Low‐Temperature Chemical Synthesis of High‐Purity Diacylglycerols (DAG) from Monoacylglycerols (MAG)

A chemical method was developed for low‐temperature synthesis of DAG from MAG followed by an easy purification procedure in order to obtain high‐purity DAG. Solvent‐assisted and solvent‐free reaction conditions were used, combined with different catalysts (sodium methoxide, p‐toluenesulfonic acid, methanesulfonic acid, and sulfuric acid). All reactions were performed at 35 and 70 °C. By increasing both acidity and polarity of the catalyst the equilibrium shifts towards the formation of DAG. When using sulfuric acid in solvent‐assisted condition at 70 °C, 88 % conversion was obtained after 20 min of reaction (77 % w/w DAG in the reaction mixture after evaporation of the solvent). After purifying by means of column chromatography, 96 % pure DAG were obtained. The overall yield of DAG was 81 %.     

Enzymatic Production of Diacylglycerols from High-Acid Soybean Oil

In this study, high-acid soybean oil, with acid values (Av) ranging from 10 to 50, was enzymatically deacidified for diacylglycerol (DAG) production. The effects of glycerol amounts were studied intensively. The glycerol amount could be calculated theoretically based on the Av of the raw oil (1 mol glycerol with 2 mol oleic acid to form 1 mol DAG, and 1 mol glycerol with 2 mol soybean oil to form 3 mol DAG). A total of 60–62% of DAG could be obtained and the free fatty acid (FFA) content was reduced to 0.36–0.66%. Increased glycerol did not lead to DAG content improvement. However, the glycerol amount based on just the deacidification theoretical calculation (1 mol glycerol with 2 mol oleic acid to form 1 mol DAG) was not feasible to reduce the FFA content. Moreover, Novozym 435 was rather stable in the present reaction procedure, no loss of activity was observed after 10 consecutive uses.     

Enzymatic Production of Monoacylglycerols with Camellia Oil by the Glycerolysis Reaction

Three commercial immobilized lipases, Lipozyme RM IM, Lipozyme TL IM and Novozym 435, were screened for the production of monoacylglycerols (MAG) by glycerolysis of camellia oil in a solvent medium of tert-butyl alcohol. Novozym 435 showed the best performance and was selected to catalyze the glycerolysis reaction. Different reaction conditions for the batch reaction, substrate mole ratio, substrate concentration and temperature, were investigated. The optimal reaction conditions were determined as 6:1 mole ratio of glycerol to camellia oil at 40% (w/v) of substrate concentration in tert-butyl alcohol at a reaction temperature of 50 °C. Under these optimal conditions, the conversion rate of camellia oil was 98.7% (10 h), and the mixture of acylglycerols contained 82.0% of MAG. A packed-bed reactor (PBR) system with 4.5 g Novozym 435 was employed in continuous production. The resulting product mixture of acylglycerols contained 80.74% of MAG and was obtained at a flow rate of 0.25 mL/min of substrates. The long-term operation of the PBR system gave an average productivity of 0.698 kg MAG/(kg enzyme h) after 38 days of operation.     

无溶剂酶催化油脂甘油解中温度效应的研究

以荧光假单胞菌脂肪酶为催化剂 ,进行无溶剂油脂甘油解反应合成单脂肪酸甘油酯。实验结果表明 :反应 2 4h时在所有实验体系中 ,反应温度高于 46℃时 ,产物中单甘酯平衡质量分数均低于 30 % ,最佳反应温度与体系最低共熔点有关。当体系最低共熔点约在 35～ 45℃时 ,临界温度 (TC)现象较明显 ,最佳反应温度接近于此反应体系的最低共熔点。油脂熔点和体系最低共熔点低于 35℃时 ,最佳反应温度及临界温度高于最低共熔点 ;油脂熔点和体系最低共熔点高于 45℃时 ,最佳反应温度低于最低共熔点。提出了第一临界温度和第二临界温度的概念     

Enzymatic Production of Highly Unsaturated Monoacyglycerols and Diacylglycerols and Their Emulsifying Effects on the Storage Stability of a Palm Oil Based Shortening System

MDs [monoacylglycerols (MAGs) and diacylglycerols (DAGs) mixture] are widely‐used emulsifiers in specialty fats industrial production. An enzymatic production of highly unsaturated MDs (HUSMDs) and its effects on the storage stability of a palm oil‐based shortening system are reported. Oleic acid and corn oil were used to produce HUSMDs in a bubble column reactor (BCR) system in the presence of Novozyme 435. Under the optimized reaction conditions, the content of HUSMDs in the products was above 82 wt% with 46.67 wt% of MAGs and 35.56 wt% DAGs, respectively. Moreover, in the subsequent evaluation of MDs’ effects on the storage stabilities of a palm oil‐based shortening system (IEPO), HUSMDs proved to be a potent emulsifier with decent aeration properties and a possible alternative to saturated MAGs and DAGs (SMDs) made from fully hydrogenated high erucic acid colza oil. Compared with SMDs, HUSMDs decreased the crystallization rate significantly. The microstructure of them shows improved stability of β′ crystals, and no obvious aggregation of crystals was recorded in IEPO with HUSMDs, which also demonstrated the most stable hardness.     

Production of Structured Triacylglycerol via Enzymatic Interesterification of Medium-Chain Triacylglycerol and Soybean Oil Using a Pilot-Scale Solvent-Free Packed Bed Reactor

Oils rich in medium- and long-chain triacylglycerols (MLCT) serve as functional oils to help reduce body fat accumulation and weight gain. However, most of the MLCT-rich products on the market are physical blends of medium- and long-chain triacylglycerols (MCT and LCT, respectively) that are not structured triacylglycerols (TAG). In this study, an efficient pilot-scale packed bed reactor (PBR) of immobilized lipase from Thermomyces lanuginosus (Lipozyme® TL IM, Novozymes, Bagsvaerd, Denmark) was employed for producing structured MLCT via 1,3-specific interesterification of TAG enriched in caprylic and capric acyl groups and soybean oil (SBO). The PBR was operated under continuous recirculation mode in the absence of solvent. Optimal reaction conditions were determined to be: caprylic/capric TAG: SBO ratio (45:55 w/w), reaction temperature (75 °C) and residence time (16.0 min) on MLCT production were studied. When employing a pilot-scale PBR (100 kg day⁻¹) under optimal conditions, a product containing 76.61 wt% MLCT was produced. Lipozyme TL IM was reused for 25 successive batch reactions (125 kg substrates) with no significant reduction in catalytic efficiency. The light yellow MLCT-enriched product had a high level of saturated fatty acids (SFA, 82.74 wt%) in its sn-2 position as a result of the enzyme's 1,3-positional specificity. One-stage molecular distillation and methanol extraction were used to remove the free fatty acids, mono-, and diacylglycerols generated from hydrolysis. With distillation temperature of 150 °C and oil-to-methanol ratio of 1:3 v/v, MLCT content was further increased to 80.07 wt%. The enzymatic PBR was therefore effective in producing structured MLCT at a pilot-scale under solvent-free conditions.     

Production of Monoacylglycerols from Fully Hydrogenated Palm Oil Catalyzed by Hydrotalcite Loaded with K2CO3

This study reports a new method of producing high-purity monoacylglycerols (MAGs) by glycerolysis of fully hydrogenated palm oil (FHPO) catalyzed by hydrotalcite loaded with K₂CO₃ (K₂CO₃/HT). The effects of reaction temperature, reaction time, catalyst (K₂CO₃/HT) loading, and mass ratio of FHPO to glycerol on glycerolysis were investigated. The selected conditions included a reaction temperature of 200°C, K₂CO₃/HT loading at 0.8 wt.% (FHPO mass), a 5:2 mass ratio of FHPO to glycerol, and a reaction time of 2 h. Under these selected conditions, the yield of MAGs in the acylglycerol phase reached 46.8 wt.%. A two-stage molecular distillation was introduced to purify MAGs, and the final MAG product was obtained with a purity of 96.6 wt.% and a recovery of 96.8%. Furthermore, the recycled K₂CO₃/HT was reactivated with restored catalytic efficiency through impregnation, carbonation, and recalcination.     

Preparation of Docosahexaenoic Acid-Rich Diacylglycerol-Rich Oil by Lipase-Catalyzed Glycerolysis of Microbial Oil from Schizochytrium sp. in a Solvent-Free System

Docosahexaenoic acid (DHA)-rich diacylglycerol (DAG)-rich oil was prepared by lipase-catalyzed glycerolysis of microbial oil from Schizochytrium sp. in a solvent-free system. The reaction parameters including lipase type, substrate molar ratio, temperature, lipase concentration, and reaction time were screened. The selected conditions were determined as follows: Novozym® 435 (Novozymes A/S, Bagsvaerd, Denmark) as biocatalyst at 8 wt%, substrate ratio (DHA-rich microbial TAG/glycerol) of 1:1 mol/mol, temperature of 50 °C, and reaction time of 12 hours. Under these conditions, the triacylglycerol (TAG), DAG, and monoacylglycerol (MAG) contents in the product were 36.4%, 48.2%, and 15.4%, respectively. The lipase was reused successively for 18 cycles without significant loss of activity under the conditions given above. Fatty acid composition analysis of the final product showed that the contents of DHA in TAG, DAG, and MAG were 53.9%, 44.9%, and 34.8%, respectively. DHA-rich DAG has the potential to be used as an ingredient in infant formula to increase the bioavailability of DHA.     

Influence of Water on Enzymatic Esterification of Racemic Ketoprofen with Ethanol in a Solvent-Free System

Topics in Catalysis - The effect of water added in the kinetic resolution of rac-ketoprofen with ethanol catalyzed with Candida antarctica lipase B was investigated under reaction conditions and at...     

在无溶剂系统中由植物油生产脂肪酸酯的一条新颖酯交换反应路线（英）

研究了长链醇和甲酯使用耐热的固定化脂肪酶生产蜡酯的技术。酯交换反应是将两种反应是将两种反应物以不同的化学计量混合,在低浓度酶制剂存在下,于５５℃－６５℃温度范围内连续搅拌完成。最适宜的操作温度为６０℃,油酸甲酯五硬脂醇的摩尔比为１：０．５。一般能够得到高酯化率。基质抑制作用由硬脂醇引起。动力学参数的研究证实了这些结论。     

智能化管线系统在采油厂输油系统的建设

河南油田管线具有线长、面广的特点,管线沿途环境复杂,穿越城镇人口密集区、河流等,安全风险管控难度大,发生事故后,社会负面影响大。为实现对管道的全过程、全生命周期的管理,建立了以管线数字化管理,完整性管理,管线运行管理为目标的智能化管线建设工程。     

Infrared Assisted Production of 3,4-Dihydro-2(1H)-pyridones in Solvent-Free Conditions

A green approach for the synthesis of a set of ten 4-aryl substituted-5-alcoxy carbonyl-6-methyl-3,4-dihydro-2(1H)-pyridones using Meldrum's acid has been devised, the absence of solvent and the activation with infrared irradiation in addition to a multicomponent protocol are the main reaction conditions. The transformations proceeded with moderated yields (50-75%) with a reasonable reaction rate (3 h). It is worth noting that two novel molecules of the new class of the bis-3,4-dihydropyridones were also obtained. In addition, a comparison without the use of infrared irradiation was performed.     

Characterization and comparison of oleogels and emulgels prepared from Schizochytrium algal oil using monolaurin and MAG/DAG as gelators

Oleogels and emulgels were developed with winterized algal oil from Schizochytrium spp. rich in ω-3 fatty acids (FAs) to overcome physical limitations of using a highly unsaturated lipid source in food applications. Both gel types were developed using monolaurin or a combination of mono- and diacylglycerols (MAG/DAG) as the gelator at concentrations of 8%, 10%, or 12% (w/w) in oil or emulsion. A 30-day oxidation study was conducted using peroxide value, p-Anisidine value, and change in FA composition to measure the level of oxidation. Oleogel and emulgel samples exhibited a higher oxidative stability than bulk algal oil and oil-in-water emulsion as control groups, respectively. The 12% monolaurin oleogel outperformed others in oxidative stability, preventing oxidation of approximately 11.66% and 7.86% of EPA and DHA, respectively, compared to algal oil. Physical characteristics including thermal behavior, solid fat content (SFC), rheology, morphology, and polymorphism were studied. Results indicated that MAG/DAG oleogels and monolaurin emulgels were the most physically stable. The SFC of 12% MAG/DAG oleogel at 30°C was 10.27% whereas 12% monolaurin oleogel was only 4.51%. Both gel types developed with monolaurin and MAG/DAG could be used for different applications as they exhibited desirable qualities such as oxidative stability and improved physical characteristics.     

Diacylglycerols from butterfat: Production by glycerolysis and short-path distillation and analysis of physical properties

The aim of this paper was to develop a process for the production of DAG from butterfat through glycerolysis and short-path distillation and to evaluate the physical properties of the DAG in comparison with the original butterfat. Chemical glycerolysis produced a mixture of acylglycerols containing DAG together with MAG and TAG. From the mixture of glycerolysis products, MAG were removed through three consecutive distillations (vacuum <0.001 mbar) at 150°C. TAG were separated from DAG by distillation at 210°C, which gave a product with more than 80% DAG in the distillates. Distillation temperatures had significant effects on acyl migration. The formation of desirable 1,3-DAG was favored at higher temperatures. Under 210°C distillation, the equilibrium ratio of 6∶4 was obtained between 1,3-DAG and 1,2(2,3)-DAG. The FA profile of the DAG product was relatively similar to the original butterfat. The total DAG recovery was around 77% in the pilot-scale production. The different patterns of m.p. were observed between butterfat and the DAG fraction produced as well as the MAG fraction collected. Solid fat content profiles of the DAG fraction and its mixtures with rapeseed oil possessed trends similar to those of the corresponding butterfat and its mixtures with rapeseed oil. Compared with butterfat, the DAG fraction behaved differently in its thermal profiles, crystallization patterns, and rheological properties; for example, the dropping point was 13°C higher for the latter than for the former, and the crystal pattern was mostly β form for the latter, whereas the former was the β′ form.     

Quantification of the Molecular Species of TAG and DAG in Lesquerella (Physaria fendleri) Oil by HPLC and MS

Ten diacylglycerols (DAG) and 74 triacylglycerols (TAG) in the seed oil of Physaria fendleri were recently identified by high‐performance liquid chromatography (HPLC) and mass spectrometry (MS). These acylglycerols (AG) were quantified by HPLC with evaporative light scattering detector and electrospray ionization mass spectrometry of the lithium adducts of the AG in the HPLC fractions of lesquerella oil. The MS¹ ion signal intensities of molecular ions [M + Li]⁺ in HPLC fractions of an HPLC peak were used to estimate the ratios of AG in the HPLC peak. The ratios of TAG with the same mass in HPLC fractions were estimated by the ratios of the sums of MS² ion signal intensities from the neutral loss of the three fatty acids [M + Li ? FA]⁺. The ratio of DAG with the same mass were estimated by the ratio of the sums of two MS² ion signal intensities [M + Li ? FA]⁺ and [FA + Li]⁺ from the two different FA of a DAG. We have estimated the contents of ten molecular species of DAG and 74 molecular species of TAG in P. fendleri oil using this new method. The content of ten DAG combined was about 1 % and 74 TAG was about 98 %. The contents of DAG in decreasing order were: LsLs (0.25 %), LsLn (0.25 %), LsO (0.24 %), and LsL (0.11 %); and the contents of TAG in decreasing order were: LsLsO (31.3 %), LsLsLn (24.9 %), LsLsL (15.8 %), LsL‐OH20:2 (4.3 %), LsO‐OH20:2 (2.8 %), and LsLn‐OH20:2 (2.5 %).     

The Effects of High Levels of Fats Rich in Erucic Acid (from Rapeseed Oil) or Cetoleic and Cetelaidic Acids (from Partially Hydrogenated Fish Oil) in a Short-Term Study in a Non-Human Primate Species I

Three experimental groups of primates (cynomolgus monkeys Macaca fascicularis) were adapted to high-fat diets and maintained on the diets for four months. One group (control) was fed a diet containing 25% of lard and corn oil in a 3 : 1 mixture and the other groups received either 25% of rapeseed oil or of partially hydrogenated herring oil. Docosenoic acids were approximately 25% of the rapeseed oil (as erucic acid) and of the partially hydrogenated herring oil (as a mixture of cetoleic acid and cetelaidic acid). Monitoring of physiological parameters did not reveal any important differences between groups. Fecal fatty acids and depot fatty acids showed differences in details of composition from the fatty acids in the diets. These are discussed in terms of intestinal microorganism activity, absorption processes, and in vivo alterations in the primates. In the two experimental groups skeletal and cardiac muscle showed lipidosis. This was especially evident in the apexes of the hearts of animals fed the rapeseed oil and partially hydrogenated herring oil. Fatty acid details from depot fat and cardiac apex triglycerides showed differences and further differences were discerned among the isomeric docosenoic and eicosenoic acids of the cardiac triglycerides. The histopathology of the primate hearts showed a few mild foci of inflammation in all groups which could not be associated with diet, whereas the same diets fed to male weanling rats induced the severe necrotic lesions widely associated with such diets. It is concluded that different species of animals show physiologically different responses to fat-based dietary factors and that further experiments with primates and with oils containing docosenoic acids are required to determine what, if any, cardiac problems exist.     

Identification of TAG and DAG and their FA Constituents in Lesquerella (Physaria fendleri) Oil by HPLC and MS

Castor oil has many industrial uses because of its high content (90 %) of the hydroxy fatty acid, ricinoleic acid (OH¹²18:1⁹). Lesquerella oil containing lesquerolic acid (Ls, OH¹⁴20:1¹¹) is potentially useful in industry. Ten molecular species of diacylglycerols and 74 molecular species of triacylglycerols in lesquerella (Physaria fendleri) oil were identified by electrospray ionization mass spectrometry as lithium adducts of acylglycerols in the HPLC fractions of lesquerella oil. Among them were: LsLsO, LsLsLn, LsLsL, LsLn–OH20:2, LsO–OH20:2 and LsL–OH20:2. The structures of the four new hydroxy fatty acid constituents of acylglycerols were proposed by the MS of the lithium adducts of fatty acids as (comparing to those in castor oil): OH¹²18:2^9,14 (OH¹²18:2^9,13 in castor oil), OH¹²18:3^9,14,16 (OH18:3 not detected in castor oil), diOH^12,1318:2^9,14 (diOH^11,1218:2^9,13 in castor oil) and diOH^13,1420:1¹¹ (diOH20:1 not detected in castor oil, diOH^11,1218:1⁹ in castor oil). Trihydroxy fatty acids were not detected in lesquerella oil. The differences in the structures of these C18 hydroxy fatty acids between lesquerella and castor oils indicated that the polyhydroxy fatty acids were biosynthesized and were not the result of autoxidation products.     

Ultrasound- and Microwave-Assisted Extractions Facilitate Oil Recovery from Gilthead Seabream (Sparus aurata) By-Products and Enhance Fish Oil Quality Parameters

This research aimed to analyze ultrasound (UAE) and microwave-assisted extraction (MAE) as novel technologies for utilizing gilthead seabream (Sparus aurata) by-products to produce high-quality fish oil for human consumption. The impacts of extraction parameters, namely, temperature, time, solvent-to-solid ratio, and their interactions on the extraction yield, are investigated using response surface methodology (RSM), and a central composite rotatable design. The optimized conditions are 15.47 mL g⁻¹ of solvent-to-solid ratio, 38 min, and 42 °C for UAE and 15.84 mL g⁻¹ of solvent-to-solid ratio, 18 min, and 40 °C for MAE. Under optimal conditions, the maximum extraction yields are 38.40 and 36.70% (g/g) for UAE and MAE, respectively. Both UAE and MAE have significantly higher mass transfer rates (61.70 and 121.58 g h⁻¹, respectively) than Soxhlet extraction (10.78 g h⁻¹). The fatty acid composition, physicochemical, and oxidation analyses of fish oils confirm the suitability of both UAE and MAE for the recovery of high-quality oils from fish processing by-products. The valorized oils mainly include unsaturated fatty acids (≈75%) and are rich in oleic acid. Furthermore, scanning electron microscopy analysis reveals that the key driving force for fast oil extraction is the structural degradation of fish by-products caused by ultrasound and microwave. Practical Applications: Due to environmental and economic viewpoints, the validation of fish oil from fish industry by-products has become a popular research topic recently. Alternative recovery techniques such as ultrasound- (UAE) and microwave-assisted extraction (MAE) protocols may have additional benefits in producing functional oils. Interactive effects of process parameters determine the success of the extraction technique; therefore optimization is a critical approach when applying the extraction protocols. This study shows that UAE and MAE techniques significantly enhanced oil extraction rate from gilthead seabream (Sparus aurota) by-products at lower temperatures and by using lower amounts of solvent. UVA and MAE increase oxidative stability and do not change the fatty acid composition. Hence, the by-product of the gilthead seabream can be a sustainable and food-grade fish oil source and UAE and MAE can be a good alternative to the conventional (Soxhlet) extraction by providing high yield and quality oil.     

Enzymatic Interesterification of Palm Stearin and Coconut Oil by a Dual Lipase System

Enzymatic interesterification of palm stearin with coconut oil was conducted by applying a dual lipase system in comparison with individual lipase-catalyzed reactions. The results indicated that a synergistic effect occurred for many lipase combinations, but largely depending on the lipase species mixed and their ratios. The combination of Lipozyme TL IM and RM IM was found to generate a positive synergistic action at all test mixing ratios. Only equivalent amount mixtures of Lipozyme TL IM with Novozym 435 or Lipozyme RM IM with Novozym 435 produced a significant synergistic effect as well as the enhanced degree of interesterification. The interesterification catalyzed by Lipozyme TL IM mixed with thermally inactivated immobilized lipase preparations indicated that the carrier property may play an important role in affecting the interaction of two mixed lipases and the subsequent reactions. A dual enzyme system, consisting of immobilized lipases and a non-immobilized one (Lipase AK), in most cases apparently endows the free lipase with a considerably enhanced activity. 70% Lipase AK mixed with 30% immobilized lipase (Lipozyme TL IM, RM IM and Novozym 435) can achieve an increase in activity greater than 100% over the theoretical value when the reaction proceeds for 2 h. The co-immobilization action of the carrier of the immobilized lipases towards the free lipase was proposed as being one of the reasons leading to the synergistic effect and this has been experimentally verified by a reaction catalyzed by a Lipase AK-inactivated preparation. No apparently synergistic effect of the combinations of Lipozyme TL IM and RM IM was observed when the dual enzyme systems applied to the continuous reaction performed in a packed bed reactor. In brief, this work demonstrated the possibility of increasing the reaction rate or enhancing the degree of conversion by employing a dual lipase system as a biocatalyst.