Chemo-enzymatic synthesis of amino acid-based surfactants

The application of lipases to the synthesis of amino acid-based surfactants was investigated. Low yields (2–9%) were obtained in the acylation of free amino acids, such as l-serine and l-lysine, as well as their ethyl esters and amides with fatty acids, owing in part to low miscibility of the reactants. When the N-carbobenzyloxy (Cbz)-l-amino acids were used in an effort to improve miscibility of the amino acid derivatives with the acyl donor, a dramatic improvement was observed for N-Cbz-l-serine (92% yield) but not for N _α-Cbz- or N _ζ-Cbz-l-lysine (7 and 2% yield, respectively). As an alternative, and efficient synthesis of N _ζ-acyl-l-lysines was developed, based on the regiospecific chemical acylation of copper(II) lysinate. In pursuit of a general route to amino acid-fatty acid surfactants, the utility of a polyol linker was investigated. Thus, the glycerol ester of N _α′ N _ζ-di-Cbz-l-lysine was prepared and evaluated as a substrate for acylation. As expected, this and other glycer-1-yl esters of N-protected amino acids were excellent substrates for lipase-catalyzed acylation. Their reaction with myristic acid in the presence of Novozyme resulted in the regioselective acylation of the primary hydroxyl group of the glycerol moiety to afford the corresponding 1-O-(N-Cbz-l-aminoacyl)-3-O-myris-toylglycerols with conversions of 50–90%. These were readily deprotected to give a range of 1-O-(aminoacyl)-3-O-myristoyl-glycerols with overall yields of 27–71%.     

Clarity of blends of double-fractionated palm olein with low-erucic acid rapeseed oil

Double-fractionated palm olein (DfPOo) fractions with iodine values (IV) of 60 and 65 were each blended with low-erucic acid rapeseed (LEAR) oil in various proportions. Clarities of the blends at different temperatures were determined. Maximum levels of DfPOo-IV60 and DfPOo-IV65 in blends that remained clear at 20°C for at least 120 d were 40 and 80%, respectively. At 15°C, the maximum levels were 10 and 40%, and at 10°C, 10 and 20%, respectively. At 5°C, only a blend of 10% DfPOo-IV65 in LEAR remained clear for 120 d. Maximum levels of DfPOo-IV60 and DfPOo-IV65 in blends that passed the cold test were 30% for both palm oleins. Maximum levels of the palm oleins in blends with LEAR were higher than those of blends with soybean oil. Cloud points were lower in palm olein/LEAR blends than those of palm olein/soybean oil blends, probably because LEAR contains less saturated fatty acids than soybean oil.     

化妆品中果酸的限量及检测

本文叙述了化妆品中果酸的种类及对皮肤的作用机理，讨论了果酸促进皮肤细胞更新能力和刺激性之间的关系以及化妆品中果酸的浓度限量问题，并介绍了一种应用高效液相色谱法检测化妆品中五种果酸含量的新方法。     

Direct ethoxylation of fatty methyl ester over Al-Mg composite oxide catalyst

For the purpose of estimating the reaction mechanism of the direct ethoxylation of a fatty ester in the presence of an Al-Mg composite oxide catalyst, a labeled fatty methyl ester C₁₁H₂₃CO¹⁸OCH₃ containing ¹⁸O isotope was synthesized and directly ethoxylated. The product was evaluated by gas chromatography-mass spectrometry (GC-MS). The GC-MS spectra showed that the ¹⁸O isotope label was present only in the methoxy group at the molecular end of the ethoxylated fatty methyl ester. This supports the reaction mechanism of coordination anionic polymerization where the bond between the acyl and methoxy groups of the fatty methyl ester molecule was broken, caused by the bifunctional effect of the acid-base active sites; an intermediate chemisorption species was formed; and then ethylene oxide was addition-polymerized sequentially, in parallel.     

脂肪醇聚氧乙烯(3)醚低温浑浊原因的探讨

通过在AEO3中添加不同加成数的AEO进行低温浑浊试验，并分析比较AEO3低温分层后的上清液与下层浑浊物中AEO的分布，发现EO加成数在5以上的AEO是导致AEO3低温浑浊的原因之一。在AEO3及其上清液中分别添加不同质量分数的脂肪醇、水以及醋酸钠进行低温浑浊试验，发现脂肪醇、水分和醋酸钠不是造成AEO3低温浑浊的原因，但会使AEO3在低温下容易冻结。     

聚乙二醇对脂肪醇聚氧乙烯醚低温浑浊影响的研究

通过一系列低温浑浊试验考察了聚乙二醇含量与分子质量对脂肪醇聚氧乙烯醚(AEO3)低温浑浊的影响，并分析AEO3低温分层后的上清液和下层浑浊物中聚乙二醇的含量与分布，发现分子质量在600以上的聚乙二醇是影响AEO3低温浑浊的重要原因。     

Antioxidant efficacy of amino acids in methyl linoleate at different relative humidities

Antioxidant efficacy of the amino acids methionine, tryptophan, aspartic acid, serine, alanine and arginine in methyl linoleate were compared to a methyl linoleate control at 2,50 or 79% relative humidity (RH) at 37°C. Antioxidant efficacy varied with RH and the individual amino acids. Arginine had the highest antioxidant efficacy at all RH values compared to the control. The efficacy of alanine was equal to that of arginine at RHs of 50 and 79% but was lower at 2% RH. The presence of aliphatic, alkaline amino, hydroxyl or thiol groups in the side chain of the amino acids increased the antioxidant efficacy at high RHs.     

Fatty acid selectivity of lipases: Erucic acid from rapeseed oil

The fatty acid selectivity of several commercial lipases was evaluated in the hydrolysis of high-erucic acid rapeseed oil (HEARO). The lipase ofPseudomonas cepacia catalyzed virtually complete hydrolysis of the oil (94–97%), while that ofGeotrichum candidum discriminated strongly against erucic acid, especially in esterification. A two-step process is suggested for obtaining a highly enriched erucic acid in which theG. candidum lipase is employed to selectively esterify the fatty acid residues of unsaturated C-18, and shorter chain acids, from a mixture of HEARO fatty acids obtained from total hydrolysis of the oil withP. cepacia lipase.     

FA composition and regiospecific analysis of Acer saccharum (sugar maple tree) and Acer saccharinum (silver maple tree) seed oils

GC analysis was performed to determine regiospecific distribution and FA composition in seed oils of the Aceraceae species, Acer saccharum and A. saccharinum. The oil content in the seeds was low at 5.0% in A. saccharum and 5.8% in A. saccharinum, and the main FA were linoleic (30.8 and 29.4%), oleic (21.3 and 27.6%), palmitic (10.1 and 10.5%), and cis-vaccenic (9.4 and 7.9%) acids, respectively. In addition, both oils contained long-chain monoenes of the n−9 and n−7 groups, including 11-eicosenoic, 13-docosenoic, 15-tetracosenoic, 13-eicosenoic, and 15-docosenoic acids, whereas γ-linolenic acid accounted for 0.8% of total FA in A. saccharum, and 0.5% in A. saccharinum. Regiospecific analysis, performed using the methodology of dibutyroyl derivatives of MAG, indicated that linoleic, oleic, and linolenic acids were mainly esterified at the internal position of TAG in both seed oils, whereas long-chain monoenes of the n−7 group were almost exclusively esterified on the external positions.     

Effects of physical refining on contents of waxes and fatty alcohols of refined olive oil

Changes in the contents of waxes and fatty alcohols during deodorization/physical refining of bleached olive oil were studied. Experiments were carried out with 1.85% acidity oil, which was physically refined in a discontinuous deodorizer of 250-kg maximum capacity using nitrogen as stripping gas instead of steam. The variables studied were load and temperature of oil in the deodorizer as well as N₂ flow. Analyses of waxes and alcohols were carried out at different operation times. The maximum content of wax was always observed when the oil reached the deodorization temperature. The variation in the wax content depended on temperature and N₂ flow. Wax decomposition started and continued during the operating time, and a progressive decrease, which was pronounced between 3 and 4 h, was observed. Small changes in waxes were observed between 4 and 5 h. Total content of fatty alcohols diminished throughout the operating time, and changes did not depend on the variables studied.