Amides ofa-sulfonated palmitic and stearic acids

Summary Carboxylic acid amides of α-sulfopalmitic and α-sulfostearic acids were prepared from ammonia, ethylamine, ethanolamine, isopropylalcoholamine, diethanolamine, and N-methyltaurine, and were isolated as the sodium, ammonium, or ethanolammonium salt. A satisfactory method was found to be the reaction of the sulfocarboxylic acid with an excess of thionyl chloride, and further reaction of the acid chloride with an amine in a chlorinated solvent. More work is needed on the application of direct amidation methods to the preparation of these compounds. The solubility of the α-sulfonated amides increased with substitution of alkyl, hydroxyalkyl, and sulfoalkyl groups at the nitrogen atom. Ethanolammonium N-hydroxyethyl-α-sulfopalmitamide, ethanolammonium N-hydroxyethyl-α-sulfostearamide, sodium N-(2-hydroxypropyl)-α-sulfostearamide, sodium di-(N-hydroxyethyl)-α-sulfostearamide, and disodium N-methyl,N-(2-sulfoethyl)-α-sulfostearamide have aqueous solubility in excess of 10% at room temperature. Most of the sodium salts of the α-sulfonated amides have good or excellent stability to calcium and other divalent ions and are excellent lime soap dispersing agents. Presented at the fall meeting, American Oil Chemists' Society, Los Angeles, Calif., September 28–30, 1959. Enstern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Oxidative desaturation of α-linolenic,linoleic, and stearic acids by human liver microsomes

The desaturation of stearic, linoleic, and α-linolenic acids by human liver microsomes were studied. The microsomes were isolated from liver biopsies obtained during operations. It was shown that human liver microsomes are able to desaturate 1-¹⁴C-α-linolenic acid to octadeca-6,9,12,15-tetraenoic acid; 1-¹⁴C-linoleic acid to γ-linolenic acid; and 1-¹⁴C-stearic acid to oleic acid in the same system described in the rat. However, the desaturation activity obtained was low compared to other mammals. This effect was attributed to fasting, premedication, or the anaesthesia.     

Adsorption of dimer,trimer, stearic,oleic, linoleic,nonanoic and azelaic acids on ferric oxide

The adsorption isotherms of solutions of dimer, trimer, stearic, oleic, linoleic, nonanoic and azelaic acids in organic solvents, (mostly hexane) have been determined on an alpha ferric oxide with a surface area (B.E.T. N₂ adsorption) of 99 m² (99 × 10²⁰ A²) per gram. They all showed limiting adsorption as grams adsorbed per gram of iron oxide beyond a concentration of about 1 g/100 cc, analagous to the Langmuir type monolayer isotherm. Areas per molecule were calculated and compared with areas of close-packed models in positions parallel to and perpendicular to the surface. The calculated areas corresponded more closely to the flat or parallel positions. Heats of adsorption were determined and were in the range of 27–71 kcal/eq, suggesting chemisorption of the COOH group at the surface. The value of dimer acid suggests that both COOH groups are chemisorbed. Models show that the parallel position permits both COOH groups to touch the surface. The perpendicular position generally does not permit both COOH groups to touch the surface. Dimer acid showed a value (71 kcal/eq) higher than the monobasic acids (44–55 kcal/eq), possibly due to interaction of the ring structure (partly aromatic) with the surface. Azelaic acid from an 80–20t-butanol-hexane solvent showed a lower value of 27 kcal/eq, possibly due to adsorption of a hydrogenbonded alcohol-acid moiety as such. Journal Series No. 547, General Mills, Inc. Research Laboratories.     

Plasma clerance and hepatic utilization of stearic,myristic and linoleic acids introducedvia chylomicrons in rats

The primary objective of the present study was to compare the rates of plasma clearance and hepatic utilization of stearic (18∶0), myristic (14∶0) and linoleic (18∶2) acids, as introducedvia chylomicrons. Lymph chylomicrons were specifically labeledin vivo with [¹⁴C]stearic and (SA), [¹⁴C]myristic acid (MA), or [¹⁴C]linoleic acid (LA) by infusing donor rats intraduodenally with the labeled fatty acids in a lipid emulsion. Following intravenous injection of recipient rats with the labeled chylomicrons, the rates of plasma clearance and incorporation of the label in triglycerides (TG), phospholipids (PL) and other lipids in the liver were compared at 5, 15 and 30 min. [¹⁴C]SA was cleared at a slightly faster rate (t_1/2=7.0 min) than [¹⁴C]MA (t_1/2=8.1 min) and [¹⁴C]LA (t_1/2=8.0 min) (P<0.05). [¹⁴C]SA was accumulated in the liver at a significantly faster rate than [¹⁴C]MA and [¹⁴C]LA. At the peak (15 min) of hepatic uptake, 30.3% of [¹⁴C]SA, 26.2% of [¹⁴C]LA and 21.9% of [¹⁴C]MA were recovered in the liver. At 30 min, 33.5% of [¹⁴C]SA was taken up by the liver, whereas 27.8% of [¹⁴C]LA and only 15.2% of [¹⁴C]MA were removed. In the liver, the percentage of [¹⁴C]SA incorporated into PL steadily increased with time, whereas the percent-age incorporated into TG decreased. [¹⁴C]SA was preferentially incorporated into PL at all time intervals, as compared with [¹⁴C]MA and [¹⁴C]LA. At 30 min, 38.6% of [¹⁴C]SA was found in PL, and only 5.2% of [¹⁴C]MA and 12.0% of [¹⁴C]LA were present in PL. A large proportion of hepatic [¹⁴C]MA remained unesterified (free fatty acid) throughout the 30-min period, with a small proportion incorporated into PL and TG. Of the total liver¹⁴C radioactivity recovered at 30 min, 63.8% of [¹⁴C]MA, 48.8% of [¹⁴C]LA and 25.5% of [¹⁴C]SA were found unesterified. During 30 min, a significantly greater amount of [¹⁴C]MA (76.9%) was oxidized in both the liver and the peripheral tissue combined, compared with [¹⁴C]LA (64.7%) and [¹⁴C]SA (61.2%). A higher proportion of [¹⁴C]LA was incorporated into TG than into PL at all time intervals. No differences were noted in the relative distribution of¹⁴C in cholesterol and other lipids among the three fatty acids. Using labeled fatty acids incorporatedin vivo into chylomicrons, the present study demonstrated that SA, MA and LA are distinctly different in their metabolic behavior. During the initial 30 min after their entry into the blood, 92–95% of the fatty acids were cleared. During this early phase of metabolism, [¹⁴C]SA was preferentially utilized for liver PL synthesis, whereas [¹⁴C]LA was better incorporated into TG. [¹⁴C]MA was poorly incorporated into hepatic lipids, but was preferentially oxidized in the liver or utilized by the peripheral tissue.     

Glucose fermentation in the presence of linoleic,oleic and stearic acids by a mixed culture

Long Chain Fatty Acid (LCFA) mixtures containing linoleic, oleic and stearic acids plus carbohydrates are found in a variety of effluents arising from fried food manufacture and milk processing. Accumulation of Volatile Fatty acids (VFAs) due to the presence of LCFAs may impair the operation of an anaerobic system treating effluents containing a mixture of triglycerides and carbohydrates. In this study, the effects of linoleic (C18:2), oleic (C18:1), and stearic (C18:0) acids on glucose fermentation were investigated at 21 °C using a culture acclimated to glucose. In cultures receiving ≥300 mg dm^?3 LCFAs, residual amounts of glucose remained after approximately 8 h and none was detected after 24 h. Acetate degradation was inhibited in the presence of 300 or more mg dm^?3 linoleic acid (LA), oleic acid (OA), or stearic acid (SA) with more acetate accumulation observed in cultures receiving LA. In comparison to the controls, similar amounts of propionate accumulation were observed in cultures receiving ≤100 mg dm^?3 of each LCFA. However, in cultures receiving ≥300 mg dm^?3 LCFAs, more propionate accumulated with complete removal observed within 20 days for only those cultures receiving oleic or stearic acids. Butyrate accumulation was observed only in cultures receiving ≥300 mg dm^?3 LA and none was detected after 10 days of incubation. Copyright © 2004 Society of Chemical Industry     

双酰亚胺型均苯四甲酸及复合酸镧盐的合成与应用

采用水热法制备了4,4'-亚甲基-二苯基-二-(1″,2″)-酰亚胺-二-(4″,5″)-苯二甲酸酐(简称酰亚胺四酸酐)以及双硬脂酸单4,4'-亚甲基-二苯基-二-(1″,2″)-酰亚胺-二-(4″,5″)-苯二甲酸二镧(简称复合酸镧盐La-1),应用红外光谱与热失重法对其结构进行表征,并将La-1应用于聚酰胺66(PA 66)以改善PA 66热氧化稳定性,且与硬脂酸镧(La-2)、均苯四甲酸镧(La-3)、双硬脂酸单均苯四甲酸二镧(La-4)进行比较。结果表明:通过正交实验得出,酰亚胺四酸酐合成的最优反应条件为酰亚胺化反应温度135℃,时间5 h,二甲苯与产物水质量比6∶1,均苯四甲酸酐(PMDA)与4,4'-二氨基二苯甲烷(DDM)摩尔比2.3∶1.0;傅里叶变换红外光谱表征所合成的酰亚胺四酸酐和La-1为目标产物;La-3的热分解温度大于550℃,高于PA 66的热分解温度,La-1,La-2,La-3的热稳定性均弱于纯PA 66;La-3,La-4对PA 66的抗黄变性效果比La-1,La-2的要好,这是由于硬脂酸长链热稳定性差及芳香酸镧中的邻苯二甲酸结构中残存羟基量对PA 66热氧化稳定性造成影响的缘故。     

Hyperchlorinated fatty acids: II. Photochlorination of stearic acid in carbon tetrachloride,reaction study

The free radical chlorination of stearic acid in carbon tetrachloride was studied with variation of the chlorine flow rate, the active light intensity and the initial fatty acid concentration. In addition the variation of temperature with time was measured. The chlorine flow rate affects only the reaction time and modifies neither the chlorine content of the products obtained nor the yield, approximating 100%. On the other hand, the initial fatty acid concentration seems to be the prime factor determining the chlorine content of the products. Similarly, the onset of the polymerization of the chlorinated monomers depends essentially on the initial fatty acid concentration. These polymers are probably chlorinated polyesters. This behavior can be explained by the incursion of radical ions RCOO·⁺ resulting from irradiation of exciplexes formed by interaction between the more or less highly chlorinated fatty acid and the solvent. These interactions take place when the fundamental complex occupies a critical volume, which depends on the acid concentration.     

Metabolism in humans ofcis-12,rans-15-octadecadienoic acid relative to palmitic,stearic, oleic and linoleic acids

Mixtures of triglycerides containing deuterium-labeled hexadecanoic acid (16∶0), octadecanoic acid (18∶0),cis-9-octadecenoic acid (9c–18∶1),cis-9,cis-12-octadecadienoic acid (9c, 12c–18∶2) andcis-12,trans-15-octadecadienoic acid (12c,15t–18∶2) were fed to two young-adult males. Plasma lipid classes were isolated from samples collected periodically over 48 hr. Incorporation and turnover of the deuterium-labeled fats in plasma lipids were followed by gas chromatography-mass spectrometry (GC-MS) analysis of the methyl ester derivatives. Absorption of the deuterated fats was followed by GC-MS analysis of chylomicron triglycerides isolated by ultracentrifugation. Results were the following: (i) endogenous fat contributed about 40% of the total fat incorporated into chylomicron triglycerides; (ii) elongation, desaturation and chain-shortened products from the deuterated fats were not detected; (iii) the polyunsaturated isomer 12c,15t–18∶2 was metabolically more similar to saturated and 9c–18∶1 fatty acids than to 9c,12c–18∶2 (iv) relative incorporation of 9c,12c–18∶2 into phospholipids did not increase proportionally with an increase of 9c,12c–18∶2 in the mixture of deuterated fats fed; (v) absorption of 16∶0, 18∶0, 9c–18∶1, 9c,12c–18∶2 and 12c,15t–18∶2 were similar; and (vi) data for the 1- and 2-acyl positions of phosphatidylcholine and for cholesteryl ester fractions reflected the known high specificity of phosphatidylcholine acyltransferase and lecithin:cholesteryl acyltransferase for 9c,12c–18∶2. These results illustrate that incorporation of dietary fatty acids into human plasma lipid classes is selectively controlled and that incorporation of dietary 9c,12c–18∶2 is limited. These results suggest that nutritional benefits of diets high in 9c,12c–18∶2 may be of little value to normal subjects and that the 12c,15t–18∶2 isomer in hydrogenated fat is not a nutritional liability at the present dietary level.     

Ring position in cyclopropene fatty acids and stearic acid desaturation in hen liver

Four cyclopropene fatty acids, having the double bond of the cyclopropene ring at the 8,9, 9,10, 10,11 and 11,12 positions, respectively, were tested as inhibitors of stearic acid desaturation by the desaturase enzyme system of hen liver. The first three were powerful inhibitors, but the last was not. The cyclopropene acids with the 9,10 and 10,11 double bonds were equally strong inhibitors, while the acid with the 8,9 double bond was less effective. To account for the specificity of those cyclopropene fatty acids in which the C9 or C10 carbon atom is included in the cyclopropene ring, it is suggested that the conformation and structure of the CoA derivatives of these acids is such that they can irreversibly occupy the site on the enzyme responsible for 9,10-desaturation.     

The fate and intermediary metabolism of stearic acid

Coming from the Greek for “hard fat”, stearic acid represents one of the most abundant FA in the Western diet. Otherwise known as n-octadecanoic acid (18∶0), stearate is either obtained in the diet or synthesized by the elongation of palmitate, the principal product of the FA synthase system in animal cells. Stearic acid has been shown to be a very poor substrate for TG synthesis, even as compared with other saturated fats such as myristate and palmitate, and in human studies stearic acid has been shown to generate a lower lipemic response than medium-chain saturated FA. Although it has been proposed that this may be due to less efficient absorption of stearic acid in the gut, such findings have not been consistent. Along with palmitate, stearate is the major substrate for the enzyme stearoyl-CoA desaturase, which catalyzes the conversion of stearate to oleate, the preferred substrate for the synthesis of TG and other complex lipids. In mice, targeted disruption of the stearoyl-CoA desaturase-1 (SCD1) gene results in the generation of a lean mouse that is resistant to diet-induced obesity and insulin resistance. SCD1 also has been shown to be a key target of the anorexigenic hormone leptin, thus underscoring the importance of this enzyme, and consequently the cellular stearate-to-oleate ratio, in lipid metabolism and potentially in the treatment of obesity and related disorders.     

Efficient preparation of highly substituted thiophenes and thiophene-based arylacetic acids

An efficient and one-step method for the preparation of highly substituted thiophenes and thiophen-2-yl-acetic acid derivatives was developed. Hence, thioacetomorpholides were smoothly reacted with α-bromo carbonyl compounds in [bmim]OH as an efficient dual catalyst-reaction medium to produce the title compounds in good yields.     

Lipase specificity toward some acetylenic and olefinic alcohols in the esterification of pentanoic and stearic acids

The esterification of five medium- and long-chain acetylenic alcohols (2-nonyn-1-ol, 10-undecyn-1-ol, 6-octadecyn-1-ol, 9-octadecyn-1-ol, and 13-docosyn-1-ol), seven olefinic alcohols (cis-3-nonen-1-ol, 10-undecen-1-ol, cis-6-octadecen-1-ol, cis-9-octadecen-1-ol, trans-9-octadecen-1-ol, trans-9, trans-11-octadecadien-1-ol, cis-9, cis-12-octadecadien-1-ol), and four short-chain unsaturated alcohols (allyl alcohol, 3-butyn-1-ol, 3-pentyn-1-ol, and cis-2-penten-1-ol) with pentanoic or stearic acid in the presence of various lipase preparations was studied. With the exception of 2-nonyn-1-ol, where Lipase AY-30 (Candida rugosa) was used as the biocatalyst, the esterification of C₁₁, C₁₈, and C₂₂ acetylenic alcohols with pentanoic acid appeared to be generally unaffected by the presence of an acetylenic bond in the alcohol as relatively high yields of the corresponding esters (78–97%) were obtained. However, medium- and long-chain olefinic alcohols were discriminated by Lipase AY-30, Lipolase 100T (Rhizomucor miehei), and especially by porcine pancreatic lipase (PPL), when esterification was conducted with pentanoic acid. Esterification of medium-and long-chain acetylenic or olefinic alcohols with a long-chain fatty acid, stearic acid, was very efficient except when Lipase AY-30 and Lipolase 100T were used. Short-chain unsaturated alcohols were much more readily discriminated. 3-Pentyn-1-ol and 3-butyn-1-ol were difficult (<5% yield) to esterify with pentanoic or stearic acid in the presence of Lipase AY-30 and PPL, respectively. Very low yields (<26%) of esters were produced when 3-butyn-1-ol and 3-pentyn-1-ol were reacted with pentanoic or stearic acid, when catalyzed by lipase from Candida cylindracea, No reaction took place between 3-butyn-1-ol and stearic acid in the presence of Lipase AY-30. Esterification of short-chain acetylenic and olefinic alcohols was most efficiently achieved with Lipolase 100T (Rhizomucor miehei), Lipozyme IM20 (Rh. miehei), or Novozyme 435 (Candida antarctica) as the biocatalyst.     

Inhibition by cyclopropene fatty acids of the desaturation of stearic acid in hen liver

The mechanism of the hardening of body fats of animals by dietary lipids which contain cyclopropene fatty acids has been studied. Dietary methyl sterculate increased the stearic acid content of egg yolk lipid and decreased the activity of the stearic acid desaturase system of hen liver. The cyclopropene fatty acids were specific inhibitors of the stearic acid desaturase system of hen livers since other fatty acids, including two possible metabolites of sterculic acid, failed to inhibit the system at equivalent concentrations. Sterculic acid was a more effective inhibitor of the system than malvalic acid. Kinetic studies have shown that the inhibition is irreversible. Apparent kinetic constants were determined for the system. The results support the hypotheses that cyclopropene fatty acids inactivate an essential component of the desaturase system, probably by combination with-SH groups, and that this inhibition causes many of the effects of dietary cyclopropene fatty acids, including permeability disorders of eggs. Based on a paper presented at the AOCS Meeting, Philadelphia, October 1967.     

Quantitative analysis of synthetic mixtures of triacylglycerols with fatty acids from caprylic to stearic

Separation and quantitation of triacylglycerols tricaprylin to tristearin was achieved by high-performance liquid chromatography with refractive index detection and an eluent composed of propionitrile and butyronitrile (80:20, vol/vol). Peak identification was based on the logarithms of retention times, and quantitation was achieved by way of theoretical relative response factors. The validity of the response factor calculations was tested by analysis of primary standard mixtures of saturated triacylglycerols and of triacylglycerols obtained by interesterification of binary mixtures of monoacid triacylglycerols.     

Ultraviolet absorption spectra: Some substituted benzoic acids

The u.v. absorption spectra of 22 monosubstituted and 19 disubstituted benzoic acids have been studied in water or aqueous dioxan over a pH range of about 1–8. The isosbestic points have been measured and the results are discussed.     

Phase investigations of fats. II. Systems containing oleic and stearic acids and an organic solvent

1. The ternary systems oleic acid-stearic acid-commercial hexane and oleic acid-stearic acid-acetone containing varying amounts of the three components have been equilibrated at 0°C., −10°C., −20°C., −30°C., and −40°C.
2. From compositional data of the liquid and solid phases in equilibrium at each isotherm, ternary phase diagrams have been constructed. From these diagrams it is possible to predict the degree of separation which can be obtained with any given mixture of oleic and stearic acids, using either acetone or commercial hexane as solvent.
3. With practical solvent ratios the phase diagrams at −20°C., −30°C., and −40°C., exhibit closed areas representing liquid phase composition. The liquid phase boundaries have been established for each isotherm investigated.
4. The intersolubilizing effect of oleic acid on stearic acid, greater in commercial hexane than in acetone, and the possible formation of mixed crystals of oleic and stearic acid have been noted.
5. Oleic acid of high purity can be obtained as one of the practical applications of these data.

     

硬脂酸皂化值测定用盐酸标准溶液的不确定度评定

对硬脂酸皂化值测定用盐酸标准溶液(0.5 mol·L-1)配制和标定过程中的不确定度来源进行分析,并对标定结果进行不确定度评估.结果表明,盐酸标准溶液不确定度的主要来源是滴定体积的不确定度分量,其中滴定管检定引入的标准不确定度分量影响最大.本方法评定的盐酸标准溶液的浓度为(0.505 0士0.001 2)mol,L-1.     

The preparation of stearic acid from castor oil

Summary By de-hydroxylating the 12-hydroxystearic acid, which may be prepared in a pure state by the alcoholysis of fully hydrogenated castor oil, there may be obtained in at least 40% yield an exceptionally pure stearic acid whose solidification point is the same as that of a similar product previously reported by others (1). Avoided by the procedure described are recourse to the necessity of preparing lead soaps for the removal of unsaturated fatty acids and the drudgery of repeated crystallizations as prescribed by other published methods. From the doctoral dissertation of D. A. Roth. University of Wisconsin, May, 1944.     

Preparation and conductivity of substituted germanic heteropoly acids polyethylene glycol hybrid materials

In this work, the polyethylene glycol (PEG) hybrid materials composited with substituted germanic heteropoly acids were prepared. Infrared (IR) spectra revealed that the Keggin structure characteristic of the GeM₁₁VO₄₀^5? anion were present in the hybrid materials. At room temperature (20°C), the conductivity of the products is 4.07 × 10^?3 S cm^?1 and 2.12 × 10^?3 S cm^?1, respectively. The results indicated that the conductivity of substituted germanic heteropoly acids PEG hybrid materials is higher than that of the corresponding pure substituted germanic heteropoly acids. According to the experimental results, we proposed a possible mechanism of the proton conduction of the hybrid materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

An STM investigation of the adsorption of mixtures of fatty acids and substituted acids at the solution-graphite interface

Scanning tunneling microscopy (STM) is used to investigate the adsorption on graphite of two-solute mixtures from phenyloctane solvent at room temperature. The first mixture is composed of the co-solutes hexadecanoic acid (HA) and 2-Br-hexadecanoic acid (2BrHA), while the second mixture is composed of co-solutes tetracosanoic acid (TA) and octadecanoic acid (OA). While the HA/2BrHA solution exhibits a miscible co-adsorbed surface structure, the TA/OA solution reveals a quasi-segregated surface structure where there is a sharp transition from full surface coverage by one solute to full coverage by the second as the composition of the solution mixture is varied. A one-dimensional Ising model is used to model the adsorption behavior of both systems, and it is shown that both the HA/2BrHA and OA/TA mixtures correspond to two different limits of this model. The HA/2BrHA mixture exhibits similar, weak interactions between adsorbed molecules, corresponding to one limit of the Ising model, which also corresponds to competitive Langmuir adsorption. Another limit of the Ising model is reached when there are significantly different interactions between the different co-adsorbates on the surface, a situation present in the OA/TA mixture resulting in a significantly different co-adsorption behavior.