Trends in industrial markets for fats and oils and derivatives

During the past decade, research by industry and government has developed numerous new chemical markets for fats and oils derivatives. Lower prices for competitive raw materials have forced some of these new products into specialty markets. Economic factors, such as the continual growth of the chemical industry, population increases, and high consumer demand, have allowed for steady growth in the fat-derivative market. New fat-type plasticizers are currently consuming about 60 million pounds of fats annually. Synthetic lubricants will probably be consuming 20 million pounds of fatty diesters annually by 1965. Animal feeds consume approximately 600 million pounds of fats and fat derivatives annually and may eventually become the leading domestic nonfood market for fats. The protective coating market as an outlet for fats continues to decline, and the continuing shift to nonfat materials and changes in pain formulas indicate that, while the demand for protective coatings may increase, the use of fats in their manufacture may not share in the increase. Nonfat chemical raw materials provide intense price competition for fatty raw materials. Fat prices are influenced by the demand for use in food, soap, paints, and possibly animal feeds rather than by the demand for use as chemical raw materials. Presented before the American Oil Chemists' Society, New York, October, 17, 1960.     

The lead dioxide electrode

The recent literature dealing with the redox mechanism of the lead-acid cell positive electrode is reviewed. The basis electrochemistry of lead dioxide in its various polymorphic modifications and states of subdivision is considered in relation to the important aspects of electrode technology of which the major industrial application of the material is the conventional lead-acid cell. The proposed mechanism of the reduction (discharge) of lead dioxide in various acidic solutions are considered in relation to the present state of electrode kinetic theory. The reverse reaction by which lead dioxide is formed and the parasitic intrusion of the self discharge are dealt with as a precursor to the total cyclic process. It is concluded that in a number of respects the mechanisms proposed do not adequately represent the totality of the experimental observations. Such shortcomings are emphasized and extensions to present research are proposed.     

Potentiostatic step experiments on pasted Pb-Sb and Pb-Sn-Ca electrodes

A range of cyclic electrochemical experiments have been carried out on electrodes of porous PbO₂ supported on a number of Pb-Sb and Pb-Sn-Ca alloys using micro-computer controlled potentiostatic stepping techniques. The results show that, in certain cases, the differences in electrochemical behaviour of the PbO₂ can be interpreted as being due to the effect of the support alloy.     

The reaction of activated vinyl compounds with cotton cellulose via internal catalysis

The reactions of a variety of activated vinyl compounds with cotton cellulose fabric containing quaternary ammonium hydroxide substituents were explored. Each reaction, catalyzed by the basic groups in the cellulose, was followed to or near the point of leveling off. The results are analyzed and discussed in terms of accessibility of the cellulosic compositions and in terms of the efficiency of the quaternary ammonium substituents as catalysts for the addition reactions. Estimates of relative forward rate constants (k_f) and equilibrium constants (K) for the reactions were made. The values of k_f for reactions of the vinyl compounds with the quaternary ammonium celluloses show a relative order which is similar to that for the reactions of the vinyl compounds with simple alcohols. Evidence is presented to indicate that, in some cases, the addition of vinyl compounds is accompanied by anionic-catalyzed graft polymerization.     

Polymerization of 2-phenyl-aziridine

Summary The ring-opening polymerization of 2-phenyl aziridine was studied with several catalyst systems: boron trifluoride etherate, chlorhydric acid, perchloric acid, dimethyl sulfate and methyl triflate. The corresponding polyamine was obtained as a pale yellow solid with a number average molecular weight around 2,000–3,000.A kinetic study is discussed in the case of perchloric acid and methyl triflate.     

Detoxification of cereal plant allelochemicals by aphids: Activity and molecular weights of glutathioneS-transferase in three species of cereal aphids

The activity and molecular weights of glutathioneS-transferase were studied in three species of cereal aphid:Metopolophium dirhodum, Sitobion avenae, andRhopalosiphum padi. The highest level of glutathioneS-transferase activity was recorded in extracts fromM. dirhodum and the lowest fromS. avenae, and extracts of larvae were more active than those from adults. The activity of this enzyme was higher in extracts ofS. avenae andR. padi previously fed on a moderately resistant wheat variety than on a susceptible variety. Gel filtration followed by SDS-PAGE revealed three protein bands in the active fractions. The first had a molecular weight of 28,500 and the second of 27,500 and were present in all three species of aphid. The third protein differed in the three species, having a molecular weight of 26,000 inS. avenae, 25,500 inM. dirhodum, and 24,000 inR. padi.     

Nuclear spin—lattice relaxation and molecular motions in isotactic poly(but-1-ene) and (but-1-ene)—propylene copolymers in solution

¹³C spin—lattice relaxation times have been measured at 25.15 MHz on poly(but-1-ene) and (but-1-ene)—propylene copolymers, as a function of molecular weight and concentration in 1,2,4-trichlorobenzene, and over the 50°–150°C temperature range. Maximum nuclear Overhauser enhancement was observed for all carbons. Independence of T₁ from molecular weight and bulk sample viscosity for solutions less concentrated than 50% w/v, indicates that relaxation is dominated by local conformational rearrangements rather than by overall tumbling of the macromolecule. Relaxation studies on copolymers show that this segmental motion affects only short sequences of the chain. No influence of stereochemical configurations is observed. Relaxation data for backbone carbons was interpreted in terms of a single τ isotropic motional model. Internal rotations of side CH₂ and CH₃ groups were analysed using the two and three correlation times Woessner models, and show little dependence on an eventual anisotropy of chain motion. Similar temperature dependence (18–21 kJ/mol) is observed for chain and side carbons, and even if internal reorientation of side CH₃ groups is much more rapid, it appears interlinked with segmental motion.     

Metabolism of an n-paraffin,heptadecane, in rats

¹⁴C-heptadecane incorporated in rat diet was largely absorbed, and a balance study showed extensive¹⁴CO₂ excretion (65%). There was no elimination of the hydrocarbon in the urine, and only minute quantities of labeled metabolites. Radioactivity in the feces was entirely in heptadecane. About 7% of the heptadecane absorbed was stored in the carcass, whereas the rest was ω-oxidized to heptadecanoic acid. This fatty acid was incorporated into neutral lipids and phospholipids, underwent the normal fatty acid degradation pathway, and contributed to the synthesis of lipids, including fatty acids, squalene and cholesterol, and nonlipids (7–10%). Heptadecanoic acid was desaturated to heptadecenoic acid. The even distribution of radioactivity in the fatty acids of the various phospholipid classes indicated that heptadecane did not interfere with the biochemical mechanisms of these functional lipids.     

Substrate-mediated interactions and intermolecular forces between molecules adsorbed on surfaces

Adsorbate interactions and reactions on metal surfaces have been investigated using scanning tunneling microscopy. The manners in which adsorbates perturb the surface electronic structure in their vicinity are discussed. The effects these perturbations have on other molecules are shown to be important in overlayer growth. Interactions of molecules with surface steps are addressed, and each molecule's electron affinity is shown to dictate its adsorption sites at step edges. Standing waves emanating from steps are demonstrated to effect transient molecular adsorption up to 40 A away from the step edge. Halobenzene derivatives are used to demonstrate how the surface is important in aligning reactive intermediates.