with particle size of 2–4 μm. Effects of temperature and heating time on the morphology and the particle sizes of the synthesized Ti₃SiC₂ powders are not obvious.     

Structural characterization of maleic anhydride grafted polyethylene by C NMR spectroscopy

Maleic anhydride grafted polyethylene, [2,3-¹³C₂] MA-g-PE, which was synthesized with ¹³C labeled maleic anhydride [2,3-¹³C₂] MA in solution, was characterized by ¹³C NMR spectroscopy in order to make clear the structure of graft groups. The results reveal that [2,3-¹³C₂] MA-g-PE has succinic anhydride oligomeric grafts with a terminal unsaturated MA ring in addition to well-known saturated succinic anhydride oligomeric grafts and that the former grafts are longer but fewer than the latter.