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Aim To investigate the effect of diet upon liver function tests and serum lipids within the restricted environment of a Phase I unit. Methods An open randomized three-way crossover study was designed with subjects consuming three types of diet. The diets comprised, a balanced normal calorie diet, a high-carbohydrate high-calorie diet and a high-fat high-calorie diet. Each diet was consumed in a randomized sequence over 8 days with a recovery period of 14 days between periods. The blood concentrations of various laboratory parameters were measured at intervals throughout each dietary period and during the recovery periods. Results Blood transaminase activity and triglyceride concentrations increased significantly whilst subjects consumed a high-carbohydrate high-calorie diet but not when fed either a high-fat high-calorie diet or a balanced normal calorie diet. Conclusions The rises in transaminases and triglycerides were caused by the carbohydrate content of the diet rather than its calorific value. Sucrose rather than starch was the carbohydrate which caused the rise in transaminases and triglycerides. The importance of controlling diet in Phase I studies is stressed.

The phospholipid and sterol contents of plasma membranes isolated from stele and cortex of maize roots were compared. The major sterol present in both tissues was stigmasterol which was found in significantly higher quantities in the cortex (27.4 μg mg -1 membrane protein) compared to the stele (17.4 μg mg -1 ). Other sterols detected included sitosterol, campesterol and small quantities of cholesterol. The major phospholipids found were phosphatidylethanolamine (PE) and phosphatidylcholine (PC), with PC more abundant in the stele

Nitric oxide (NO) is a potent vasodilator that regulates pulmonary vascular tone. During ascent to high altitude, pulmonary vascular tone increases leading to pulmonary hypertension. To explore the mechanisms underpinning this effect, we investigated the relationship between exhaled NO ( P E NO ; nmHg) and pulmonary artery systolic pressure (PASP; mmHg) in 11 healthy adults during hypoxic challenge at sea level [with oxygen saturations ( S P O 2 ) of 80% and 90%] and at intervals during graded ascent to 5050 m. During normobaric hypoxia, PASP progressively increased from 22.7 mmHg to 33.5 mmHg (p = 0.006), whilst P E NO remained unchanged. In contrast, during ascent to high altitude, PASP increased progressively from 22.7 mmHg to 39.1 mmHg (p P E NO decreased from 18.8 nmHg to 9.0 nmHg (p P E NO had no significant effect on PASP at altitude (p = 0.309). These findings indicate that although exhaled NO decreases with altitude, it does not appear to be a major contributor to hypoxic pulmonary vasoconstriction.

A 30-year-old man was admitted unconscious to a peripheral hospital after consuming 120 mg of methadone to celebrate his release from prison. On arrival his creatinine was 1.93 mg/dl and his creatine kinase 68645 (IU/l). After reversal of his opiate intoxication, he began complaining of burning pain and weakness in both legs. Over the next 36 h his creatinine increased to 11.4 mg/dl with worsening metabolic acidosis, and he became anuric. He was transferred to our unit for dialysis. Due to persistent bilateral leg pain and a right-sided foot-drop an MRI (Figure ​(Figure1)1) was performed, which demonstrated bilateral gluteal oedema (panel C, arrows) consistent with rhabdomyolysis, causing compression of the right sciatic nerve at the sciatic notch (panel D, arrow). He required seven dialysis sessions before his renal function began to recover, and when reviewed 1 month post-discharge his creatinine was 1.5 mg/dl and he was receiving physiotherapy for a persistent foot drop. Fig. 1 Coronal (A and C) and axial (B and D) short tau-inversion recovery MRI sequences from a normal individual on the left (A and B) and showing high signal intensity in the glutei bilaterally in the patient on the right (C and D). Rhabdomyolysis describes the breakdown of striated muscle fibres, which results in the release of intracellular contents [1]. Of the many compounds liberated, myoglobin in particular is implicated in the development of renal failure, through precipitation and obstruction of tubules and free radical generation [2]. MRI has become the imaging modality of choice to define the extent of muscle damage in rhabdomyolysis, especially when fasciotomies are considered [3]. Short tau-inversion-recovery (STIR) sequences provide excellent differentiation between affected (hyperintense signal) and unaffected tissues with greater sensitivity than other imaging techniques and without exposure to radiation. Conflict of interest statement. None declared.

Previous work in our laboratory has demonstrated the existence of high affinity binding sites for the plant growth regulator ethylene. The ethylene binding protein (EBP), from Phaseolus cotyledons, shows many of the characteristics of a functional receptor for ethylene, has been purified on SDS-PAGE and polyclonal antibodies raised in rabbits. Current work involves the investigation of the ethylene transduction signal in a number of ethylene-responsive tissues.

Soybean and linseed oils were selectively hydroenated with copper-on-silica gel catalyst. The linolenate content of the oils was reduced to diene and monoene with no appreciable increase in saturates. Hydrogenated soybean oils contained 68–76% monoene, 11–18% diene, 0% conjugated diene and triene, 1–6% conjugatable diene, 0–0.3% conjugatable triene, and 23–40% isolatedtrans double bonds. Hydrogenated linseed oils contained 44–54% monoene, 35–45% diene, 0% conjugated diene and triene, 0–7% conjugatable diene, 0–02% conjugatable triene, and 44–59% isoaltedtrans double bonds. Esters of fatty acids, derived from these selectively hydrogenated oils, were prepared with trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, ethylene glycol, C18 saturated cyclic alcohols, primary C12–C18 saturated (nC12, nC14, nC16, nC18) alcohol, and primary C16–C18 saturated (nC16, nC18) alcohol blends. Measurements of viscosities and of smoke, flash, and fire points indicate that these esters are possible replacements for sperm oil. Certain of them, after sulfurization, also have potential as extreme pressure lubricant additives.

Rates of removal of nitrate, phosphate, and potassium from irradation-sterilized soil were measured. The soil was either uninoculated, or colonized by mycelium of Rhizoctonia solani (Kuhn) or Phycomyces blakesleeanus (Burgeff), and distilled water was then allowed to drain through it. Retention of nitrate and phosphate was increased significantly by colonization of the soil, but potassium retention was increased by colonization only when the rate of leaching was rapid. re]19740329

When nitrogen fixation in peas was partially replaced by nitrate assimilation as the source of nitrogen, an increase was found in the amount of soluble nitrogen that could be extracted from the fruits of the plants, and within this soluble fraction, increases were found in the levels of some of the acidic amino acids. Levels of protein amino acids in the peas were generally unaffected by the type of nitrogen source except for the level of aspartic acid which was about 20 per cent lower in peas supplied with nitrate. No differences were found in the proportions of the essential amino acids.

Molecular distillation of deodorizer condensates followed by chromatography on alumina, gave substantial quantities of hydrocarbons free of other unsaponifiable constituents. Squalene comprised 50% of the hydrocarbon fraction and contained practically all the unsaturation. A crystalline, saturated hydrocarbon fraction of 4.2% was composed primarily of C29 and C31 paraffins. An unresolved fraction was composed of two major components, each estimated to contain about 30 or 35 carbon atoms. Minor amounts of many hydrocarbons with chain lengths of 15\s-35 carbon atoms were present but not completely identified. C14 analysis showed that the hydrocarbons are natural to soybean oil and they are not artifacts arising from petroleum solvent residues.

Variables affecting the use of stannic chloride as a catalyst for initiating polymerization of conjugated and nonconjugated soybean vinyl ether were studied. Molecular weight of the polymers increased with an increase in catalyst and a decrease in initiation temperature, and it decreased when the amount of moisture in the solvent, the amount of free fatty alcohol in the monomer, or the ratio of solvent to monomer was increased. Aromatic and aliphatic hydrocarbon solvents were superior to halogenated solvents for conducting polymerizations. Similar results were obtained with nonconjugated monomers except that viscosities of the polymers were considerably lower than those of polymers of the same molecular weight obtained from conjugated monomer.

Adducts of methyl linoleate with itaconic and citraconic anhydrides have been prepared. Each adduct was separated into monomeric and polymeric components. With ethylene diamine, the itaconic and citraconic polymeric adducts gave gelled products at 170° in one hour and 3.5 hours, respectively. The adduct of citraconic anhydride and monomeric distillate gave a tough, tacky resin which did not gel during a reaction time of 20 hours at 170°–180°.

Free radical additions of hydrogen sulfide, ethanedithiol, and 1,6-hexanedithiol have been made to methyl oleate and linseed oil with ultraviolet radiation. Reactions were carried out in dichloromethane at −70C and in benzene at 25C. With the dithiols, a new dibasic ester has been prepared from methyl oleate in which bridging is accomplished through a dithiol moiety. Hydrogen sulfide has been added to linseed oil in suitable solvents at both −70C and 25C. It appears that zero-order kinetics control the additions at both temperatures. Infrared data show a linear relationship between mercapto absorption and the amount of sulfur incorporated. Nuclear magnetic resonance (NMR) spectra demonstrate a decrease in olefinic protons with an increase in sulfur content. Fair agreement on the extent of reaction exists between data from NMR, sulfur content, and infrared analyses. Hydrogen sulfide-treated linseed oil films air-dry slowly at room temperature; at 250C for 1 hr under a CO2 atmosphere these oils cure to brown films with Sward Rocker values of 24 to 32 and pencil hardness values of five to greater than six. Pencil hardness and alkali resistance increased with sulfur content. The film from the 4.2% sulfur sample resisted alkali at room temperature for 24 hr.

A polyaldehydie product called aldehyde oil was prepared by the ozonization of soybean oil, followed by reductive decomposition of the ozonolysis products. Reductive decomposition by chemical means gave 85–90% yields of carbonyl in the aldehyde oil. Catalytic reduction gave 75–80% yields. Partially-hydrogenated soybean oil gave more efficient results than did unhydrogenated oil. The polyfunctional aldehyde oil was found to undergo condensation reactions with phenolic compounds, urea, amines, and polyols to give cross-linked polymers.

Methyl 9(10)-formylstearate from hydroformylated oleate is autoxidized effectively to the corresponding carboxystearate in the presence of metal naphthenates at 20 C. Up to 95% conversion is obtained by treatment with Ca naphthenate for 24 hr. Catalyst activity based on disappearance of formylstearate approximates the following order: Co>Pb>Mn>Ce>Fe>Zr>Ca. Decreasing yields of carboxyester obtained with different catalysts follow the approximate order: Ca>Pb≈Fe≈Zr≈Mn>Co>Ce. The active redox metal catalysts such as Co, Ce and Mn produce varying amounts of methyl stearate, epoxy-, keto- and hydroxystearate as side products. Ca naphthenate minimizes free radical decarbonylation and other side reactions. Mechanisms are proposed for the formation of side products.

Adducts of maleic anhydride with methyl oleate, methyl linoleate, and monomeric distillate have been prepared. Reaction of the adducts with ethylene diamine gave a linear, soluble polyamide in the case of the oleate adduct, but gelation occurred at a low degree of reaction with other adducts. The linoleate adduct was separated into monomeric and polymeric components. It is suggested that this polymeric component is responsible for the rapid gelation of polyamides from the adducts of methyl linoleate and monomeric distillate.

Anticipated reduction in cost of hydrazine, resulting from its increased production as a rocket fuel, suggests the need to reconsider this chemical as an industrial reactant for fats. Hydrazinc reduces the individual double bonds of linolenic acid (9,12,15-octadecatrienoic acid) nonselectively and without altering the position of residual unsaturation; thus the monoene fraction from hydrazine-reduced linolenic acid consists of an equimixture of the 9-, 12-, and 15-octadecenoate acids. Equal amounts of the C9, C12, and C15 dibasic acids are derived from this fatty acid mixture by oxidative cleavage along with the corresponding monobasic acids.

Inter-esterification and isomerization reactions offer opportunities to modify drying oils by changing the arrangement of the acids in the fats and oils and by changing the arrangement of double bonds and the groups around the double bonds in the fat acid chains. Although much work has been completed, much more remains to be done.

Research conducted at the Northern Laboratory on vegetable oils during the past two decades includes polymerization, isomerization, flavor stability, and structure. Some early accomplishments—dimeric fatty acids and their derivatives, conjugated oils and their aftertack as well as the use of citric acid to inactivate iron in soybean oil—and more recent accomplishments—aldehyde oils, cyclic fatty acids, and tests for hidden oxidation and hydrazine reduction—are among the subjects reviewed.

In exploratory tests, mono-, di-, and trialdehyde oils and methyl azelaaldehydate (MAZ), preferably in the form of their acetals, reacted with various polyols with few exceptions to produce potentially useful derivatives. The polyols included pentaerythritol, methyl glucoside, glucose, sorbitol and poly (vinyl alcohol) (PVA). Preliminary evaluation of some of the derivatives was carried out in several applications. Among the more promising were: films derived from MAZ and glucose or PVA; melt adhesives for nonpolar substrates from trialdehyde oil and methyl glucoside; and molding compounds derived from MAZ and PVA.

The acetone-insoluble material from soybean “lecithin” has been fractionated by submitting alcohol-soluble and alcohol-insoluble portions to countercurrent distribution between hexane and methanol. The alcohol-soluble portion was found to contain lecithin, cephalin, and sugars or glycosides; the alcohol-insoluble portion was separated into two major inositol-containing phosphatides and sugars or glycosides. While the commonly accepted value of 30–35% for lecithin in the phosphatides was confirmed, it appears that the accepted value of 65% of cephalin needs revision. The approximate composition for one sample of soybean phosphatides is estimated to be 29% lecithin, 31% cephalin, and 40% inositol-phosphatides.

A liquid-partition chromatographic method was developed to determine dimers in fats. Silicie acid treated with 20% methanol in benzene served as the immobile phase. A mixture of 2% methanol in benzene was the mobile solvent. Chromatographic separation of free fatty acids from oxidized-deodorized oils gave three well-isolated fractions composed of unoxidized acids, dimeric or polymeric fatty acids, and polar fraction (ethyl ether eluate). Recovery of acidic materials from the column was essentially quantitative (96–100%), reproducibility was good, and the standard error of regression was ±0.26.

A chromatographic study was carried out to investigate the nature of polymeric products in edible oils. Dimers from low-temp oxidation of methyl linoleate were compared with thermal dimers from high-temp polymerization of conjugated methyl linoleate. The distilled dimers were subjected to liquid-partition chromatographic separations on silicic acid columns as methyl esters, as free acids, and as methyl esters prepared by saponification and reesterification. Chromatographically isolated dimer fractions were also rechromatographed before and after each treatment.

Both soybean and linseed alcohols were heated with potassium hydroxide and boric anhydride at 300°C. for 3 to 4 hrs. Products obtained under these conditions contained no unreacted starting alcohol, and each one appeared to be a mixture of condensed alcohols with average molecular weights of 720–860. Infrared spectroscopic studies and chemical analyses indicate that little or no ethers, esters, or carbonyl compounds were present in the final product from either alcohol. Such reactions as thermal cross-linking of the unsaturated side chains probably account for higher molecular weight products than those obtained in the Guerbet reaction of stearyl alcohol. Condensed alcohols from soybean and linseed alcohol were esterified with acrylic, sorbic, maleic, and soybean fatty acids to yield products with low acid numbers. Preliminary experiments demonstrated that these alcohols and their esters showed promise as materials for protective coatings. Films from these alcohols and esters were cast from toluene containing a cobalt naphthenate drier and were baked at 150°C. for 1 hr. or at 200°C. for 20 min. All of the baked films were hard to moderately hard and showed good resistance to aqueous alkali and organic solvents. In general, films from soybean condensed alcohol and its esters were harder than those from linseed condensed alcohols, but the linseed films were superior in alkali and solvent resistance. A soybean fatty acid ester of soybean condensed alcohol air-dried to a soft film in 3 days.

Circumstantial evidence has long pointed to linolenic acid as the unstable precursor of “reversion” flavors in soybean oil. Direct evidence has now been obtained from two sources: a) A qualitative study of the flavors after storage of soybean oil in which the linolenic acid content has been significantly lowered by furfural extraction, and b) organoleptic identification studies of stored soybean oil, stored cottonseed oil, and a cottonseed oil into whose glyceride structure linolenic acid has been introduced with the use of an interesterification catalyst. It is concluded that linolenic acid is an unstable precursor of “fishy-painty-grassy-melony” flavors in soybean oil.

Certain ester-acetal derivatives of azelaaldehydic acid have been evaluated as a new type of plasticizer of PVC. In gerneral, these compouonds have high compatibility and impart excellent low-temperature, mechanical, heat- and light -stability properties to the plasticized PVC. The 2-ethylihexyl ester bis (2-methoxyethyl) acetal, in particular, appeared to have the best combination of properties for a useful plasticizer. The results indicate that a unique and useful type of plasticizer-stabilizer can be obtained from derivatives of azelaaldehydic acid.

The acrylic esters of carnuba wax alcohols and the vinyl esters of nonhydroxy carnuba wax acids have been synthesized. The acrylic and vinyl esters have been homopolymerized and copolymerized with vinyl chloride. Acrylonitrile–acrylic ester copolymers also have been prepared. The copolymers were quite brittle when molding was attempted.

Yield improvements in carbonyl compounds obtained by catalytic hydrogenation of methyl oleate ozonolysis products have been achieved by use of catalyst poisons and by the proper choice of catalyst support. Byproduct dimethyl azelate formation with palladium on charcoal was about 20% in the absence of a poison; 10%, with sodium acetate present in the support; 8%, with triethyl amine in solution. Palladium on calcium carbonate-lead acetate gave about 7%, palladium on zine oxide with pyridine or lead acetate present gave 9%. The literature is reviewed on the catalytic hydrogenation of methoxy hydroperoxides derived from ozonolyses in methanol.

New polymeric coating materials have been prepared by a triethylenediamine-catalyzed reaction of hydroxyl-terminated polyesteramides (HTPA) from soybean or linseed oils with diisocyanates. Eight dibasic acids or anhydrides were reacted with excess N,N-bis(2-hydroxyethyl) fatty amide to yield HTPA; those containing 10 mole per cent excess gave isocyanate-modified polymers with best overall film properties. Reactivity of four diisocyanates with a linseed-HTPA was measured by disappearance of the isocyanate band in the infrared. Depending on chemical composition, structure and curing conditions, films prepared from these polymers have a wide range of drying characteristics, hardness and chemical resistance. Drying times of linseed HTPA-urethane polymer films varied from 0.3 to 48 hr, hardness values (Sward) were from 4 to 70, alkali resistance ranged from 2 to 126 min and the hydrochloric acid and xylene resistances were good to excellent. Impact resistance exceeded 160 in.-lb for all films except two. The soybean-derived polymer films likewise exhibited a wide range of properties; they chiefly differed from linseed-derived films in having greater flexibility and improved alkali resistance.

A table oil or a salad and cooking oil must serve both as an oil for salad dressings ;nd for cookino potatoes in a deep-fat fryer. BI;nds of peanut and unhydrogenated soybean oil that have been treated with a metal inactivating agent such as citric acid were scored fairly high by a research taste panel after aging for 4 or 8 days at 60 C. Heating the samples to frying temperature resulted in significantly higher room odor scores for peanu t oil than for the blends. Blends of hydrogenated or hydrogenated-winterized soybean oil with peanut oil were generally scored abou t equ al to peanut oil in room odor tests. Potatoes fried in these oils were generally given comparable and not significantly different scores.

Liquid C-18 saturated monocarboxylic acids, which are termed “cylic acids” because they contain a ring structure, have been prepared by the action of excess sodium hydroxide on linseed oil in ethylene glycol at elevated temperatures, followed by distillation and hydrogenation of the resulting free fatty acid monomers and by separation of the straight-chain components by low-temperature crystallization from acetone. In a survey of other possible catalysts and reaction conditions, cyclic acid yields were improved from the previously reported 32.4 g to 43.5 g of cyclic acid per 100 g of linseed fatty acids by removing water from the starting materials and using the monosodium derivative of ethylene glycol as catalyst. The corresponding amount of polymer formed decreased because of a decrease in hydroxylation and subsequent polyester formation.

Penetrations of concrete specimens by solutions of boiled linseed oil in mineral spirits and emulsions of boiled linseed oil were measured. Concrete specimens were cured with polyethylene sheet (removable) and wax-based and resin-based compounds prior to penetration tests. Penetration was greatest at 35 days and least at four and seven days after curing. Penetration at 105 days was only slightly less at 35 days. Maximum penetrations were obtained with solutions more dilute than 50 volume per cent of linseed oil in mineral spirits. Penetrations on polyethylene-, wax- or resin-cured specimens varied from 1.5 to 3 mm when 50 volume per cent linseed oil solution or emulsion was spread on the specimen at the rate of 0.16 lb/yd2.

Reductive ozonolysis of appropriate alkyl soyates in various participating media producted methyl, ethyl,n-propyl, isopropyl andn-butyl azelaaldehydates in good yield and high purity (98+%). The participating media examined were: methyl, ethyl,n-propyl andn-butyl alcohols; mixtures of an alcohol and acetic acid; water; and mixtures of water and acetic acid. Any combination of solvent and ester, except methanol-methyl soyate, allowed good separation by fractional distillation of ester and acetal impurities from the azelaaldehydate. A preparative method was developed by which high purity ethyl azelaaldehydate is produced from soybean oil by reductive ozonolysis in water. The only major impurity by this method was ethyl hydrogen azelate, which was easily removed with a bicarbonate wash. After a single fractional distillation with a short Vigreux column, the azelaaldehydate was obtained in 78% yield and 98+% purity. Physical properties and spectral (IR, NMR and mass spectroscopy) and chromatographic data were determined for the pure alkyl azelaaldehydates. Several of these properties were also determined for acetal and diester byproducts.

Hydrolytic, reductive and pyrolytic decompositions of ozonolysis products formed in water were surveyed as potential preparative routes to aldehydes. Water is an effective ozonolysis medium and reacts with the transient zwitterion formed during ozonolysis in the same manner as participating solvents. Reductive decomposition proved to be superior to either hydrolytic or pyrolytic decomposition for the preparation of aldehydes. Pyrolytic decomposition, as carried out in the injection port of a gas chromatograph, gave varying amounts and types of products depending upon the type of ozonolysis product used. Interconversion of the various types of ozonolysis products, including ozonides, methoxy hydroperoxides, acetoxy hydroperoxides and hydroxy hydroperoxides, does not occur except under acid catalysis.

Copolymers and terpolymers, based on vinyl ethers from linseed conjugated fatty alcohols and selected as having the most potential for commercial use, were evaluated as chemically resistant coatings, metal-decorating coatings, small-applicance and architectural finishes, wire coatings, and adhesives. Studies show these materials to have promise in areas where a high-temperature baking schedule can be tolerated and where color is not of prime importance. Good compatibility with most commonly used pigments was observed. As wire coatings, film showed good continuity and had superior dielectric strength and resistance to cut-through; however, improvement in flexibility and adhesion to copper would be needed for successful application. Performance as adhesives was disappointing, since curing in the absence of air was poor. The polymers showed some promise as can coatings, but the need for modifications in them was demonstrated.

Liquid C-18 saturated monocarboxylic acids that fail to crystallize at −70°C. have been prepared from linseed oil, linolenic acid, and tung oil. Heating one part of linseed oil in three parts of glycol (weight-volume ratio) at 295°C. for 1 hr. with 25% excess sodium hydroxide, followed by distillation and hydrogenation of the resulting free fatty acid monomers and separation of the straight-chain components by low temperature crystallization from acetone, yielded these liquid acids.

Metal-inactivating agents, such as citric acid, sorbitol, lecithin, and carboxymethylmercapto succinic acid, are not active in unheated vegetable oils. Apparently trace metals present in normal glyceride oils are held within a complex of unknown structure. After heating an oil, the metals can be complexed by metal-inactivating agents, such as citric acid. The release of metals appears to be associated closely with the breakdown of the fatty acid hydroperoxides. Formation of some association or complex between the metal and the hydroperoxide group or between the metal and the unsaturated linkage of the fatty hydroperoxide is suggested. The metals are held very tenaciously within this unknown structure. Although the metal is not available as an uncomplexed metallic ion, it does behave as a very strong pro-oxidant catalyst. The application of heat releases the metal so it can be complexed by added metal inactivators.

Synthetic oils have been prepared from residual dimerized fat acids with soybean and linseed fat acids by esterification with polyalcohols, and with or without maleic anhydride or phthalic anhydride. Preliminary evaluation indicates that these oils give films which dry faster and are more resistant to water and alkali than linseed oil films. This enhancement of water and alkali resistance may result from an increase in C-C bonds present in the films. Ester gum varnishes made from these oils were not markedly superior to similar varnishes made from linseed oil.

The preparation and properties of various polyamides, copolyamides, and modified polyamides, of polymeric fat acids have been described. These polymers are of interest because of their unusual properties and because of the unsaturation and relatively high molecular weight of the polybasic acids involved. Despite the presence of tribasic acids in polymeric fat acids, ungelled polymers having molecular weights of 3,000 to 5,000 are obtainable. A brief discussion has been given concerning the application of theoretical principles of polymerization to the preparation of these polymers. Possible industrial uses for the polyamides are indicated.

Methyl esters from vernonia oil containingcis-12,13-epoxy-cis-9-octadecenoate were reacted with acetone in the presence of a boron trifluoride catalyst to yieldtrans-12,13-0-isopropylidene-9-ene derivative I. Epoxidation of the unsaturation followed by reaction with acetone gave the isomerictrans,trans-di-0-isopropylidene deriva-tivesIII of 9,10 :12,13-tetrahydroxystearates. The carboxylic acids of III were converted to vinyl esters and subsequent hydrolysis of the isopropy-lidene groups with boric acid produced vinylthreo-9,10threo-12,13-tetrahydroxystearates. By the same sequence of reactions monoepoxidized methyl linoleate yielded an optically inactive de-rivative which had identical refractive index, IR spectrum, and GLC data toIII from vernonia methyl esters.

When autoxidized fatty esters and purified fatty hydroperoxides were decomposed in the absence of oxygen at 210°C., the principal reaction was dimerization of the fatty acid chains with elimination of the hydroperoxide groups. Dimers isolated by molecular distillation (60 to 90% of the polymer) have approximately 1 mole hydroxyl, 0.5 mole carbonyl, and two double bonds per mole of dimer. Diene conjugation in the dimers from polyunsaturated fat hydroperoxides varied from 10 to 23%. The infrared spectra of the dimers were similar to those of the original fatty esters except for one striking band at 2.9 μ, which is attributed to the secondary hydroxyl group. Thecis-trans diene in the polyunsaturated hydroperoxides was isomerized to thetrans-trans configuration on dimerization. The methyl oleate hydroperoxide dimer showed only absorption for isolatedtrans double bond. The dimer was not split either by catalytic hydrogenation or by hydrogen iodide, indicating a carbon-carbon bond between the monomer units. On oxidation with permanganate and periodate, the dimeric acids behaved like a monounsaturated mixture containing double bonds in the C6, C7, C8, C9, and C10 positions in the oleate dimer and in the C8, C9, and C10 positions in the safflower ester dimer. Although the dimers showed no peroxidic oxygen iodometrically with potassium iodide, a reduction occurred with hydriodic acid that may indicate the presence of intramolecular peroxide groups and/or allylic alcohol or carbonyl groups. Bromination with N-bromosuc-cinimide and dehydrobromination with N,N-dimethyl aniline produced no aromatization. Subsequent oxidation of the dehydrobrominated dimer yielded 2.6% residue, which was not aromatic. This evidence indicates that the dimer does not have a six-membered cyclic structure. Dimerization of the hydroperoxides is suggested as occurring through alkyl or alkoxy hydroperoxide radicals to give carbon-carbon linked fatty acid dimers and some higher polymeric units.

3,9-Bis(7-carbomethoxyheptyl)-2,4,8,10-tetraoxaspiro[5.5]-undecane (the pentaerythritol acetal of methyl azelaaldehydate) in the presence of basic catalysts underwent condensation polymerization with ethylene glycol to give linear polymers, either alone or in conjunction with other dibasic esters. These linear poly(ester-acetals) were susceptible to crosslinking by p-toluenesulfonic acid and by various metal oxides and salts, such as zinc oxide, zinc acetate, litharge, and magnesium oxide. The crosslinked polymers were insoluble, infusible, transparent solids which were strongly adherent to glass.

A study has been made of the effectiveness of various polycarboxylic acids and polyhydric alcohols in improving the stability of soybean oil. Certain observations have been made regarding the structural groups required and the possible mechanism of reaction. Since salts and esters of organic acids are inactive, free carboxyl groups are required. Among the four carbon atom dicarboxylic acids activity increases with the number of hydroxyl groups. Within the polyalcohols activity increases with the increase in number of hydroxyl groups. Steric immobility and loss of hydroxyl groups by dehydration reduces activity. Evidence is presented which attributes to citric acid and certain polyhydric alcohols the role of metal scavenger. For example, it has been demonstrated that the addition of citric acid and sorbitol to soybean oil containing prooxidant metallic salts effectively increases the oxidative and flavor stability of the oil. By using a sample of treated soybean oil with no detectable tocopherols, in order to eliminate synergistic effects of citric acid, it has been shown that the prooxidant effect of iron stearate is counteracted by the presence of citric acid. The demonstration that polyhydric alcohols increase the flavor and oxidative stability is compatible with their known metal complexing properties. Evidence is presented which indicates a relationship between flavor stability and oxidative stability.

Citric acid and sorbitol were tested on a commercial scale and their use was found to improve the oxidative and flavor stability of soybean oil.

Oxidative stabilities of soybean oil and lard are improved by the addition of either sorbitol or citric acid. Sufficient sorbitol gives enough improvement in stability so that added citric acid gives no increased stability. Unless sorbitol acts as a neutral synergist, forms a powerful acidic synergist in trace amounts or a new antioxidant, the antioxidant activity of citric acid appears to come from its inactivating capacities for metals.

3,9-Bis(7-carbomethoxyheptyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (the pentaerythritol acetal of methyl azelaaldehydate) was found to undergo condensation polymerization with diamines to give linear polymers, either alone or in conjunction with dimethyl azelate. These novel, linear poly(amide-acetals) were susceptible to crosslinking by p-toluenesulfonic acid and by various metal oxides and salts, such as zinc oxide, zinc acetate, litharge, and magnesium oxide. The crosslinked polymers were insoluble, infusible, transparent solids which were strongly adherent to glass.

Styrenation of fatty vinyl ether polymers in dipentene at 145–165C gives products containing from 20 to 67% styrene by weight but little or no unreacted monomeric styrene remained. After 27 mounths no gelation occurred in these products. Apparently dipentene serves as an effective chain transfer agent during styrenation, keeps the growing polymer chains short, and reduces crosslinking reactions. The amount and type of unsaturation needed in the fatty side chains of the polymer to produce homogeneous products were studied. Ultraviolet and infrared analyses were useful in determining the function of unsaturation in these reactions.

Several acetals and an enol ether were prepared from methyl 9(10)-formylstearate and characterized with respect to their thermal, spectroscopic and chromatographic properties. These low-melting (below −80 C) compounds were generally compatible as secondary poly(vinyl chloride) plasticizers and imparted low-temperature properties that were intermediate between those obtained with dioctyl phthalate and dioctyl sebacate.

In the dextrose-free recipe at 41°F. for the copolymerization of butadiene and styrene, using 6 × 10−4 mole of initiator per one hundred grams of monomers, methyl oleate peroxide (MOP) and methyl linoleate peroxide (MLP) gave higher polymerization rates and conversions than cumene hydroperoxide (CHP), and they gave as high rates of conversion as p-menthane hydroperoxide (PMHP). In the peroxide-dextrose recipe at 122°F., at both low and high dextrose levels, only about one-half as much MOP (1.5 × 10−4 mole) as CHP or PMHP was employed on a molar basis to achieve the same conversion and polymerization rate. In the low dextrose-redox recipe at 41°F., using 6 × 10−4 mole of initiator per one hundred grams of monomers, MLP gave slightly higher conversions than CHP or PMHP, but in the amine recipe at 41°F., MLP gave lower conversions.