乙二醇单丁醚为溶剂制备共轭亚油酸的研究

以乙二醇单丁醚作为溶剂,KOH作催化剂,碱催化异构化法用豆油制备共轭亚油酸。通过正交设计,紫外光谱分析考察了4种因素对亚油酸转化率的影响,并得出制备高亚油酸油脂合适的工艺条件:反应温度135℃,反应时间3 h,强碱催化剂与原料质量比为0.4∶1,原料与溶剂质量比为2∶3。在此条件下,亚油酸的平均转化率达到96.8%。结果表明,该溶剂能使反应在均相体系中较为温和的温度条件下较短的时间内完成。     

The mechanism and kinetics of the electrochemical cleavage of azo bond of 2-hydroxy-5-sulfophenyl-azo-benzoic acids

The electrochemical reduction of 2-hydroxy-5-[(4-sulfophenyl)azo]benzoic acid, 2-hydroxy-5-[(3-sulfophenyl)azo]benzoic acid, 2-hydroxy-5-[(2-sulfophenyl)azo]benzoic acid and 2-hydroxy-5-azo-benzoic acid has been carried out in aqueous solutions at glassy carbon electrode using cyclic voltammetry and chronoamperometry. The position of sulfo substituent relative to azo bridge as well as pH of the solution have significant impact on the electrochemical behavior of these compounds. It has been proposed that these compounds are reduced predominantly as hydrazone tautomers resulting in corresponding hydrazo compounds. The overall electrochemical reduction follows DISP2 mechanism, ultimately leading to the 5-amino salicylic acid and sulfanilic acid. The rate determining step is the homogenous redox reaction between intermediate hydrazo compound and 5-amino salicylic acid quinoneimine. The mechanism is proposed in which activated complex of 5-amino salicylic acid quinoneimine and intermediate hydrazo compound is formed with the simultaneous loss of one proton.     

Lipid hydrolysis and oxidation on the surface of milled rice

The changes in milled rice FFA content and composition and in conjugated diene (CD) content and bacterial, yeast, and mold counts were determined at 24, 37, and 50°C and 70% RH over 50 d. There was a rapid rate of FFA formation during the first few days of storage, which was optimal at 37°C, but that slowed after 2, 4, and 5 d at 37, 24, and 50°C, respectively. There was a second increase in FFA after about day 12 that increased with increasing temperature, indicating nonlipase hydrolysis. Linoleic and oleic acids were the main components of the total FFA produced on the surface of milled rice. The pattern of CD development followed that of FFA increase. Bacterial growth correlated with increased FFA levels after 12 d of storage, suggesting that bacterial lipase rather than bran lipase may be responsible for rice lipid hydrolysis     

Lipase-catalyzed synthesis and properties of estolides and their esters

Eight lipases were screened for their ability to synthesize estolides from a mixture that contained lesquerolic (14-hydroxy-11-eicosenoic) acid and octadecenoic acid. With the exception ofAspergillus niger lipase, all 1,3-specific enzymes (fromRhizopus arrhizus andRhizomucor miehei lipases) were unable to synthesize estolides.Candida rugosa andGeotrichum lipases catalyzed estolide formation at >40% yield, with >80% of the estolide formed being monoestolide from one lesquerolic and one octadecenoic acyl group:Pseudomonas sp. lipase synthesized estolides at 62% yield, but the product mixture contained significant amounts of monoestolide with two lesquerolic acyl groups as well as diestolide. ImmobilizedR. miehei lipase was chosen to catalyze the esterification of mono-and polyestolide, derived synthetically from oleic acid, with fatty alcohols or α,ω-diols. Yields were >95% for fatty alcohol reactions and >60% for diol reactions. In addition, the estolide linkage remained intact through the course of the esterification process. Esterification of estolides improved the estolide’s properties—for example, lower viscosity and higher viscosity index—but slightly raised the melting point. Estolides and, particularly, estolide esters may be suitable as lubricants or lubricant additives.     

Monooxygenase system of <Emphasis Type="Italic">Bacillus megaterium</Emphasis> ALA2: Studies on palmitic acid oxidation products

We identified many novel oxygenated FA produced from linoleic acid by microbial strain ALA2: 12,13,17-trihydroxy-9(Z)-octadecenoic acid (12,13,17-THOA); 12,13,16-trihydroxy-9(Z)-octadecenoic acid (12,13,16-THOA); 12-hydroxy-13,16-epoxy-9(Z)-octadecenoic acid; and 12,17;13,17-diepoxy-16-hydroxy-9(Z)-octadecenoic acid. 12,13,17-THOA, the main product, inhibits the growth of some plant pathogenic fungi. Recently, we reclassified strain ALA2 as Bacillus megaterium ALA2 NRRL B-21660 and opened a possible link with the well-studied catalytically self-sufficient P450 monooxygenase of Bacillus megaterium ATCC 14581 (NRRL B-3712) and B. subtilis strain 168 (NRRL B-4219). Now we have found that strain ALA2 also oxidizes palmitic acid into three oxygenated products: 13-, 14-, and 15-hydroxy palmitic acids. This indicates that strain ALA2 also possesses a monooxygenase system similar to the abovementioned well-known strains. These data facilitate studies on the oxygenase system of strain ALA2.     

国内外AE／AES生产现状及市场分析

介绍国内外脂肪醇聚氧乙烯醚(AE)和脂肪醇聚氧乙烯醚硫酸盐(AES)的生产现状及供需情况.2003年全球AE的总产能为391.7万t/a,总产量为155.8万t,总消费量为148.3万t;AES的总产能为377.5万t/a,产量约为300万t,消费量约为90万t.2004年我国AE的产能已超过50万t/a,但产量只有15万t,消费量为30.5万t;AES的总产能为37.95万t/a,产量为14万t,市场需求约10万t.最后补充介绍乙氧基化的技术进展.     

Adsorption isotherms of sesame oil in a concentrated miscella system

The adsorption of peroxides, unsaturated carbonyls, free fatty acids and carotenoids from unrefined sesame oil on vegetable carbon (5%, w/w) in a miscella system was studied. Three different solvent conditions (hexane/ethanol, 100:0, 95:5 and 75:25, vol/vol), combined in a factorial design with five levels of solvent (0, 10, 20, 30 and 40%, w/w), were used to develop the miscella. Equilibrium adsorption was not achieved during the 100 min of adsorption, mainly because the oil components were involved in oxidation reactions during the adsorption process. However, for a given solvent concentration, adsorption of the oil components showed a significant linear regression on their respective initial concentration in the miscella (C_i). Peroxides and carbonyls showed, at all solvent levels investigated, an affinity for the carbon more independent of their C_i than free fatty acids and carotenoids. In general, at the same C_i, a higher adsorption was achieved as solvent concentration increased. The results indicated that free fatty acid adsorption may depend on competitive adsorption based on molecule hydrophobicity. However, in spite of the higher hydrophobicity of carotenoids, compared with free fatty acids, they might not be competing for the same adsorbing sites. Ethanol showed a prooxidant effect that increased peroxide production during adsorption but did not affect the reaction involved in carbonyl production.     

Secretion and secretory tissues of the anal sac of the mink,Mustela vison

The sulfur-rich anal sac secretion of the mink,Mustela vison, consisted of immiscible lipid (1.7% sulfur) and aqueous (0.7% sulfur) phases. Light and electron microscopy revealed secretory tissue of two types, sebaceous (holocrine) and apocrine. A major input of sulfur into the sac appeared to be associated with glycoprotein granules present in the apical portions of the apocrine cells as X-ray energy probe microanalysis showed these to contain relatively high levels of sulfur. The lipid of the secretion, presumed to be largely of sebaceous origin, consisted mainly of wax monoesters, while the aqueous phase contained volatile fatty acids, ammonia, and amines, including putrescine (1,4-diaminobutane). The identity of the major headspace volatiles was confirmed by NMR, MS, and Raney nickel desulfuration as being 2,2-dimethylthiacyclobutane and 3,3-dimethyl-1, 2-dithiacyclopentane. These compounds were not detected by GC-MS in the headspace volatiles of the anal sac secretions of eight other mustelid species examined. Other sulfur compounds detected included isomeric dimethylthiacyclobutanes, a number of disulfides and 3-methyl-but-3-enyl methyl sulfide (isopentenyl methyl sulfide). The significance of these findings is discussed.     

Differently sized native milk fat globules separated by microfiltration: fatty acid composition of the milk fat globule membrane and triglyceride core

The aim of this study was to characterize the fatty acid composition of the core and membrane of differently sized milk fat globules separated by microfiltration, which can now be used to manufacture dairy products. Native milk fat globules of various mean diameters, ranging from d₄₃ = 2.3 µm to 8.0 µm, were obtained using microfiltration of raw whole milk. After milk fat globule washing, the milk fat globule membrane (MFGM) and the triglyceride core (TC) were separated by manual churning. After total lipid extraction from each fraction, their fatty acid composition was characterized using methyl ester analysis by gas chromatography. Regardless of season, no significant differences were observed in the fatty acid composition of the MFGM phospholipids. Conversely, significant differences were found in the fatty acid composition of TC; particularly, small fat globule TC contained more medium‐chain fatty acids and less stearic acid than large fat globule TC. These results show that the previously observed differences in total fatty acid composition among differently sized milk fat globules are due to their triglyceride composition and MFGM amount rather than to the composition of the MFGM.     

气相色谱-质谱联用法测定金属皂中的多环芳烃

建立了金属皂中16种美国环保局(EPA)优先监控的多环芳烃的气相色谱-质谱(GC/MS)联用测定方法,样品先用二甲基亚砜萃取,再用环己烷进行反萃取,经硅胶柱净化后,用GC/MS分离测定。优化了16种多环芳烃(PAHs)的分离测定条件,结果16种PAHs的平均回收率为75.32%￣98.72%,精密度实验相对标准偏差(RSD)为2.19%￣6.93%,检测限(S/N=5)为0.002￣0.010mg/kg。该方法灵敏度高、准确性好,完全可以满足金属皂中多环芳烃的检测要求。