Glycerolysis Products Research Articles

In vitro digestion study comparing a predigested glycerolysis product versus long-chain polyunsaturated fatty acid-rich oils (LCPUFA) as a strategy for administering LCPUFA to preterm neonates

Background & aimsMaintaining an adequate supply of arachidonic acid (ARA) and docosahexaenoic acid (DHA) is essential for optimal growth of preterm infants. This study aims to evaluate and compare the digestibility and bioaccessibility of ARA and DHA oils compared to their predigested product through an in vitro digestion model. MethodsAn in vitro gastrointestinal digestion model was used in two stages: gastric digestion and intestinal digestion. Samples of two polyunsaturated rich oils (ARA and DHA oils) and their predigested product (2:1, ARA: DHA) produced by enzymatic glycerolysis have been digested for 120 min. The final digestion product obtained was composed of three phases: an upper oily phase (OP) containing the undigested species, an intermediate micellar phase (MP) containing digested and bioaccessible lipids, and a precipitate phase (PP) with insoluble compounds. The reaction was monitored by taking aliquots and their subsequent lipid extraction and analysis. ResultsPoorer digestibility for ARA and DHA oils was observed based on the percentage of the oily phase (26.7% and 20%, respectively) found compared to the glycerolysis product (GP) oily phase (13.9%). The highest micellar phase was found in the GP (approx. 83%). On the other hand, the monoglyceride (MAG) content was lower in the digestion product (DP) from ARA and DHA oils, 4.3% and 9.2%, respectively, compared to the MAG observed in the DP of GP (15%). ConclusionConsidering the percentage of oily phase, micellar phase, and the MAG content, it can be concluded that the GP is more digestible and ARA and DHA are more bioaccessible than in its precursor oils.

Rheological properties of ethylcellulose oleogels of oil glycerolysis products as functional adipose tissue mimetics

Comparative analysis of the rheological behavior of fat analogues and adipose tissue is useful as a means of better understanding the behavior of these ingredients in reformulation and cooking processes. Fat mimicking oleogels were developed based on various enzymatically glycerolized oils and ethylcellulose (EC) of differing molecular weights at a 5% concentration. The dynamic rheological behavior of the oleogels and adipose tissue of different origins (pork, beef, lamb) was studied via amplitude and frequency sweeps. Glycerolized oils and their oleogels behaved as solid-like materials, as elastic moduli were greater than viscous moduli throughout the linear viscoelastic region. Addition of EC produced a more deformable and cohesive product. Solid fat content was a dominant contributor to viscoelastic properties of GP-EC oleogels. Oil systems containing higher levels of saturated fatty acids such as palm olein and shea olein exhibited a more rigid structure, with stiffness comparable to that of pork and beef adipose tissue. Whereas tigernut, peanut, and rice bran oil oleogels were significantly softer and more deformable. Temperature sweep experiments were conducted to visualize the general softening behavior during cooking. The melting of fat dramatically softened both adipose tissue and oleogels. However, the microstructure of adipose tissue was intricately linked to its protein matrix at elevated temperatures, leading to substantial increase of elasticity from 50 °C to 80 °C. Oleogels exhibited thixotropic behavior by recovering their elasticity and functionality over time once the force is removed. This characteristic minimizes the shear related issues during and after the gel-setting process.

Ethylcellulose oleogels of oil glycerolysis products as functional adipose tissue mimetics

Replicating the functionality of animal fat with its plant/microbial counterparts plays a key role in successful design of plant-based analogues of animal-derived foods. Given the intricate structure of animal adipose tissue, merely substituting animal fats in plant foods with saturated bulk fats and oils often results in compromised mechanical and sensory attributes. Animal adipose tissue is comprised of adipocytes encapsulated by connective tissue. Simply replacing this tissue with coconut oil will not succeed in creating a true meat mimetic. Enzymatically glycerolized oils are derived from the conversion of native triacylglycerols in oils into partial glycerides. They are a promising fat alternative that could diminish the need for tropical and hydrogenated oils in plant-based meat products. Oils can be converted into fats using a mild enzymatic reaction without the use of hydrogenation or addition of saturated hardstocks. In this study, we explored the potential of oleogels made from glycerolysis products to mimic adipose tissue. Utilizing various enzymatically structured oils, we formulated oleogels with ethylcellulose (EC) of differing molecular weights (EC20 and EC45) at a 5% concentration. The thermal, microstructural, and mechanical properties of the oleogels were compared to those of whole pork, beef, and lamb adipose tissue. In general, the thermal and structural characteristics of both EC45 and EC20 oleogels closely matched those of the glycerolysis products they originated from. Mechanical properties largely depended on the solid fat content, with oleogel systems richer in saturated fatty acids exhibiting more ordered and rigid structure, akin to adipose tissue. Additionally, pronounced resemblance was observed in thermal softening behavior of some of oleogel systems and that of animal adipose tissue. Our findings highlight the potential of EC oleogels from glycerolysis products in creating meat substitutes, thus preventing the characteristic oil-loss from plant-based meat alternatives when cooked, which lead to dry and grainy sensory textures.

Glycerolysis of palm kernel oil catalized by MgO on mono and diglyceride composition and their antibacterial activity

Monoglyceride and diglyceride are known as emulsifiers that have been used in the food industry. Furthermore, both mono and diglyceride also have the potential to be utilized as antibacterial compounds. Both of them can be produced from natural source, such as palm kernel oil, via glycerolysis reaction. This study aims to determine the effect of temperature and time of glycerolysis reaction on the composition of mono and diglyceride and their capability as an antibacterial agent. This study used a split-plot design with the temperature of glycerolysis as the main plot (80°C, 90°C, and 100°C) and the time of glycerolysis as the subplot (3, 4, and 5 hours). Several parameters were analyzed, including acid value, percent conversion, and antibacterial activity. Then, Gas Chromatography-Mass Spectrometry (GC-MS) was used to analyze glycerolysis products. Our results showed that the variations in temperature and time of glycerolysis had no effect on acid numbers, percentage conversion, and antibacterial activity. In addition, the glycerolysis products have a higher zone of inhibition against Bacillus subtilis compared to Escherichia coli. The highest percentage of conversion was obtained at glycerolysis temperature of 100°C and 5 hours. From the results of GC-MS analysis, monolaurin was obtained at 12.06 percent area.

Enzymatic glycerolysis for the conversion of plant oils into animal fat mimetics

Substituting animal-based fats with plant-based fats of similar stability and functionality has always posed a significant challenge for the food industry. Enzymatic glycerolysis products are systems formed by converting native triacylglycerols in liquid oils into monoacylglycerols and diacylglycerols, mainly studied in the last few years for their unique structural ability. This study aims to modify and scale up the glycerolysis process of different plant oils, e.g., shea olein, palm olein, tigernut, peanut, cottonseed, and rice bran oils, with the goal of producing animal fat mimetics. The reactions were conducted at 65 °C, with a plant oil:glycerol molar ratio of 1:1, and without the addition of water, using a lab-scale reactor to convert up to 2 kg of oil into solid fat. Product characteristics were comparable at both laboratory and pilot plant scales, supporting the commercial viability of the process. Oil systems containing higher levels of both saturated and monounsaturated fatty acids, such as shea olein and palm olein, displayed higher solid fat content at elevated temperatures and broader melting profiles with significantly higher melting points. Comparison of the thermal softening behavior and mechanical properties of these systems with those of pork, beef, and lamb fat showed their high potential to replace adipose fat in the new generation of plant-based meat analogs.

Oxidative stability of microalgae oil and its acylglycerol mixture obtained by enzymatic glycerolysis and the antioxidant effect of supercritical rosemary extract

The oxidative stability of microalgae oil (MO) and its enzymatic glycerolysis product (GP) have been determined by using the accelerated oxidation methods differential scanning calorimetry (DSC) and Rancimat at temperatures in the range 50–90 °C. Kinetic analyses of MO and GP provide Arrhenius activation energy and activation enthalpy and entropy, temperature coefficients, Q10 and oxidative stability index at 20 °C (OSI20), based on secondary and tertiary oxidation products. Susceptibility of microalgae oil to oxidation has been compared to that of fish and vegetable oils, with OSI20 values of 647 h for MO and 381 h for GP. The tcoeff and Q10 values are very similar to those observed for fish and vegetable oils. Protective effect from oxidation of a supercritical rosemary extract (RE) for both MO and GP have been evaluated. In the presence of this antioxidant, up to twofold increase of OSI20 has been obtained for MO. Lower protection for GP was observed. Activity antioxidant Index (AAI), related to the mechanism of action of the antioxidant, should be carefully examined for a reliable determination of OSI20 values.

Enzymatic Glycerolysis of Palm Kernel Olein-Stearin Blend for Monolaurin Synthesis as an Emulsifier and Antibacterial.

Monolaurin is a monoacylglycerol, which can act as an emulsifier and antibacterial. Palm kernel oil is a monolaurin raw material that can be fractionated into palm kernel olein (PKOo) and palm kernel stearin (PKS). Therefore, this study prepares monolaurin through enzymatic glycerolysis of the PKOo-PKS blend. The effects of enzyme concentration, molar ratio of oil to glycerol, solvent to oil ratio, and reaction temperature on the products of glycerolysis were investigated. The best conditions were selected for further production, purification, and characterization of the monolaurin. The results showed that the best glycerolysis condition was obtained with an enzyme concentration of 10% w/w, an oil–glycerol molar ratio of 1:4, a solvent–oil ratio of 2:1 v/w, and a glycerolysis temperature of 40 °C with a stirring speed of 600 rpm based on the monoacylglycerol (MAG) concentration. The identification of the sample with FTIR and NMR indicated that the purified glycerolysis product is the monolaurin. The thermal analysis showed a large endothermic peak with a melting point of 35.56 °C. The purified monolaurin has a HLB value of 5.92, and an emulsion capacity and stability of 93.66 ± 1.85% and 89.54 ± 3.36%, respectively. The minimum inhibitory concentration (MIC) of the monolaurin for Escherichia coli FNCC 0091 and Staphylococcus aureus FNCC 0047 were at 500 ppm, and 100 ppm for Bacillus subtilis FNCC 0060.

Lipase-catalyzed glycerolysis extended to the conversion of a variety of edible oils into structural fats

Lipase-catalyzed glycerolysis was recently shown to be a viable technique to structure cottonseed and peanut oils into structural fats by converting native triacylglycerols into partial glycerides without changing overall fatty acid composition. Here, this approach was extended to a variety oils of differing fatty acid compositions. Reactions were performed at 65 ​°C for 48 ​h at a triacylglycerol:glycerol molar ratio of 1:1, using the non-regiospecific Candida antarctica lipase B. In all oil systems, a 20 ​°C increase in crystallization onset temperature was observed following glycerolysis. Solid fat content increases resulting from glycerolysis were greatest for oils containing >10% saturated fat along with a high oleic acid content. The solid fat content of tigernut oil at 5 ​°C increased from 8% to 34% following glycerolysis. Tigernut glycerolysis product was used to make margarine with plasticity similar to commercial margarine and butter. This research demonstrates that glycerolysis is a general strategy to convert liquid oils into structural fats used in food applications, and thus replace palm oil and hydrogenated fats.

In vitro digestibility and bioaccessibility of lipid-based delivery systems obtained via enzymatic glycerolysis: a case study of rosemary extract bioaccessibility.

This work studies the effect of enzymatic glycerolysis on digestibility and bioaccessibility of ratfish liver oil (RLO) rich in alkylglycerols (AKGs), as well as the capability of the glycerolysis product (GP) to act as lipid-based delivery system (LBDS) for a supercritical rosemary extract. For comparison purposes, digestibility and bioaccessibility of two additional lipid systems i.e. original RLO and RLO with addition of GRAS monoolein (MO) as emulsifier agent (RLO + MO), have been evaluated. We have studied the efficiency of the GP and RLO + MO lipid systems as LBDS by combining them with a supercritical rosemary extract (RE), i.e. RE lipid-based formulations. In vitro digestibility and bioaccessibility of un-loaded lipid systems, RE lipid-based formulations and un-carried RE have been determined. The results show a higher digestibility and bioaccessibility of the GP as compared to those of original RLO and RLO + MO. Likewise, a substantial improvement of RE bioaccessibility has been observed when GP is used as lipid carrier of RE. The present work demonstrates that enzymatic glycerolysis is an efficient strategy to obtain highly bioaccessible and potentially bioactive alkylglycerol-based delivery systems, which can be used to increase the bioaccessibility of low water-soluble bioactive compounds.

Glycerolysis of Poly(lactic acid) as a Way to Extend the "Life Cycle" of This Material.

The article concerns the use of glycerolysis reaction as an alternative method of processing post-production and post-consumer waste from poly(lactic acid) (PLA). Management of waste is a very important issue from an environmental protection and economic point of view. Extending the “life cycle” of PLA is extremely important because it allows to make the most of this material. It also limits economic losses resulting from its disposal in the biodegradation process at the same time. This paper presents a method of glycerolysis of poly(lactic acid) waste using various amounts of anhydrous glycerol (mass ratio from 0.3 to 0.5 parts by weight of glycerol per 1.0 part by weight of PLA). This process was also carried out for pure, unmodified PLA Ingeo® (from NatureWorks) to compare the obtained results. The six liquid oligomeric polyhydric alcohols were obtained as a result of the synthesis. Then, they were subjected to physicochemical tests such as determination of color, smell, density, viscosity, and pH. In addition, the obtained raw materials were subjected to analytical tests such as determination of the hydroxyl value, acid value, water content, and elemental composition. The average molecular weights and dispersity were also tested by gel permeation chromatography (GPC). The assumed chemical structure of the obtained compounds was confirmed by spectroscopic methods such as FTIR, 1H NMR, 13C NMR. Glycerolysis products were also subjected to differential scanning calorimetry (DSC) to determine thermal parameters. The obtained research results have allowed the precise characterization of newly obtained products and determination of their suitability, e.g., for the synthesis of polyurethane (PUR) materials.

P-3-8 サトウキビバガスのマイクロ波グリセロリシスにより分離した抗ウイルス活性物質の構造と作用機構の解析

P-3-8 サトウキビバガスのマイクロ波グリセロリシスにより分離した抗ウイルス活性物質の構造と作用機構の解析

Poly(urea-urethane) nanoparticles using mono- and diacylglycerol from glycerolysis of castor oil as biopolyol and stabilizer

Vegetable oils as renewable raw materials for polymer synthesis are considered a clean and environment-friendly alternative to substitute partially, and to some extent totally, petroleum-based monomers. In this work, enzymatic glycerolysis of castor oil with Novozym 435 (C. antarctica lipase B) as catalyst was performed in a solvent-free system at 70 °C. The glycerolysis product was used as biopolyol and stabilizer for the synthesis of poly(urea-urethane) (PUU) nanoparticles via miniemulsion polymerization. Results showed that the PUU particles size increased with solids content and z-average particle diameters ranging from 167 to 282 nm when the solids content was increased from 20 to 40 wt%. All lattices were stable towards sedimentation, although the latex with lower particle size exhibited a higher stability. Thereby, this work showed a green route to produce stable PUU lattices from renewable resources without the use of any additional surfactant.

Lipase-catalyzed glycerolysis of anchovy oil in a solvent-free system: Simultaneous optimization of monoacylglycerol synthesis and end-product oxidative stability

The production of mono- and diacylglycerols rich in polyunsaturated fatty acids is achieved in this study, by solvent-free glycerolysis of anchovy oil with lipase PS-DI from Burkholderia cepacia. Attention is focused on the oxidative stability of the reaction products, determined in terms of induction time (It). The effects of glycerol/triacylglycerol molar ratio, enzyme concentration, and reaction temperature on mono- and diacylglycerol production and It are all assessed. The operating conditions that optimized monoacylglycerol yields and oxidative stability were a glycerol/triacylglycerol ratio of 3/1, 9.0% (w/w) Lipase PS-DI, a stirring rate of 200 rpm, and a reaction time of 4 h, at 45.8 °C, producing a content of 24.8% and 51.9% of mono- and diacylglycerols, respectively, over an It of 1.41 h. The glycerolysis conditions determined by simultaneous optimization strategy increased the oxidative stability of the glycerolysis products by 68%, which rose from 0.84 h (individual optimization) to 1.41 h.

Separation of glycerolysis product using hexane

Hexane is non-polar solvent and it can dissolve triglyceride and free fatty acid. The aim of this research is to get the hexane ratio to the glycerolysis product that can produce product that has the best characteristics. The study was conducted in five stages. In the first stage, the physicochemical properties of palm oil were analysed. In the second stage, palm oil glycerolysis was conducted. In the third stage, glycerolysis product was extracted by using hexane in various concentrations. In the following stage, physicochemical properties of extracted products were analysed. In the last stage, data were subjected to an analysis of variance. Results showed that ratio between glycerolysis product to hexane in this work did not significantly (α=0.05) affect the yield, the free glycerol content, and the ability of extracted products to reduce the surface tension of water. It was also found that the best treatment had yield of 28.5%. It was able to lower water surface tension from 72.00 to 31.80 dynes/cm and had free glycerol content of 2.40%. Base on this work, we found that further research need to be done.

Improving Yield of 1,3-Diglyceride by Whole-Cell Lipase fromA. NigerGZUF36 Catalyzed Glycerolysis via Medium Optimization

1,3-Diglyceride (1,3-DG) has attracted considerable attention as a healthful food oil component. In this study, we reported a novel method to synthesis of 1,3-DG via glycerolysis of triglyceride (TG) catalyzed by whole-cell lipase from a new isolated strain, Aspergillus niger GZUF36. The glycerolysis products include major diglyceride and minor monoglyceride. To improve yield of 1,3-DG, the optimized medium for the strain was obtained by combination of single-factor experiments, Plackett-Burman (PB), the steepest ascent and Box-Behnken design (BBD). Using the optimized medium, yield of 1,3-DG synthesized by the whole-cell lipase was 26.90 mol% and 1.42-fold yield was improved. The optimized medium lays the foundation for further studies of the reaction system for synthesis of 1,3-DG. The whole-cell catalyzed-glycerolysis process represents a significant advance toward achieving economical production of 1,3-DG at industrial scale.

Production of extremely pure diacylglycerol from soybean oil by lipase-catalyzed glycerolysis

Research work was objectively targeted to synthesize highly pure diacylglycerol (DAG) with glycerolysis of soybean oil in a solvent medium of t-butanol. Three commercial immobilized lipases (Lipozyme RM IM, Lipozyme TL IM and Novozym 435) were screened, and Novozym 435 was the best out of three candidates. Batch reaction conditions of the enzymatic glycerolysis, the substrate mass ratio, the reaction temperature and the substrate concentration, were studied. The optimal reaction conditions were achieved as 6.23:1 mass ratio of soybean oil to glycerol, 40% (w/v) of substrate concentration in t-butanol and reaction temperature of 50 °C. A two-stage molecular distillation was employed for purification of DAG from reaction products. Scale-up was attempted based on the optimized reaction conditions, 98.7% (24 h) for the conversion rate of soybean oil, 48.5% of DAG in the glycerolysis products and 96.1% for the content of DAG in the final products were taken in account as the results.

Regiospecific Analysis of Mono‐ and Diglycerides in Glycerolysis Products by GC × GC‐TOF‐MS

AbstractComprehensive bidimensional gas chromatography coupled with time‐of‐flight mass spectrometry (GC × GC‐TOF‐MS) was used for the characterization of regiospecific mono‐ and diglycerides (MG‐DG) content in the glycerolysis products derived from five different lipids included lard (LA), sun flower seed oil (SF), corn oil (CO), butter (BU), and palm oil (PA). The combination of fast and high temperature non‐orthogonal column set namely DB17ht (6 m × 0.10 mm × 0.10 μm) as the primary column and SLB‐5 ms (60 cm × 0.10 mm × 0.10 μm) as the secondary column was applied in this work. System configuration involved high oven ramp temperature to obtain precise mass spectral identification and highest effluent's resolution. 3‐Monopalmitoyl‐sn‐glycerol (MG 3‐C16) was the highest concentration in LA, BU and PA while monostearoyl‐sn‐glycerol (MG C18) in CO and 1,3‐dilinoleol‐rac‐glycerol (DG C18:2c) in SF. Principal component analysis accounted 82% of variance using combination of PC1 and PC2. The presence of monostearoyl‐sn‐glycerol (MG C18), 3‐Monopalmitoyl‐sn‐glycerol (MG 3‐C16), 1,3‐dilinoleol‐rac‐glycerol (DG C18:2c), 1,3‐dipalmitoyl‐glycerol (DG 1,3‐C16), and 1,3‐dielaidin (DG C18:1t) caused differentiation of the samples tested.

Enzymatic Glycerolysis of Palm and Palm Kernel Oils

Glycerolysis of palm and palm kernel oils were carried out using commercial lipases from Candida antarctica (Novozym 435) and Mucor miehei (Novozym 388) as catalyst (500 units lipase/g oil) at 40°C and with an oil:glycerol molar ratio of 1:2 in a solvent-free system. Novozym 435 catalyzed the glycerolysis of palm and palm kernel oils giving reaction products in similar compositions. Partial acylglycerols contents of the glycerolysis products obtained from palm and palm kernel oils were 64% (wt) and 66% (wt), respectively. However, partial acylglycerols contents of the glycerolysis products obtained from palm and palm kernel oils conducted with Novozym 388 as catalyst at the same conditions were 44% (wt) and 56% (wt), respectively. On the other hand, free fatty acid contents of the glycerolysis products of palm and palm kernel oils obtained using Novozym 388 were higher, 25–30% (wt), than those obtained by Novozym 435, 4–5% (wt). The monoacylglycerols fraction with the highest content of oleic acid, 62.7% (wt), was obtained from the palm kernel oil glycerolysis reaction catalyzed by Novozym 435.

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

AbstractThe 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.

Solvent-free glycerolysis of palm and palm kernel oils catalyzed by commercial 1,3-specific lipase from Humicola lanuginosa and composition of glycerolysis products

Glycerolysis of palm and palm kernel oils were conducted using a commercial 1,3-specific lipase from Humicola lanuginosa (trade name: SP 398) as catalyst (500 units lipase g−1 oil) at 40 °C and oil:glycerol (1:2 mol mol−1) in a solvent-free system. After 24 h, the glycerolysis products of palm and palm kernel oils consisted of 23% triacylglycerols, 18% monoacylglycerols, 38% diacylglycerols and 18% triacylglycerols, 31% monoacylglycerols, 42% diacylglycerols, respectively. The monoacylglycerol fraction of the glycerolysis product of palm oil was enriched in oleic acid. Palmitic acid content of the monoacylglycerol fraction of the same product was less than that of the original oil. Under the same conditions, monacylglycerol fraction of the palm kernel oil glycerolysis product was enriched in palmitic, stearic and oleic acids.