Continuous production of structured phospholipids in a packed bed reactor with lipase from <Emphasis Type="Italic">Thermomyces lanuginosa</Emphasis>

The possibilities of producing structured phospholipids between soybean phospholipids and caprylic acid by lipase-catalyzed acidolysis were examined in continuous packedbed enzyme reactors. Acidolysis reactions were performed in both a solvent system and a solvent-free system with the commercially immobilized lipase from Thermomyces lanuginosa (Lipozyme TL IM) as catalyst. In the packed bed reactors, different parameters for the lipase-catalyzed acidolysis were elucidated, such as solvent ratio (solvent system), temperature, substrate ratio, residence time, water content, and operation stability. The water content was observed to be very crucial for the acidolysis reaction in packed bed reactors. If no water was added to the substrate during reactions under the solvent-free system, very low incorporation corporation of caprylic acid was observed. In both solvent and solvent-free systems, acyl incorporation was favored by a high substrate ratio between acyl donor and phospholipids, a longer residence time, and a higher reaction temperature. Under certain conditions, the incorporation of around 30% caprylic acid can be obtained in continuous operation with hexane as the solvent. Presented at the 95th American Oil Chemists' Society Annual Meeting and Expo in Cincinnati, Ohio, May 10, 2004.     

Quantitation of acyl migration during lipase-catalyzed acidolysis, and of the regioisomers of structured triacylglycerols formed

Various MLM-type (M, medium-chain fatty acids; L, long-chain fatty acids) structured triacylglycerols were produced in pilot- or small-scale packed-bed reactors by lipasecatalyzed acidolysis. The incorporation and acyl migration of octanoic acid were measured by gas chromatography and Grignard degradation, and ranged from 39.0 to 48.7% and 0.6 to 9.3%, respectively. Quantitation of triacylglycerol molecular species was performed by ammonia negative ion chemical ionization (NICI) mass spectrometry (MS). The proportion of ACN (acyl carbon number) 34 species that contained one C₁₈ fatty acid and two C_8∶0′ in samples analyzed, varied from 12.5 to 23.2%. The selected regioisomers MLM and MML within the ACN 34 species group were quantified by NICI tandem MS (MS/MS) and were in the range of 97.1 to 98.4% and 1.6 to 2.9%, respectively. There was no correlation between the level of acyl migration during lipase-catalyzed esterification and the level of regioisomers of the selected MLM-type triacylglycerols in the structured lipid samples.     

非水相介质杂醇油酶法转化天然酯类香料的研究

为提高杂醇油的利用率和附加值,研究非水相条件下杂醇油的脂肪酶催化酯化反应,优化其转化为天然酯类香料的工艺条件.结果表明,酶用量、分子筛用量、乙酸加入次数及间隔时间、摇床转速、反应温度、反应时间等因素条件对产物酯的生成有重要影响,采用间歇式加酸、加入适量分子筛吸水剂可明显提高混合酯得率.在正已烷10mL、杂醇油3ml、乙酸1.5mL的反应体系中,正交试验设计优化后的工艺条件(乙酸异戊酯产率最高时):脂肪酶Novozym435FG用量70mg、乙酸分6次加入、加入乙酸间隔时间3h、分子筛用量2g、摇床转速140r/min、反应温度45℃、反应时间36h.该条件下,乙酸异戊酯、乙酸异丁酯和乙酸丙酯的产率分别为90.1％,91.3％,78.1％.     

非水相中脂肪酶催化合成糖酯类食品添加剂的研究进展

糖酯类食品添加剂是同时含有亲水和疏水基团、HLB值为1～16的一种非离子型表面活性剂,具有无臭、无味、无毒及优良的表面性能等特点,在食品工业中具有诱人的应用前景。脂肪酶非水相催化合成糖酯有着化学合成法无可比拟的优点,已引起众多研究者的广泛关注。本文就非水相中催化合成糖酯所用脂肪酶的来源、非水相体系、酶的催化活性、糖酯类食品添加剂的检测方法及其在食品工业中的应用进行了综述,并展望其发展前景。     

Lipozyme RM IM脂肪酶催化苦瓜籽油和癸酸合成功能性油脂

以苦瓜籽油为原料,利用癸酸在脂肪酶Lipozyme RM IM的催化下进行结构修饰,来降低苦瓜籽油中桐酸的含量。选取底物物质的量的比、加酶量、反应温度、反应时间为影响因素,采用响应面分析法进行反应条件优化,得最佳反应条件为底物物质的量的比(苦瓜籽油:癸酸)=1:4、加酶量(占底物质量的质量分数)12.5%、反应温度60℃、反应时间14.8h。在此最优反应条件下得到的新油脂中癸酸含量为47.12%,同时桐酸含量由反应前苦瓜籽油中的56.17%降为25.46%。     

13C3-三硬脂酸甘油酯的合成与表征

以¹³C₃-甘油和硬脂酸为原料,在无溶剂的条件下,采用Lipozyme酶为催化剂,直接酯化合成¹³C₃-三硬脂酸甘油酯,产率为80%,产物无需纯化。经差示扫描量热分析（DSC）、红外光谱（FT-IR）、核磁共振（H NMR）、质谱（MS）分析表征,结果表明,产物为目标产物¹³C₃-三硬脂酸甘油酯,化学纯度＞98%,同位素丰度＞99%,产物可作为同位素内标物使用。     

Rapid synthesis of fatty acid esters for use as potential food flavors

Lipase-catalyzed esterification has been performed in hexane to generate novel mixtures of fatty acid esters from specially chosen combinations of fatty acids and alcohols. By varying the alcohol and enzyme compositions in the enzymatic reactions, different ester mixtures were produced, which were further purified and analyzed for ester composition by gas chromatography-mass spectrometry. Depending on the combination of alcohols and enzymes used, the final ester mixture exhibited significant compositional variation. These mixtures could be manipulated at the synthesis step, thereby enabling a high degree of product control. Such manipulation over enzyme-catalyzed ester synthesis in mixtures may be useful in the preparation of ester flavors for use in the food industry.     

影响酶法酯交换中甘二酯含量的因素研究

甘二酯是酶法酯交换过程中重要的中间体.较高的甘二酯含量影响最终产品的纯度,也导致副产物的产生.研究了酶法催化酯交换过程中反应温度、反应时间、水含量、酶用量、底物比对甘二酯含量的影响.实验结果表明,反应体系中酶量是影响甘二酯含量的最大影响因素,且为正相关.在符合产品结构的较优的反应中,甘三酯含量为88.2%,甘二酯含量为6.9%.     

Characterization of primary fatty amides produced by lipase-catalyzed amidation of hydroxylated fatty acids

A novel hydroxylated primary fatty amide was produced from lesquerolic acid by direct amidation with ammonia catalyzed by immobilized Pseudozyma (Candida) antarctica lipase B (Novozym 435) in organic solvent. The amides of ricinoleic acid and oleic acid were also produced for comparison. The hydroxy FA were transformed at comparable rates to that of oleic acid. The rate of amide formation was greater for the longerchain lesquerolic acid than for ricinoleic acid. All products exhibited characteristic primary-amide mass spectrum peaks with a base peak at m/z 59 and a strong ion fragment at m/z 72. Other peaks present are consistent with cleavage on either side of the hydroxyl position. The mass spectra, together with ¹H and ¹³C NMR data, suggest that the products of lipase-catalyzed direct amidation of ricinoleic acid and lesquerolic acid are 12-hydroxy-9(Z)-octadecenamide and 14-hydroxy-11(Z)-eicosenamide, respectively.     

A process for the preparation of food-grade rice bran wax and the determination of its composition

A two-step method was developed for the preparation of food-grade wax. The first step involved the solventdefatting of crude wax, which gave a dark brown, dry, powdered wax with a m.p. of 75–79°C. The major impurity in the defatted wax was the dark brown resinous matter. In the second step, the resinous matter was removed by bleaching with sodium borohydride in isopropanol. This step yielded a pale yellow, odorless wax with purity higher than 99% and with a m.p. of 80–83°C. The resinous matter was a mixture of aliphatic aldehydes, fatty alcohols, and FA. High-temperature GC analysis of the purified rice bran wax indicated that it contained 11 major and 9 minor types of saturated wax esters. The major and minor peaks contained C₄₄–C₆₄ and C₄₅–C₅₉ wax esters, respectively. Rice bran wax was mainly a mixture of saturated esters of C₂₂ and C₂₄ FA and C₂₄ to C₄₀ aliphatic alcohols, with C₂₄ and C₃₀ being the predominant FA and fatty alcohol, respectively. The alcohol portion of the wax esters also contained small amounts of branched and odd carbon number fatty alcohols.