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The interesterification process allows structured lipids (SLs) to be obtained with a modified triacylglycerol (TAG) structure, in which the unfavorable saturated fatty acids (SFAs) are replaced with nutritionally significant fatty acids (FAs) such as monounsaturated (MUFAs) and polyunsaturated (PUFAs). Oxidative stability is crucial for the quality of SLs. This study aimed to characterize and evaluate the FA profile and oxidative stability of SLs synthesized by the enzymatic interesterification of hemp seed oil (HO) and coconut oil (CO) blends. Blends were prepared in three ratios (75% HO:25% CO, 50% HO:50% CO, and 25% HO:75% CO) and interesterified using sn-1,3 regiospecific lipase for 2 or 6 h. FA composition, the FA distribution of TAGs, acid value (AV), peroxide value (PV), and oxidation time were analyzed and compared to non-interesterified blends. Results showed no significant difference in the SFA:MUFA ratios between interesterified and non-interesterified blends with the same proportions. Lauric acid predominantly occupied the sn-2 position in all blends. Interesterified blends had higher AVs, exceeding codex standards, while PVs remained within the acceptable limits. Blends with 75% HO had lower oxidation times compared to those with 75% CO, with no significant difference between interesterified and non-interesterified blends. In the interesterification process of the studied blends, new TAGs with a modified structure were created, which may affect their physical and nutritional properties. This process also had a significant effect on the AV and PV levels, but not on the oxidation time of the modified blends. Therefore, it is necessary to remove free FAs after the enzymatic process to produce SLs characterized by improved hydrolytic stability. This will lead to better technological properties compared to the original oils. Further research is also necessary to enhance the oxidation stability of SLs obtained from blends of CO and HO to improve their storage stability.

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The aim of this study is to combine flaxseed oil (FO), rich in α-linolenic acid (ALA), with Sunite sheep tail fat (STF) through a lipase-catalyzed transesterification reaction, in order to produce an edible oil with a fatty acid ratio suitable for human needs. Initially, the optimal conditions for esterification were determined using the Box-Behnken design, with the measurement criterion being the content of ALA at the sn-2 position. The results indicated that the highest content of sn-2 ALA was obtained under the conditions of using 6.8 wt% Lipozyme®RMIM as the catalyst, a reaction temperature of 57°C, a reaction time of 3.3 h, and a substrate mass ratio of 5.6:4.4 for STF and FO. This led to the rapid breaking and recombining of molecular bonds, resulting in the interesterified fat (IF) with the highest content of ALA at the sn-2 position. Comparing STF and FO, IF exhibited excellent fatty acid composition and content. Furthermore, IF had a lower melting point and crystallization temperature compared to STF, and its solid fat content decreased with increasing temperature, completely melting at temperatures above 30°C. Thus, IF is a synthesized fat with excellent properties from both animal and vegetable sources.

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Medium and long-chain triacylglycerol (MLCT) rich in n-3 polyunsaturated fatty acids (PUFAs) were obtained in three-hour interesterification of fish oil with medium-chain triacylglycerol (MCTs), using lipase bio-imprinted with surfactant as a catalyst. Initially, for bio-imprinted lipase preparation, the interesterification reaction conditions were optimized, resulting in a lipase with 1.47 times higher catalytic activity compared to control (non-bio-imprinted). Afterwards, the reaction conditions for MLCT synthesis were optimized, using bio-imprinted lipase as a catalyst. The reaction reached equilibrium within first three hours at 70 °C temperature, 4 wt% lipase load, and molar ratio of substrate 1:1.5. Under these conditions, final product contained 18.52% MCT, 56.65% MLCT, and 24.83% long-chain triacylglycerol (LCT). To reduce the MCT content, a solvent extraction process was performed, yielding 2.42% MCT, 56.19% MLCT, and 41.39% LCT. The obtained structured lipids (SLs), enriched in n-3 PUFAs, offer significant health benefits, enhanced bioavailability, with potential applications in functional foods and nutraceuticals.

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This paper reports the preparation of margarine fat using Lipozyme TL IM as a catalyst and peony seed oil (PSO), palm stearin (PS) and coconut oil (CO) as raw materials. The results indicate that there were no significant changes in fatty acid composition before or after interesterification of the oil samples. However, the total amount of medium- and long-chain triglycerides (MLCTs) increased from 2.92% to 11.38% in sample E1 after interesterification, mainly including LaLaO, LaMO, LaPM, LaOO, LaPO and LaPP. Moreover, the slip melting point (SMP) of sample E1 decreased from 45.9 °C (B1) to 33.5 °C. The solid fat content (SFC) of all the samples at 20 °C was greater than 10%, indicating that they could effectively prevent oil exudation. After interesterification, the samples exhibited a ß' crystal form and could be used to prepare functional margarine.

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This work presents the experimental assessment of a 20 mL batch reactor's efficacy in converting plastic and oil residues into biofuels. The reactor, designed for ease of use, is heated using a metallic system. The experiments explore plastic solubilization at various temperatures and residence times, employing a mixture of distilled water and ethylene glycol as the solvent. Initial findings reveal that plastic solubilization requires a temperature of 350 °C with an ethylene glycol mole fraction of 0.35, whereas 250 °C suffices with a mole fraction of 0.58. Additionally, the study includes a process simulation of a plant utilizing a double fluidized bed gasifier and an economic evaluation of the interesterification/pyrolysis plant. Simulation results support project feasibility, estimating a total investment cost of approximately $12.99 million and annual operating expenses of around $17.98 million, with a projected payback period of about 5 years.

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Lipases with high interesterification activity are important enzymes for industrial use. The lipase from Burkholderia stagnalis (BsL) exhibits higher interesterification activity than that from Burkholderia plantarii (BpL) despite their significant sequence similarity. In this study, we determined the crystal structure of BsL at 1.40 Å resolution. Utilizing structural insights, we have successfully augmented the interesterification activity of BpL by over twofold. This enhancement was achieved by substituting threonine with serine at position 289 through forming an expansive space in the substrate-binding site. Additionally, we discuss the activity mechanism based on the kinetic parameters. Our study sheds light on the structural determinants of the interesterification activity of lipase.

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The relationship between batch and continuous enzymatic interesterification was studied through enzymatic interesterification of beef tallow. The interesterification degree (ID) during the batch reaction was monitored based on triacylglycerol composition, sn-2 fatty acid composition, solid fat content, and melting profile and was described by an exponential model. A relationship equation featuring reaction parameters of the two reations was established to predict the ID and physicochemical characteristics in continuous interesterification. The prediction of the ID based on triacylglycerol composition was reliable, with an R2 value greater than 0.85. Interesterification produced more high-melting-point components for both reactions, but the acyl migration in the batch-stirring reactor was much greater, resulting in faster crystallization, a more delicate crystal network, and lower hardness. The relationship equation can be employed to predict the ID, but the prediction of physicochemical properties was constrained by the difference in acyl migration degree between the two reactions.

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Candida antarctica lipase B (CALB) is regarded as non-regiospecific. This study aimed to investigate the regiospecificity of CALB in the solvent-free interesterification of high-oleic sunflower oil with stearic acid ethyl ester for 1,3-distearoyl-2-oleoylglycerol (SOS)-rich fat preparation using a packed bed reactor. The content ratio of 1,2-distearoyl-3-oleoylglycerol (SSO) to SOS (denoted by SSO/SOS content) obtained using Lipozyme 435 (a commercially immobilized CALB; 0-4.1%), at residence times (1-32 min) was similar to that obtained using Lipozyme RM IM (0-3.0%), but lower than that obtained using Lipozyme TL IM (6.0-39.4%). When immobilized on Lewatit VP OC 1600, Lipozyme CALB had an SSO/SOS content of 0-10.4%, which was greater than that of Palatase 20,000 L (0-1.1%) but was lower than that of Lipozyme TL 100 L (8.8-97.7%). Our findings suggest that immobilized CALB shows distinct sn-1,3 regiospecificity in the interesterification of triacylglycerol with fatty acid ethyl esters.

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Elongation of the Very-Long-Chain Fatty Acids-4 (ELOVL4) enzyme that is expressed in neuronal tissues, sperm, and testes mediates biosynthesis of very-long-chain polyunsaturated fatty acids (VLC-PUFAs) from dietary long chain PUFAs (LC-PUFAs). The VLC-PUFAs are critical for neuronal and reproductive function. Therefore, mutations in ELOVL4 that affect VLC-PUFA biosynthesis contribute to retinal degenerative diseases including Autosomal Dominant Stargardt-like Macular Dystrophy (STGD3). Recent studies have also shown not only a depletion of retinal VLC-PUFAs with normal aging but also a more significant loss of VLC-PUFAs in donor eyes of patients with age-related macular degeneration (AMD). However, currently, there are no natural sources of VLC-PUFAs to be evaluated as dietary supplements for the attenuation of retinal degeneration in animal models of STGD3. Here, we report the development of a novel chemical approach for elongation of eicosapentaenoic (C20:5 n-3) and docosahexaenoic (C22:6 n-3) acids from fish oils by 6 carbon atoms to make a unique group of VLC-PUFAs, namely all-cis-hexacosa-11,14,17,20,23-pentaenoic acids (C26:5 n-3) and all-cis-octacosa-10,13,16,19,22,25-hexaenoic acids (C28:6 n-3). The three-step elongation approach that we report herein resulted in a good overall yield of up to 20.2%. This more sustainable approach also resulted in improved functional group compatibility and minimal impact on the geometrical integrity of the all-cis double bond system of the VLC-PUFAs. In addition, we also successfully used commercial deep-sea fish oil concentrate as an inexpensive material for the C6 elongation of fish oil LC-PUFAs into VLC-PUFAs, which resulted in the making of gram scales of VLC-PUFAs with an even higher isolation yield of 31.0%. The quality of fish oils and the content of oxidized lipids were key since both strongly affected the activity of the PEPPSI-IPr catalyst and ultimately the yield of coupling reactions. Downstream enzymatic interesterification was used for the first time to prepare structured glycerolipids enriched with VLC-PUFAs that could be evaluated in vivo to determine absorption and transport to target tissues relative to those of the free fatty acid forms. It turned out that in the synthesis of structured triacylglycerols and glycerophospholipids with VLC-PUFAs, the polarity of the immobilized lipase carrier and its humidity were essential.

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Lipases (EC 3.1.1.3) are enzymes used in the oils and fats industries to modify the physicochemical properties of triacylglycerol (TAG). Lipase-catalyzed interesterification at high temperatures is an effective method for modifying the physicochemical properties of TAG. The lipase from Burkholderia plantarii (BpL) exhibits excellent catalytic activity for non-regiospecific interesterification at high temperatures, with depressed lipase hydrolytic activity. The detailed catalytic mechanism for reactions involving catalytic residues has not been elucidated because of the lack of a conventional method for estimating interesterification activity. We used our original water-in-oil emulsion system to estimate the interesterification activity of lipases. BpL showed 10% hydrolytic and 140% interesterification activities compared to the lipase from Burkholderia cepacia, which has a high sequence homology with BpL. By comparing the sequence and crystal structure data of the lipases, we clarified that two amino acids near the active center are one of the factors controlling the hydrolytic and interesterification activities of the enzyme.

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Edible beef tallow (BT) has been widely used in Sichuan hotpot due to its unique flavor and texture. However, BT should not be consumed in excess caused by its trans-fatty acids and cholesterol issues. In this study, a BT substitute was prepared after enzymatic interesterification in a pilot-scale packed-bed reactor using soybean oil and fully hydrogenated palm oil (4:3, w/w) as feedstock. The products were characterized against BT in terms of fatty acid/triacylglycerol compositions, solid fat content, polymorphism, and melting/crystallization behaviors to select the most promising BT substitute. The optimal flow rate was 120 mL/min. Changes in volatile compounds during stir-frying and simmering were also investigated for Sichuan hotpots made with these two oils. The volatile compounds of BT substitute were similar to that of natural BT. The findings will contribute to expanding the base oil categories of Sichuan hotpot oils.

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This study aimed to produce stable plastic fat with desired physicochemical characteristics and ω-6/ω-3 fatty acid ratio (1:1-4:1) from palm stearin (PS), flaxseed oil (FSO) and cottonseed stearin (CS) via enzymatic interesterification (EIE). For the first time, the EIE variables of the blends containing PS, FSO and CS were investigated and optimized through single-factor experiments and response surface design to achieve a high interesterification degree. The optimized enzymatic interesterification conditions were: 60°C, 6 wt% Lipase UM1, and 6 h. Lipase UM1 had a similar effect on ID values with commercial lipases. The EIE improved the compatibility of the lipid blends, with the interesterified product EIE-721 (7:2:1, PS: FSO:CS) being the best candidate base stock for shortening considering its solid fat content, desired ω-6/ω-3 fatty acid ratio, wide melting range, abundant ß' form crystal, and compact microstructure. This study provides a strategy to produce balanced ω-6/ω-3 fatty acid plastic fat through enzymatic interesterification and validates the application of Lipase UM1 in the preparation of plastic fat.

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The present study sought to develop a novel healthy margarine fat with low levels of trans and saturated fatty acids in order to promote healthier alternatives. In this work, tiger nut oil was first used as a raw material to prepare margarine fat. The effects of mass ratio, reaction temperature, catalyst dosage, and time on the interesterification reaction were investigated and optimized. The results showed that, the margarine fat with ≤40% saturated fatty acids was achieved using a 6:4 mass ratio of tiger nut oil to palm stearin. The ideal interesterification parameters were 80 °C, 0.36% (w/w) catalyst dosage, and 32 min. Compared with physical blends, the interesterified oil had lower solid fat content (3.71% at 35 °C), lower slip melting point (33.5 °C), and lower levels of tri-saturated triacylglycerols (1.27%). This investigation provides important information for the utilization of tiger nut oil in healthy margarine formulation.

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In the present work, the acid-catalyzed interesterification of glyceryl trioctanoate (GTO) with ethyl acetate was investigated as a model reaction for the one-step production of biofuel and its additives. The activity of heterogeneous acid catalysts, such as silica-based propyl-sulfonic ones, was evaluated. Propyl-sulfonic groups were grafted on both amorphous and mesoporous silica oxide (SBA-15, KIT-6) using different functionalization processes and characterized by N2 adsorpion-desorption isotherm (BET), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, and potentiometric titration. During the optimization of the reaction conditions with the most active catalyst (Am-Pr-SO3H), it was shown that the addition of ethanol allowed a total conversion of GTO together with 89% and 56% yield of ethyl octanoate and triacetin, respectively. The catalytic performance is strictly correlated to the catalyst features, in terms of both the acid capacity and the porous structure. Moreover, the catalytic performance is also affected by a synergistic mechanism between silanols and Pr-SO3H groups towards the 'silanolysis' of ethyl acetate. The overall results show that the presence of ethanol, the reaction time, and the amount of catalyst shifts the reaction towards the formation of the biofuel mixture composed by ethyl octanoate and triacetin.

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The natural properties of oils and fats do not always allow for their direct use in industry (e.g., for food, cosmetics, and pharmaceuticals). Furthermore, such raw materials are often too expensive. Nowadays, the requirements for the quality and safety of fat products are increasing. For this reason, oils and fats are subjected to various modifications that make it possible to obtain a product with the desired characteristics and good quality that meets the needs of product buyers and technologists. The modification techniques of oils and fats change their physical (e.g., raise the melting point) and chemical properties (e.g., fatty acid composition). Conventional fat modification methods (hydrogenation, fractionation, and chemical interesterification) do not always meet the expectations of consumers, nutritionists, and technologists. In particular, Hydrogenation, while it allows us to obtain delicious products from the point of view of technology, is criticised for nutritional reasons. During the partial hydrogenation process, trans-isomers (TFA), dangerous for health, are formed. One of the modifications that meets current environmental requirements and trends in product safety and sustainable production is the enzymatic interesterification of fats. The unquestionable advantages of this process are the wide spectrum of possibilities for designing the product and its functional properties. After the interesterification process, the biologically active fatty acids in the fatty raw materials remain intact. However, this method is associated with high production costs. Oleogelation is a novel method of structuring liquid oils with small oil-gelling substances (even 1%). Based on the type of oleogelator, the methods of preparation can differ. Most oleogels of low molecular weight (waxes, monoglycerides, and sterols) and ethyl cellulose are prepared by dispersion in heated oil, while oleogels of high molecular weight require dehydration of the emulsion system or solvent exchange. This technique does not change the chemical composition of the oils, which allows them to keep their nutritional value. The properties of oleogels can be designed according to technological needs. Therefore, oleogelation is a future-proof solution that can reduce the consumption of TFA and saturated fatty acids while enriching the diet with unsaturated fatty acids. Oleogels can be named "fats of the future" as a new and healthy alternative for partially hydrogenated fats in foods.

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Medium-long-medium (MLM) structured lipid (SL) as a new SL is a potential functional ingredient in food and nutraceutical products, but its composition-structure-physicochemical properties relationship has not been revealed in food industry. MLM type of medium-long chain triacylglycerol (MLCT) was synthesized from Camellia oil by combi-lipase; its physicochemical properties and composition-structure relationship were investigated in this research. The higher MLCT (67.24% ± 0.09) and MLM (52.71% ± 0.53) productivities were achieved after parameter optimization. The physicochemical characterization of SLs exhibited mild thermal property, intermediate Fourier transform infrared spectroscopy absorption intensity, and better crystal morphology. Joint characterizations identified that MLM and long-medium-long type SL were rich in 1,3-dioctanoyl-2-linoleoyl glyceride (CaLCa), 1,3-dioctanoyl-2-oleoyl glyceride (CaOCa), 1,3-dilinoleoyl-2-octanoyl glyceride (LCaL), and 1,3-dilinoleoyl-2-decanoyl glyceride (LCL) components, respectively. This is ascribed to the higher proportion of caprylic and linoleic acid in 1,3-specific enzyme. The 3D structural analysis further demonstrated that the CaLCa, CaOCa, LCaL, and LCL molecules had lower steric energy to form symmetrical structure at 1,3-position. This research provides a practical method to produce MLM-type SL from edible oils and fats in food industry.

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Crude olive pomace oil (OPO) is a by-product of olive oil extraction. In this study, low-calorie structured triacylglycerols (TAGs) were produced by acidolysis of crude OPO with medium-chain fatty acids (caprylic, C8:0; capric, C10:0) or interesterification with their ethyl ester forms (C8EE, C10EE). These new TAGs present long-chain fatty acids (L) at position sn-2 and medium-chain fatty acids (M) at positions sn-1,3 (MLM). Crude OPO exhibited a high acidity (12.05-28.75% free fatty acids), and high contents of chlorophylls and oxidation products. Reactions were carried out continuously in a packed-bed bioreactor for 70 h, using sn-1,3 regioselective commercial immobilized lipases (Thermomyces lanuginosus lipase, Lipozyme TL IM; and Rhizomucor miehei lipase, Lipozyme RM IM), in solvent-free media at 40 °C. Lipozyme RM IM presented a higher affinity for C10:0 and C10EE. Lipozyme TL IM preferred C10:0 over C8:0 but C8EE over C10EE. Both biocatalysts showed a high activity and operational stability and were not affected by OPO acidity. The New TAG yields ranged 30-60 and the specific productivity ranged 0.96-1.87 g NewTAG/h.g biocatalyst. Lipozyme RM IM cost is more than seven-fold the Lipozyme TL IM cost. Therefore, using Lipozyme TL IM and crude acidic OPO in a continuous bioreactor will contribute to process sustainability for structured lipid production by lowering the cost of the biocatalyst and avoiding oil refining.

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Computationally simulated micelle models provide useful structural information on the molecular and biological sciences. One strategy to study the self-aggregation process of surfactant molecules that make up a micelle is through molecular dynamics (MD) simulations. In this study, a theoretical approach with a coarse-grained MD simulation (CG-MD) was employed to evaluate the critical micellar concentration (CMC), the micellization process, building a tridimensional (3D) model system of a micelle using data from the experimentally enzymatically modified phospholipids (PL) by phospholipase A1 (PA1). This required enzymatic interesterification of soybean phosphatidylcholine (PC) with caprylic acid, along with purification and characterization by chromatographic techniques to measure the esterified fatty acids and the corresponding PL composition. The number of molecules used in the CG-MD simulation system was determined from the experimental CMC data which was 0.025%. The molecular composition of the system is: 1 C 18:2, 2 C 8:0/8:0, 3 C 8:0/18:3n-9, 4 C 8:0/18:0, 5 C8:0/18:2n-6, 6 C8:0/18:1n-9, and 7 C 8:0/16:0. According to our theoretical results, the micelle model is structurally stable with an average Rg of 3.64 ± 0.10 Å, and might have an elliptical form with a radius of 24.6 Å. Regarding CMC value there was a relationship between the experimental data of the modified PLs and the theoretical analysis by GC-MD, which suggest that the enzymatic modification of PLs does not affect their self-aggregation properties. Finally, the micellar system obtained in the current research can be used as a simple and useful model to design optimal biocompatible nanoemulsions as possible vehicles for bioactive small molecules.Communicated by Ramaswamy H. Sarma.

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To address the problems of long reaction times and limited range of adaptation in enzymatic synthesis medium- and long-chain triacylglycerols (MLCTs), a broadly applicable solvent-free enzymatic interesterification strategy was proposed. Candida sp. lipase (CSL) was immobilized on hydrophobic hollow mesoporous silica spheres (HHSS) to construct a biocatalyst designated as CSL@HHSS with a 15.3 % immobilization yield and a loading amount of 94.0 mg/g. The expressed activity and the specific activity were 20.14 U/g and 173.62 U/g, which were 4.6 and 5.6 times higher than that of free CSL, respectively. This biocatalyst demonstrated higher activity, wider applicability, and excellent reusability. Linseed oil, sunflower oil, perilla seed oil, algal oil, and malania oleifera oil were applied as substrates to produce MLCTs with medium-chain triacylglycerols (MCT) catalyzed by CSL@HHSS through interesterification in yields ranging from 69.6 % to 78.0 % within 20 min. Specific fatty acids, including linolenic acid, oleic acid, DHA, and nervonic acid (the first reported), were introduced into MLCT's skeleton, respectively. The structures were finely analyzed and identified by GC and UPLC-MS. The catalytic efficiency value of CSL@HHSS in catalyzing interesterification between linseed oil and MCT (70 ℃, 20 min, lipase 6 wt%) is 0.86 g/g∙min, which is the highest ever reported. This paper presents an effective and sustainable strategy for functional MLCTs production.

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Palm olein (POL) was modified by enzymatic interesterification with different degrees of acyl migration in a solvent-free packed bed reactor. The fatty acid and acylglycerol composition, isomer content, thermodynamic behavior, and relationship between crystal polymorphism, solid fat content (SFC), crystal microstructure, and texture before and after modification were studied. We found that the increase in sn-2 saturation interesterification was not only due to the generated tripalmitin (PPP) but also caused by acyl migration, and the SFC profiles were changed accordingly. The emergence of high melting point acylglycerols was an important factor accelerating the crystallization rate, further shortening the crystallization induction time, leading to the formation of large crystal spherulites, thereby reducing the hardness. The transformation from the ß' to the ß form occurred during post-hardening during storage. The isomer content also affected the physicochemical properties of the modified POL.

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