Glyceride Synthesis Research Articles

Lower-dose vs high-dose oral bisphenol S action of lipid metabolism in liver of male SD rat via mediating different SREBP isoforms

Bisphenol S (BPS) is commonly used for the industrial production of thermal paper, polycarbonate plastics, epoxy resins and other materials. Studies have reported that BPS can lead to triglyceride (TAG) or/and cholesterol (CHO) accumulation in the liver in zebrafish and mice, but the reasons for the different types of lipids that accumulate in the liver following BPS exposure are unclear. Here, the influences of lower-dose (10 mg/kg body weight/day) and high-dose (50 mg/kg body weight/day) BPS exposure to male SD rats on the accumulation of different lipids in the liver were explored. The results indicated that BPS treatment increased the levels of acetyl-CoA and glycogen in the liver. A lower dose of BPS upregulated the mRNA and protein expression levels of sterol regulatory element-binding protein 1 (srebp1), which is involved in the de novo synthesis of TAG in the liver, thus promoting the synthesis of glycerides (diacetylglyceride and TAG). However, a higher dose of BPS induced CHO accumulation, but inhibited the mRNA expression of genes (i.e., srebp2, hmgcr and hmgcs) involved in the de novo synthesis of CHO in the liver. Excessive accumulation of glycerides and CHO led to destruction of the physiological structure of rat liver, causing disorders in liver function. Our data provide new insight into the different mechanisms by which glyceride and CHO accumulate in the liver after BPS exposure.

Candida antartica lipase-catalyzed esterification for efficient partial acylglycerol synthesis in solvent-free system: Substrate selectivity, molecular modelling and optimization

Partial acylglycerols are valued for their emulsifying and stabilizing properties, yet precise green synthesis remains challenging due to low yield and selectivity. This study aimed to elucidate the “lipase selectivity-substrate structure-product composition” relationship to enhance the yield of targeted partial acylglycerol. The results showed that lipase exhibited a greater selectivity towards fatty acids with shorter chain lengths and higher unsaturation. Hydroxyl donors also affected the esterification process, with the enzyme-acyl complex exhibiting selectivity towards hydroxyl donors as follows: glycerol > monoacylglycerol > diacylglycerol. Substrate ratio significantly influenced enzymatic reactions; a 10:1 ratio favored triacylglycerol formation (>80 %), while a 1:1 ratio produced > 90 % partial acylglycerols. Molecular docking simulations revealed that substrates primarily interacted with lipase through hydrogen bonding and hydrophobic interactions. A comprehensive understanding of lipase selectivity patterns could facilitate the design of more efficient reaction systems, enabling the conversion of basic lipid resources into desired high value-added products.

A decade development of lipase catalysed synthesis of acylglycerols using reactors: a systematic review

Abstract Glycerol esterification produces a variety of valuable chemicals and has been a subject of great interest in recent years. Lipase-catalysed synthesis of acylglycerols reactions have many potential applications, including in the production of structured lipids, biofuels and pharmaceuticals. It offers several benefits over traditional chemical methods, including higher selectivity, milder reaction conditions and increased sustainability. In this systematic review, we summarize 52 primary research of lipase catalysed synthesis of acylglycerol published from 2012 to 2022. Different types of reactions employed in the synthesis of acylglycerols using various lipases are thoroughly discussed. The use of lipase in as biocatalyst in the synthesis of acylglycerols is safe for consumption and sustainable as it can reduce the utilization of toxic and hazardous organic solvents and chemicals that cause harm to human health and the environment. This review serves as a reference for the research and development of acylglycerols using biocatalysts and reactors. It could be an interest to the food and pharmaceutical industries or individuals who are interested to explore this field. Several limitations associated with the overall research on production of acylglycerols are presented in the conclusion section.

Grafting of acidic ionic liquids onto the NH2-UiO-66 for butyric acid glyceride synthesis through heterogeneous catalysis of esterification

Immobilization of acid ionic liquid (AIL) for heterogeneous catalysis is benificial for products separation and recycling the AIL for continuing reuse. In this study, AIL was grafted onto the amino group functionalized zirconium-based metal organic framework (NH2-UiO-66) to catalyze esterification for short chain fatty acid glycerides synthesis. AIL of 1-(4-Sulfobutyl)-3-Methylimidazolium Hydrogen Sulfate ([HSO3-BMIM][HSO4]) was found suitable for short chain fatty acid glycerides after screening varied fatty acids with chain length from 4 to 18. [HSO3-BMIM][HSO4] was therefore grafted and butyric acid glyceride was synthesized. Reaction conditions were optimized by means of single factor study and orthogonal experiment. The reusability of the AIL@NH2-UiO-66 was evaluated. The AIL@NH2-UiO-66 showed good esterificaiton performance and fine reusability. Butyric acid conversion (converted into the glycerides of mono-, di- and tributyrin) at 62.16% was obtained under the optimum conditions. In addition, the present AIL@NH2-UiO-66 was quite stable, and 67.39% of its initial esterification activity was retained after 11 cycles of reuse, suggesting it was potential in the esterification reaction.

Preparation, acyl migration and applications of the acylglycerols and their isomers: A review

Acylglycerols in natural oils includes monoacylglycerols (MAG), diacylglycerols (DAG) and triacylglycerols (TAG). Each acylglycerol possesses different isomers, which results in variation in physicochemical and nutritional properties that can be used in various applications. Acyl migration is a spontaneous reaction involving the transition of acylglycerols into more stable isomers. Inhibition of acyl migration is beneficial for the application of different acylglycerol isomers. Whilst, the promotion of acyl migration positively impacts the synthesis of acylglycerols, altering the properties and improving the stability of the lipid system. Few studies have been performed recently on the synthesis of various acylglycerol isomers and the approach to control the acyl migration of acylglycerols. This paper discusses the preparation of acylglycerols isomers, the factors influencing acyl migration and the application of the isomers of acylglycerols, which is important for expanding the use of different isomeric acylglycerols as functional foods.

Screening Lipolytic from Soil Bacterial Contaminated Oil

Lipase (triasilglycerol acylhydrolase, E.C, 3.1.1.3) is an enzyme can hydrolyze long chains of triglycerides[1]. Lipase is a water-soluble enzyme and naturally lipase catalyze the hydrolysis of ester bonds in water insoluble lipid substrate and long-chain acylglycerol synthesis, diacylglycerol, monoacylglycerol, and glycerol[2]. Hydrolase enzyme lipase can be used potentialy produced fatty acid which precursors in the chemical industry[3]. The research aims to study the lipolytic activity of bacteria isolated from soil contaminated with oil. Screening of lipolytic bacteria was performed in Rhodamin-B agar plate containing olive oil. The lipolytic activity was determined by spectrofotometry method toward p-nitrofenil palmitat as a substrate. The result this research showed that there are 15 of 150 isolates bacteria from soil contaminated with oil was confirmed by observing the zone of hydrolysis formed around the growth of colony on Rhodamin B agar plate containing olive oil. One of the lipolytic bacteria identified as higher activity was produced lipase with activity of 7,41 U/ml

Angiotensin II induces podocyte metabolic reprogramming from glycolysis to glycerol-3-phosphate biosynthesis

Recent studies have reported that Angiotensin II (Ang II) contributes to podocyte injury by interfering with metabolism. Glycolysis is essential for podocytes and glycolysis abnormality is associated with glomerular injury in chronic kidney disease (CKD). Glycerol-3-phosphate (G-3-P) biosynthesis is a shunt pathway of glycolysis, in which cytosolic glycerol-3-phosphate dehydrogenase 1 (GPD1) catalyzes dihydroxyacetone phosphate (DHAP) to generate G-3-P in the presence of the NADH. G-3-P is not only a substrate in glycerophospholipids and glyceride synthesis but also can be oxidated by mitochondrial glycerol-3-phosphate dehydrogenase (GPD2) to regenerate DHAP in mitochondria. Since G-3-P biosynthesis links to glycolysis, mitochondrial metabolism and lipid synthesis, we speculate G-3-P biosynthesis abnormality is probably involved in podocyte injury. In this study, we demonstrated that Ang II upregulated GPD1 expression and increased G-3-P and glycerophospholipid syntheses in podocytes. GPD1 knockdown protected podocytes from Ang II-induced lipid accumulation and mitochondrial dysfunction. GPD1 overexpression exacerbated Ang II-induced podocyte injury. In addition, we proved that lipid accumulation and mitochondrial dysfunction were correlated with G-3-P content in podocytes. These results suggest that Ang II upregulates GPD1 and promotes G-3-P biosynthesis in podocytes, which promote lipid accumulation and mitochondrial dysfunction in podocytes.

Synthesis of Glycerides of Fatty Acids by Inorganic Solid Catalysts: A Review

AbstractHomogeneous catalysts in the synthesis of mono‐ and di‐glycerides have received wide acceptability due to their fast reaction rates. However, environmental issues and purification costs have led to the search for alternatives. Heterogeneous catalysts gained the attention of researchers because they can be applied to continuous processes, can be regenerated and can be used multiple times. This study reviews the available literature on solid catalysts used in the production of glycerides of fatty acids. It discusses the preparation methods, the reaction conditions and the results obtained in the three more important synthesis reactions: fatty acid esterification with glycerol, glycerolysis of fatty acid methyl ester and glycerolysis of triglycerides. The reported heterogeneous catalysts that were found to be the most active in the esterification reaction are the ones with strong acid sites. In the case of the glycerolysis, the most studied solid catalysts are Mg, Zn and Ca oxides, resulting in high monoglyceride yield.

Solvent-free synthesis of partial glycerides and structured triglycerides from soybean oil deodorizer distillate: bottom-up approach

Solvent-free synthesis of partial glycerides and structured triglycerides from soybean oil deodorizer distillate: bottom-up approach

Biodegradable Polymeric Foams Based on Modified Castor Oil, Styrene, and Isobornyl Methacrylate.

The environmental issues of petroleum-derived polymeric foams have necessitated seeking renewable alternatives. This work aims to prepare renewable free-radically polymerized polymeric foams with the ability to biodegrade. Furthermore, this work attempted to incorporate a bio-based reactive diluent, which has not been reported in the literature. The synthesis of maleated castor oil glycerides was performed with products analyzed by Fourier transform infrared spectrometry using attenuated total reflection (ATR-FTIR) and 1H nuclear magnetic resonance (1H NMR) spectroscopy. Polymeric foams were prepared using maleated castor oil glycerides via free radical copolymerization with styrene and isobornyl methacrylate as reactive diluents. Scanning electron microscopy (SEM) was used to determine anisotropic macrocellular morphology, with log-normal cell diameter distributions. The compressive mechanical and energy absorption properties were investigated; the polymeric foams displayed Young’s modulus up to 26.85 ± 1.07 MPa and strength up to 1.11 ± 0.021 MPa using styrene as the reactive diluent, and Young’s modulus up to 1.38 ± 0.055 MPa and strength up to 0.088 MPa when incorporating isobornyl methacrylate. Furthermore, a thorough analysis of the cellular structure–property relationships was performed, indicating relationships to cell diameter, cell wall thickness and apparent density. The polymeric foams displayed rapid mass loss in an aerobic soil environment with multiple erosion sites revealed by SEM. In conclusion, renewable polymeric foams with excellent compressive properties were achieved using styrene as reactive diluent, but the incorporation of isobornyl methacrylate decreased strength-related properties.

Study on the Synthesized Rosin Glyceride over LaZSM-5 Zeolite Catalyst Synthesized by the in Situ Method

LaZSM-5 zeolite was synthesized by the in situ method and used as catalysts to catalyze the synthesis of rosin glyceride. As a comparison, ZSM-5 was also synthesized and used as catalysts to catalyze the synthesis of rosin glyceride. The synthesized ZSM-5 and LaZSM-5 zeolite catalysts were characterized and analyzed. The experimental results showed that the in situ synthesis of LaZSM-5 made La into the skeleton of ZSM-5 zeolite and increased the amount of Lewis acid on the LaZSM-5 zeolite. Also, Lewis acid was the key to liquid-phase esterification reaction. Compared with ZSM-5 zeolite, LaZSM-5 zeolite contributed to a higher yield and better stability as a catalyst for the synthesis of rosin glycerides.

Acylglycerol synthesis including EPA and DHA from rainbow trout (Oncorhynchus mykiss) belly flap oil and caprylic acid catalyzed by Thermomyces lanuginosus lipase under supercritical carbon dioxide

Supercritical carbon dioxide (SCCO2) was studied as a medium for the esterification of eicosapentaenoic acid (n-3 C20:5, EPA) or docosahexaenoic acid (n-3 C22:6, DHA) and caprylic acid (C8:0, CA) in structured triacylglycerols (sTAG) using Thermomyces lanuginosus lipase as biocatalyst. Process variables (n-3 long-chain polyunsaturated fatty acid: CA, n-3 LCPUFA:CA content ratio), glycerol content (wt. %), and supercritical time, temperature and pressure were optimized by the Response Surface Methodology through a central composite design of 25–1 + star. Synthesis of sTAG with EPA, DHA and CA under SCCO2 was significantly affected by the n-3 LCPUFA:CA content ratio and supercritical time. MALDI-TOF mass spectrometry revealed that acylglycerols with the highest levels of EPA or DHA content in the sn-2 position were obtained when the following variables conditions were applied: 50% (n-3 LCPUFA:CA content ratio), 40 °C (supercritical temperature), 20 MPa (supercritical pressure), 4 h (supercritical time) and 20.0 wt. % (glycerol concentration). For such experimental conditions, esterification catalyzed by Thermomyces lanuginosus lipase under supercritical carbon dioxide allowed obtaining sTAG synthesized with 54.95% of CA, 11.64% of EPA and 13.77% of DHA.

Caffeoyl fatty acyl structural esters:enzymatic synthesis, characterization and antioxidant assessment

A novel way of lipase-catalyzed synthesis of monocaffeoyl monofatty acyl glycerols (MCMFGs), caffeic acid derivatives, with improved lipophilicity was investigated. The monocaffeoyl monopalmitoyl glycerol (MCMPG), monocaffeoyl monooleoyl glycerol (MCMOG) and monocaffeoyl monolinoleoyl glycerol (MCMLG) were prepared by Lypozyme 435 catalysis between 1-MCG and fatty acids. High 1-monocafferol glycerol (1-MCG) conversion (>98.26%) and the maximum yields of MCMPG (26.26%), MCMOP (35.37%) and MCMLP (45.43%) were obtained. The MCMFGs (>95%) were purified by preparative chromatography and their structures were verified by HPLC-MS/MS and 13C NMR. The ionization and viscosity of fatty acids were major factors during the synthesis of MCMFGs. Subsequently, the antioxidant assays supported that the MCMFGs are effective antioxidants and their antioxidant properties decreased by the “block” effect of their fatty acyl groups on catechol group. This study lighted not only the application of MCMFGs in industry, but also the further design of phenol lipids.

Immobilisation of Candida rugosa lipase on a highly hydrophobic support: A stable immobilised lipase suitable for non-aqueous synthesis

Lipase from Candida rugosa (CrL) was immobilised on highly hydrophobic, octadecyl methacrylate resin (Lifetech™ ECR8806M) via interfacial adsorption. The aim was to produce a stable biocatalyst suitable for use in a range of lipid-modifying reactions. Immobilisation was carried out in 10 mM phosphate buffer (pH 6.0) over 24 h at 21 °C. High protein binding of 58.7 ± 4.9 mg/g dry support accounted for ∼53 % of the applied protein. The activity recovery against tributyrin was 74.0 ± 1.1 %. The specific activity of immobilised CrL against tributyrin was considerably higher than that of Novozym® 435, at 1.79 ± 0.05 and 1.08 ± 0.04 U/mg bound protein, respectively. Incubation with high concentrations (10 % w/v) of both Triton X-100 and SDS resulted in only a small reduction in immobilised lipase activity. Solvent-free synthesis of glycerides by the FFA-saturated immobilised CrL was successful over 6 reaction cycles, with no apparent loss of activity.

OR20-03 Transcriptional Changes in Lipid Metabolism of Adipocytes Derived from Subcutaneous Abdominal Adipose Stem Cells of Normal-Weight Polycystic Ovary Syndrome Women

Normal-weight polycystic ovary syndrome (PCOS) women exhibit increased adipose insulin resistance in vivo (1) accompanying enhanced subcutaneous (SC) abdominal adipose stem cell (ASC) development to adipocytes with greater lipid accumulation per cell in vitro (2). To determine whether this phenomenon is associated with abnormal adipogenic gene transcription during ASC differentiation into adipocytes, SC abdominal ASCs isolated from three non-Hispanic Caucasian normal-weight PCOS women and three age- and BMI-matched controls were cultured in adipogenic differentiation medium for 3–12 days. After RNA isolation, gene expression levels were determined by RNA sequencing at days 3, 7, and 12. Differentially expressed genes were filtered for significance (padj<0.05) and fold change (>2-fold); upstream regulator genes and gene ontology (GO) functions were determined using Ingenuity Pathway Analysis. Gene set enrichment analysis (GSEA) also was used to identify enriched cellular processes (3). Differentially expressed genes in PCOS vs. control cells were either upregulated (466, 768 and 441 genes on days 3, 7 and 12, respectively) or downregulated (742, 974 and 605 genes on days 3, 7 and 12, respectively) over time, with critical genes governing adipocyte cell differentiation in PCOS cells increased 2–6 fold at days 3, 7 and 12 (PPARγ, CEBPα, ADIPOQ, AGPAT2, FABP4, LPL, PLIN1). The predicted upstream regulator genes TGFβ1 (an adipogenic inhibitor) and TNF (a pro-inflammatory adipokine) were significantly reduced in PCOS relative to control cells at all time points. The GO functions lipid oxidation and free fatty acid (FFA) beta-oxidation were enriched amongst upregulated genes in PCOS cells across all time points, while acylglycerol synthesis was increased at days 7 and 12 alone (z>2, p<0.05, all GO functions). In parallel, GSEA showed in PCOS cells significantly increased transcripts related to oxidative phosphorylation, peroxisome activity and adipogenesis at all time points (p<0.05). Thus, adipocytes derived from SC abdominal ASCs of normal-weight PCOS women exhibit early activation of adipogenic genes, potentially underlying their exaggerated lipid accumulation in vitro, as previously described (2). These PCOS-related changes in gene expression involve an increase in both oxidative phosphorylation and FFA beta oxidation, which could disrupt the balance between energy production and lipid storage, particularly when caloric intake exceeds energy utilization.

The Use of Glycerol in the Synthesis of Polycyclic Glycerides

The Use of Glycerol in the Synthesis of Polycyclic Glycerides

The Use of Glycerol in the Synthesis of Polycyclic Glycerides

The Use of Glycerol in the Synthesis of Polycyclic Glycerides

Two step-production of acylglycerols containing a high proportion of docosapentaenoic acid from marine omega-3 oil and their oxidative stability

The objective of this study was to concentrate polyunsaturated fatty acid (PUFA) from seal blubber oil in an innovative manner to produce a high content of docosapentaenoic acid (DPA) in the resultant product. It also aimed at investigating the use of lipases as catalysts for synthesizing acylglycerols from glycerol and polyunsaturated fatty acid concentrates. Additionally, study of the oxidative stability of acylglycerols synthesized by lipases was intended. A two-stage urea complexation process was used to concentrate PUFA from seal blubber oil, giving rise to a DPA content of up to 24.0% in the product. Enzymatic synthesis of acyglycerols directly from glycerol and fatty acid concentrate was studied. Three lipases were used as biocatalysts for esterification. Lipase SP435 from Candida antarctica showed the highest activity for esterification. Effects of reaction parameters, namely temperature, time course and mole ratio of glycerol to fatty acid were followed with all three lipases. The optimal reaction time was 24 hr at 30 °C at a mole ratio of glycerol to fatty acid of 14:1. The maximum degree of acylglycerol synthesis was &gt; 90%. The effect of time course and mole ratio of glycerol to fatty acid on acylglycerols distribution was also determined. The oxidative stability of different samples under Schaal-oven conditions at 60 °C showed that the oxidative stability of acylglycerols was better than that of the corresponding fatty acid esters.

Ablating both Fabp1 and Scp2/Scpx (TKO) induces hepatic phospholipid and cholesterol accumulation in high fat-fed mice

Although singly ablating Fabp1 or Scp2/Scpx genes may exacerbate the impact of high fat diet (HFD) on whole body phenotype and non-alcoholic fatty liver disease (NAFLD), concomitant upregulation of the non-ablated gene, preference for ad libitum fed HFD, and sex differences complicate interpretation. Therefore, these issues were addressed in male and female mice ablated in both genes (Fabp1/Scp2/Scpx null or TKO) and pair-fed HFD. Wild-type (WT) males gained more body weight as fat tissue mass (FTM) and exhibited higher hepatic lipid accumulation than WT females. The greater hepatic lipid accumulation in WT males was associated with higher hepatic expression of enzymes in glyceride synthesis, higher hepatic bile acids, and upregulation of transporters involved in hepatic reuptake of serum bile acids. While TKO had little effect on whole body phenotype and hepatic bile acid accumulation in either sex, TKO increased hepatic accumulation of lipids in both, specifically phospholipid and cholesteryl esters in males and females and free cholesterol in females. TKO-induced increases in glycerides were attributed not only to complete loss of FABP1, SCP2 and SCPx, but also in part to sex-dependent upregulation of hepatic lipogenic enzymes. These data with WT and TKO mice pair-fed HFD indicate that: i) Sex significantly impacted the ability of HFD to increase body weight, induce hepatic lipid accumulation and increase hepatic bile acids; and ii) TKO exacerbated the HFD ability to induce hepatic lipid accumulation, regardless of sex, but did not significantly alter whole body phenotype in either sex.

Selective synthesis of partial glycerides of conjugated linoleic acids via modulation of the catalytic properties of lipases by immobilization on different supports

Lipases B from Candida antarctica (CALB), Rhizomucor miehei (RML) and Thermomyces lanuginosus (TLL) were immobilized on octadecyl methacylate (OM) or octadecyl methacrylate (OMC) beads. Their specific activity and regioselectivity were studied in the synthesis of conjugated linoleic acid (CLA) partial glycerides, which presented nutraceutical properties.TLL derivatives were poor catalysts. Novozym® 435 was much better than Lipozyme® RM IM. RML activity (a GRAS enzyme) was modulated via immobilization. After only 3 h, OM−RML gave the highest CLA conversion (54% at 40 °C with 1:3 M ratio of glycerol to CLA). OM-RML reduced by a factor of 3.12 and 1.16 the activation energy of the reaction with Lipozyme® RM IM and Novozym® 435, respectively.The new GRAS preparation OM-RML brings forth an optimal regioselective preparation of sn-1 mono and sn-1,3 diacylglycerols rich in CLA, with a ratio of sn-1,3/sn-1,2 regioisomers of 21.8, compared to 2.3 for Novozym® 435.