Synthesis Of Structured Lipids Research Articles

Sustainable one-pot solvent-free enzymatic synthesis of capric acid-rich structured lipids to enhance the nutritional value of grape seed oil

Grape seed oil (GSO) is a valuable resource for the pharmaceutical, cosmetic, and food industries due to its fatty acid composition, which provides anti-inflammatory, cardioprotective, antimicrobial, and anticancer properties. GSO is also recognized for its sensory attributes and serves as an essential component in our dietary intake, providing vital fatty acids for metabolic reactions. The enzymatic synthesis of structured lipids (SL) using GSO was investigated in this study. The SL was created by incorporating medium chain fatty acids (capric acid – C10) at the sn-1 and sn-3 positions and long chain fatty acids in the internal position of the triacylglycerols (TAG). GSO was selected based on its composition rich in unsaturated fatty acids, mainly linoleic acid. The acidolysis reactions were catalyzed by an immobilized commercial lipase Lipozyme TLIM®. The incorporation degree of C10 into GSO reached 36%. Health lipid indices were calculated to determine the C10 incorporation effect on the improvement of nutritional quality of oil. The SL showed lower oxidative stability index (OSI) values than the original oil and higher degree of fatty acid (DFA) values. The simpler, solvent-free method not only enhances the health benefits of oils but also gives valuable properties to GSO, making it an even more attractive option for food industries.

Combining lipase enzymatic techniques and antioxidants on the flavor of structured lipids (SLs) prepared from goat butter and coconut oil

Enzymatic transesterification can improve the quality of goat butter, however, the high temperature may lead to oil oxidation and produce a bad taste. In this study, goat butter (GB) and coconut oil (CO) were combined to synthesize structured lipids (SLs) by enzymatic transesterification, and antioxidants were added to inhibit oxidation to improve the oils’ flavor. The Lipozyme TLIM and tert-butylhydroquinone (TBHQ) were screened for SLs synthesis. The contents of SLs were 56.24% under the optimal conditions of 8 h reaction time, 5°C reaction temperature, 8% enzyme dosage, and 3:1 (w/w) substrate ratio, and the addition of antioxidants had no significant effect on the contents of SLs. It was demonstrated that short-chain fatty acids in the SLs were significantly reduced by 59.2%, and the medium-chain fatty acids were increased by 54.9% compared to GB. One hundred volatile compounds were identified in the lipid samples and classified as (1) long-chain alkane aromatic components and aromatic components, which remarkably decreased by 58.9%, and (2) alcohols, aldehydes, and ketones, which increased by 12.9%, through using solid-phase microextraction coupled with gas chromatography-mass spectrometry (SPME-GC-MS) and electronic nose. The relative aroma activity value (ROAV) of 9 key volatile aroma components was higher than 1 in the SLs, which greatly contributed to the reduction of goaty flavor and increasing cream flavor. The results suggested that the goaty flavor of GB could be significantly reduced by decreasing the short-chain fatty acids contents in SLs through enzymatic transesterification with CO, while the addition of antioxidants efficiently inhibited excessive lipids oxidation and increased the content of long-chain aldehydes, ketones, and lactones, thus enhancing the cream flavor, which had great potential to be utilized as natural food flavor additives.

Enzymatic Synthesis of Structured Lipids Enriched with Medium- and Long-Chain Triacylglycerols via Pickering Emulsion-Assisted Interfacial Catalysis: A Preliminary Exploration.

Medium- and long-chain triacylglycerol (MLCT), as a novel functional lipid, is valuable due to its special nutritional properties. Its low content in natural resources and inefficient synthesis during preparation have limited its practical applications. In this study, we developed an effective Pickering emulsion interfacial catalysis system (PE system) for the enzymatic synthesis of MLCT by trans-esterification. Lipase NS 40086 served simultaneously as a catalyst and a solid emulsifier to stabilize the Pickering emulsion. Benefitting from the sufficient oil-water interface, the obtained PE system exhibited outstanding catalytic efficiency, achieving 77.5% of MLCT content within 30 min, 26% higher than that of a water-free system. The Km value (0.259 mM) and activation energy (14.45 kJ mol-1) were 6.8-fold and 1.6-fold lower than those of the water-free system, respectively. The kinetic parameters as well as the molecular dynamics simulation and the tunnel analysis implied that the oil-water interface enhanced the binding between substrate and lipase and thus boosted catalytic efficiency. The conformational changes in the lipase were further explored by FT-IR. This method could give a novel strategy for enhancing lipase activity and the design of efficient catalytic systems to produce added-value lipids. This work will open a new methodology for the enzymatic synthesis of structured lipids.

Enzymatic synthesis of structured lipids from sacha inchi (Plukenetia volubilis) oil with capric acid via acidolysis reaction in stirred tank and packed bed mini reactors

The present study describes an efficient and sustainable synthesis method for producing functional triglycerides (FTs) by conducting an acidolysis reaction of sacha inchi (Plukenetia volubilis) oil with capric acid (C10), catalyzed by Rhizopus oryzae (RO) lipase immobilized in low-cost corn cob powder, to obtain medium-large-medium chain (MLM) triglycerides. Initially, acidolysis reactions were performed between sacha inchi oil, C10, and the immobilized enzyme in a stirred tank at various temperatures (35 °C, 45 °C, 55 °C, and 59 °C), different molar ratios (1:2, 1:3, 1:4 oil:fatty acid), and various hydrolytic enzyme activities (83.6, 124, and 217 IU/mg). Subsequently, to optimize the degree of incorporation, the best condition from the stirred tank reactions (45 °C, 1:3 M ratio, and 217 U of hydrolytic activity) was selected, considering the highest nutritional quality of the lipid in terms of the migration of the sn2 position, and was tested in a packed bed reactor with a spatial time of 112 min, residence time of 107 min, and a flow rate of 0.5 mL/min. The highest incorporation degree achieved in packed bed reactor was 36% at 45 °C. Afterward, it was developed for the best condition an integrative platform for the recycling of the RO lipase immobilized in low-cost corn cob powder (up to four successive cycles without any make up). Subsequent assays on the functional triglycerides revealed atherogenic and thrombogenicity lipid index values of 0.04 ± 0.10 and 4.15 ± 0.05, respectively, which were lower than those of pure sacha inchi oil, indicating the potential to enhance the nutritional quality of the oil through C10 incorporation.

Structured Lipids Engineering for Health: Novel Formulations Enriched in n-3 Long-Chain Polyunsaturated Fatty Acids with Potential Nutritional Benefits.

Structured lipids (SLs) offer a promising avenue for designing novel formulations enriched in n-3 long-chain polyunsaturated fatty acids (LCPUFAs) with potential health benefits. Triacylglycerols (TAGs), the most common fats in the human diet, are both non-toxic and chemically stable. The metabolic efficiency and digestibility of TAGs are significantly influenced by the position of fatty acids (FAs) within the glycerol backbone, with FAs at the sn-2 position being readily absorbed. Over the past two decades, advancements in SL research have led to the development of modified TAGs, achieved either through chemical or enzymatic processes, resulting in SLs. The ideal structure of SLs involves medium-chain FAs at the sn-1,3 positions and long-chain n-3 LCPUFAs at the sn-2 position of the glycerol backbone, conferring specific physicochemical and nutritional attributes. These tailored SL formulations find wide-ranging applications in the food and nutraceutical industries, showing promise for dietary support in promoting health and mitigating various diseases. In particular, SLs can be harnessed as functional oils to augment TAG metabolism, thereby impeding the development of fatty liver, countering the onset of obesity, and preventing atherosclerosis and age-related chronic diseases. In scrutinising prevailing research trajectories, this review endeavours to provide an in-depth analysis of the multifaceted advantages and repercussions associated with the synthesis of SLs. It elucidates their burgeoning potential in enhancing health and well-being across a range of demographic cohorts. Specifically, the implications of SL utilisation are discussed in the context of healthcare environments and early childhood developmental support.

An Overview of Structured Lipid in Food Science: Synthesis Methods, Applications, and Future Prospects

Structured lipids have attracted significant interest in industries, such as food, pharmaceuticals, and cosmetics, because they can be alternatives to traditional lipids. Enzymatic synthesis techniques utilizing lipases have gained attention for structured lipids synthesis because of their site and substrate specificity. However, most lipases discovered to date exhibit sn-1,3 regiospecificity or nonspecificity, limiting the selective range of natural oils and fats that can be used as raw materials. In this review, we provide an overview of the current synthesis methods and applications of structured lipids and the limitations of existing lipases in producing structured lipids. In addition, we discuss innovative approaches, including metagenomics, and machine learning, to discover, and classify new lipases and the use of gene editing technologies for lipase engineering. These efforts aim to overcome the limitations of existing lipases and expand the range of natural oils and fats that can be used for the production of structured lipids. Therefore, this study aims to promote a better understanding of structured lipids as a material with high-added value and provides insight into ongoing research efforts in the field.

Solvent-Free Enzymatic Synthesis of Dietary Triacylglycerols from Cottonseed Oil in a Fluidized Bed Reactor.

The synthesis of structured lipids with nutraceutical applications, such as medium-long-medium (MLM) triacylglycerols, via modification of oils and fats represents a challenge for the food industry. This study aimed to synthesize MLM-type dietary triacylglycerols by enzymatic acidolysis of cottonseed oil and capric acid (C10) catalyzed by Lipozyme RM IM (lipase from Rhizomucor miehei) in a fluidized bed reactor (FBR). After chemical characterization of the feedstock and hydrodynamic characterization of the reactor, a 22 central composite rotatable design was used to optimize capric acid incorporation. The independent variables were cycle number (20-70) and cottonseed oil/capric acid molar ratio (1:2-1:4). The temperature was set at 45 °C. The best conditions, namely a 1:4 oil/acid molar ratio and 80 cycles (17.34 h), provided a degree of incorporation of about 40 mol%, as shown by compositional analysis of the modified oil. Lipozyme RM IM showed good operational stability (kd = 2.72 × 10-4 h-1, t1/2 = 2545.78 h), confirming the good reuse capacity of the enzyme in the acidolysis of cottonseed oil with capric acid. It is concluded that an FBR configuration is a promising alternative for the enzymatic synthesis of MLM triacylglycerols.

Valorization of Cereal Byproducts with Supercritical Technology: The Case of Corn

Ethanol and starch are the main products generated after the processing of corn via dry grinding and wet milling, respectively. Milling generates byproducts including stover, condensed distillers’ solubles, gluten meal, and the dried distillers’ grains with solubles (DDGS), which are sources of valuable compounds for industry including lignin, oil, protein, carotenoids, and phenolic compounds. This manuscript reviews the current research scenario on the valorization of corn milling byproducts with supercritical technology, as well as the processing strategies and the challenges of reaching economic feasibility. The main products recently studied were biodiesel, biogas, microcapsules, and extracts of enriched nutrients. The pretreatment of solid byproducts for further hydrolysis to produce sugar oligomers and bioactive peptides is another recent strategy offered by supercritical technology to process corn milling byproducts. The patents invented to transform corn milling byproducts include oil fractionation, extraction of undesirable flavors, and synthesis of structured lipids and fermentable sugars. Process intensification via the integration of milling with equipment that operates with supercritical fluids was suggested to reduce processing costs and to generate novel products.

Simultaneous Production and Immobilization of Lipase Using Pomegranate-Seed Residue: A New Biocatalyst for Hydrolysis Reactions and Structured Lipids Synthesis

Pomegranate-seed residue (PSR) was used in a new strategy for the simultaneous production of Yarrowia lipolytica lipase by submerged fermentation and its immobilization by adsorption. This biocatalyst—the fermented solid residue containing the adsorbed lipase (fermPSR)—was evaluated in hydrolysis reactions and in structured lipid synthesis. In shake flasks, yeast extract and urea were the best nitrogen sources for lipase production with PSR and their simultaneous use increased the lipase production even further. This result was confirmed in a 3.5-liter bioreactor, with lipase activity in an extracellular medium of 40 U/mL. A maximum reaction rate (Vmax) of 49.5 µmol/min/g, a Michaelis–Menten constant (Km) of 207 µmol/L, and a turnover number (Kcat) of 130 s−1 were determined for the new biocatalyst, fermPSR, for the hydrolysis of p-nitrophenyl laurate (p-NPL) into p-nitrophenol. The conversion of p-NPL into p-nitrophenol in subsequent reactions confirmed fermPSR’s potential for industrial hydrolytic reactions. The production of structured lipids from vegetable oil and free fatty acids by fermPSR evidences the versatility of this new biocatalyst.

Rational Design of Lipase ROL to Increase Its Thermostability for Production of Structured Tags.

1,3-regiospecific lipases are important enzymes that are heavily utilized in the food industries to produce structured triacylglycerols (TAGs). The Rhizopus oryzae lipase (ROL) has recently gained interest because this enzyme possesses high selectivity and catalytic efficiency. However, its low thermostability limits its use towards reactions that work at lower temperature. Most importantly, the enzyme cannot be used for the production of 1,3-dioleoyl-2-palmitoylglycerol (OPO) and 1,3-stearoyl-2-oleoyl-glycerol (SOS) due to the high melting points of the substrates used for the reaction. Despite various engineering efforts used to improve the thermostability of ROL, the enzyme is unable to function at temperatures above 60 °C. Here, we describe the rational design of ROL to identify variants that can retain their activity at temperatures higher than 60 °C. After two rounds of mutagenesis and screening, we were able to identify a mutant ROL_10x that can retain most of its activity at 70 °C. We further demonstrated that this mutant is useful for the synthesis of SOS while minimal product formation was observed with ROL_WT. Our engineered enzyme provides a promising solution for the industrial synthesis of structured lipids at high temperature.

Future of Structured Lipids: Enzymatic Synthesis and Their New Applications in Food Systems.

Structured lipids (SLs) refer to a new type of functional lipid obtained by modifying natural triacylglycerol (TAG) through the restructuring of fatty acids, thereby altering the composition, structure, and distribution of fatty acids attached to the glycerol backbones. Due to the unique functional characteristics of SLs (easy to absorb, low in calories, reduced serum TAG, etc.), there is increasing interest in the research and application of SLs. SLs were initially prepared using chemical methods. With the wide application of enzymes in industries and the advantages of enzymatic synthesis (mild reaction conditions, high catalytic efficiency, environmental friendliness, etc.), synthesis of SLs using lipase has aroused great interest. This review summarizes the reaction system of SL production and introduces the enzymatic synthesis and application of some of the latest SLs discussed/developed in recent years, including medium- to long-chain triacylglycerol (MLCT), diacylglycerol (DAG), EPA- and DHA-enriched TAG, human milk fat substitutes, and esterified propoxylated glycerol (EPG). Lastly, several new ways of applying SLs (powdered oil, DAG plastic fat, inert gas spray oil, and emulsion) in the future food industry are also highlighted.

Triglycerides of medium-chain fatty acids: a concise review.

Medium-chain triglycerides contain medium-chain fatty acid esterified to the glycerol backbone. These MCFA have a shorter chain length and are quickly metabolized in the body serving as an immediate energy source. They are known to have good physiological as well as functional characteristics which help in treating various health disorders. Naturally, they are found in coconut oil, milk fat, and palm kernel oil, and they are synthetically produced by esterification and interesterification reactions. Due to their numerous health benefits, MCT is used as a functional or nutraceutical oil in various food and pharmaceutical formulations. To increase their nutraceutical benefits and food applications MCFA can be used along with polyunsaturated fatty acids in the synthesis of structured lipids. This review aims to provide information about triglycerides of MCFA, structure, metabolism, properties, synthetic routes, intensified synthesis approaches, health benefits, application, and safety of use of MCT in the diet.

Structural Basis for the Regiospecificity of a Lipase from Streptomyces sp. W007.

The efficiency and accuracy of the synthesis of structural lipids are closely related to the regiospecificity of lipases. Understanding the structural mechanism of their regiospecificity contributes to the regiospecific redesign of lipases for meeting the technological innovation needs. Here, we used a thermostable lipase from Streptomyces sp. W007 (MAS1), which has been recently reported to show great potential in industry, to gain an insight into the structural basis of its regiospecificity by molecular modelling and mutagenesis experiments. The results indicated that increasing the steric hindrance of the site for binding a non-reactive carbonyl group of TAGs could transform the non-specific MAS1 to a α-specific lipase, such as the mutants G40E, G40F, G40Q, G40R, G40W, G40Y, N45Y, H108W and T237Y (PSI > 80). In addition, altering the local polarity of the site as well as the conformational stability of its composing residues could also impact the regiospecificity. Our present study could not only aid the rational design of the regiospecificity of lipases, but open avenues of exploration for further industrial applications of lipases.

Distigmasterol-Modified Acylglycerols as New Structured Lipids-Synthesis, Identification and Cytotoxicity.

Plant sterols, also referred as phytosterols, have been known as bioactive compounds which have cholesterol-lowering properties in human blood. It has been established that a diet rich in plant sterols or their esters alleviates cardiovascular diseases (CVD), and also may inhibit breast, colon and lung carcinogenesis. Phytosterols, in their free and esterified forms, are prone to thermo-oxidative degradation, where time and temperature affect the level of degradation. Looking for new derivatives of phytosterols with high thermo-oxidative stability for application in foods, our idea was to obtain novel structured acylglycerols in which two fatty acid parts are replaced by stigmasterol residues. In this work, asymmetric (1,2- and 2,3-) distigmasterol-modified acylglycerols (dStigMAs) were synthesized by the covalent attachment of stigmasterol residues to sn-1 and sn-2 or sn-2 and sn-3 positions of 3-palmitoyl-sn-glycerol or 1-oleoyl-sn-glycerol, respectively, using a succinate or carbonate linker. The chemical structures of the synthesized compounds were identified by NMR, HR-MS, and IR data. Moreover, the cytotoxicity of the obtained compounds was determined. The dStigMAs possessing a carbonate linker showed potent cytotoxicity to cells isolated from the small intestine and colon epithelium and liver, whereas the opposite results were obtained for compounds containing a succinate linker.

Enzymatic synthesis of capric acid-rich structured lipids and their effects on mice with high-fat diet-induced obesity

The objective of this study was to produce structured lipids (SLs) by enzymatic acidolysis using Rhizopus oryzae lipase covalently immobilized in a low-cost material. Grape seed oil was used to synthesize SLs containing the medium-chain fatty acid (C10:0) capric acid. SL synthesis led to 38.8% medium-chain fatty acid incorporation with 5 reuses of the enzymatic derivative. The reaction conditions for the synthesis of MLM-TAGs (triacylglycerols with one long- and two medium-chain acyl residues) were at a molar ratio of fatty acid:oil of 3:1, performed at 40 °C and lipase immobilized load of 5% (w/w). The in vivo effects of SLs were studied in Swiss mice fed premade diets: control (C) diet, high-fat diet (HFD) with 100% lipid content as lard, HFD with 50% lipid content as grape seed oil (HG) or HFD with 50% lipid content as capric acid-containing SLs produced from grape seed oil (HG-MCT). Mice from HG and HG-MCT groups had decreases in body weight gain and reductions in the weights of white adipose tissues. In addition, HG and HG-MCT mice had low plasma levels of glucose and total cholesterol, and improvements in the glucose tolerance. HG and HG-MCT diets have remarkable antioxidant properties, since low plasma levels of TBARS (thiobarbituric acid reactive substances, biomarkers of lipid peroxidation) were found in mice fed these diets. Interestingly, TBARS levels in HG-MCT mice were further decreased than values of HG mice. Mice fed HG and HG-MCT diets also showed preservation in the activity of the antioxidant enzyme paraoxonase 1. Both HG and HG-MCT diets promoted reduction of IL-6 and IL-10 production by splenocytes. The capric acid-containing SLs produced from grape seed oil emerges as a functional oil capable to mitigate obesity complications resulting from oxidative stress and inflammation.

Stability comparison of four lipases and catalytic mechanism during the synthesis of 1,3-di-oleic-2-medium chain triacylglycerols in a trace water-in-oil system: Experimental analyses and computational simulations.

In the present study, a kind of structured lipids, namely 1,3-di-oleic-2-medium chain (OMO) triacylglycerols, were synthesized through lipase-catalyzed reactions using coconut oil and rapeseed acid as materials in a trace water-in-oil system. Experimental analysis and computational simulations were undertaken to compare the stability of four lipases including Lipozyme RMIM, Lipozyme TLIM, Novozym 435, and Aspergillus oryzae immobilized lipase (AOIM), and illustrate catalytic mechanism of Novozym 435 during the synthesis of OMO. Fourier transform infrared and molecular dynamics simulation results demonstrated that a decrease in ordered structure (α-helix and β-sheet) led to a reduction in enzyme activity. Compared with Lipozyme RMIM and Novozym 435, Lipozyme TLIM and AOIM exhibited better stability due to a short-chain lid in TLIM, which covers activity sites, and hydrogen bonds formed between activity center of AOIM and water. Among four lipases, AOIM exhibited best catalytic performance: a OMO yield of 30.7% at 3hr and a good stability of long term (48hr). Density functional theory results demonstrated that specifically, during the synthesis of OMO triacylglycerol, the addition of Novozym 435 (derived from Candida antarctica lipase B, CALB) substantially lowered reaction barriers (64.4KJ/mol with CALB vs. 332.7KJ/mol with no lipase), aiding in the generation of OMO because of the formations of transitional tetrahedral intermediates. A trace water-in-oil system was a green and efficient alternative for lipase-catalyzed production of OMO, and this study provided crucial insights into the stability/instability and catalytic mechanisms of lipase in the synthesis of structured lipids. PRACTICAL APPLICATIONS: We compared the stability of Lipozyme RMIM, Lipozyme 435, Lipozyme TLIM, and AOIM during the synthesis of the OMO triacylglycerols in a trace water-in-oil system, where exhibited a high catalytic activity of lipase in water-oil interface. AOIM had the highest stability and showed the best catalytic performance due to the formation of hydrogen bonds. Besides, for the first time, the transition tetrahedral structure was revealed in the enzymatic synthesis of medium- and long-chain triacylglycerols. This study provides a rational approach to compare lipase stability and a possible hint to choose appropriate enzyme in a specific catalytic condition.

Enzymatic synthesis of structured lipids from grape seed (Vitis vinifera L.) oil in associated packed bed reactors.

Triacylglycerols (TAGs) can be modified to increase the absorption of fatty acids, prevent obesity, and treat fat malabsorption disorders and metabolic diseases. Medium-long-medium (MLM)-type TAGs, which contain medium-chain fatty acids in the sn-1 and sn-3 positions of the glycerol backbone and a long-chain fatty acid in the sn-2 position, show particularly interesting nutritional characteristics. This study aimed to synthesize MLM-type TAGs by enzymatic acidolysis of grape seed oil with medium-chain capric acid (C10:0) in associated packed bed reactors. The reaction was carried out during 120H, at 45°C, using lipase from Rhizomucor miehei (Lipozyme® RM IM). The residence time distribution of reagents in the reactor was quantified to evaluate the reactor behavior and to diagnose the existence of preferential paths. The reaction progress was monitored by analyzing TAG composition and, at the steady state (after 48H of reaction), the incorporation degree achieved a value of 39.91±2.77%. To enhance the capric acid incorporation, an acidolysis reaction in associated packed bed reactors was performed. The results showed a good operational stability of the biocatalyst, revealing values of half-life 209.64H, 235.63H of packed bed and associated packed bed reactor, respectively, and a deactivation coefficient 0.0061H-1 .

Effect of Solvent on Acyl Migration of 2-Monoacylglycerols in Enzymatic Ethanolysis.

Acyl migration occurs in many reactions and is the main obstacle for structured lipid synthesis. In this study, 2-monoacylglycerol (2-MAG) was prepared by enzymatic ethanolysis in three different media to evaluate the effect of environment on product composition. The contents of 2-MAG obtained in ethanol, hexane + ethanol, and t-butanol + ethanol systems were 30.6, 15.7, and 32.4%, respectively, after 3 h reaction. Afterward, the acyl migration kinetics of 2-MAG were studied in solvent and solventless systems without the use of lipase. Results indicate that 2-MAG in the solventless system had the highest acyl migration rate. The isomerization was efficiently prevented by the use of polar solvents, especially t-butanol. The rate constants were shown to be the highest and activation energy values were the lowest in solventless systems. The novel finding in this study was that solvent had inhibitory effect on 2-MAG isomerization, but the nonpolar hexane had the lowest inhibition of acyl migration compared to other solvents.

Mitochondrial fatty acid synthesis: not just another way to make fatty acids

Mitochondria are often dubbed “the powerhouse of the cell,” however this gross over‐simplification has arguably led to a paucity of knowledge concerning the many other functions of these incredibly diverse organelles. Fatty acid synthesis (FAS) is an essential cellular process, but it is a little‐known fact even among mitochondrial experts that eukaryotes actually harbor two distinct FAS systems – one in the cytoplasm, and one in the mitochondria. Although mitochondrial FAS (mtFAS) was discovered decades ago, its function(s) in mammals are still unclear. One well known product of the pathway is lipoic acid, an important lipid co‐factor for several mitochondrial dehydrogenases, however we now appreciate that mtFAS plays a far wider role in mitochondrial physiology. Here we show that while mtFAS does not directly contribute to the synthesis of structural lipids like PS, it instead is required for the production of lipids that facilitate assembly and stability of the mitochondrial electron transport chain (ETC). This novel regulatory role of mtFAS occurs via physical interaction of the acyl carrier protein and a family of late‐stage ETC assembly factors known as the LYR proteins. Notably, this effect is separate from lipoic acid production, as Lipt1 knockouts do not display the same strong ETC depletion phenotype. Proteomics and metabolomics data provide intriguing insights into the consequences of mtFAS depletion, and highlight promising future directions towards further understanding the role of this pathway in cellular metabolism.Support or Funding InformationThis work was supported partially by grants from the NIH (GM115174 and GM115129 to JR and GM97645 to SPG) and the Nora Eccles Treadwell Foundation (to JR), as well as HHMI (JR). Support for SMN was also provided by UMDF and ACS postdoctoral fellowships.

Synthesis, physicochemical properties, and health aspects of structured lipids: A review.

Structured lipids (SLs) refer to a new type of functional lipids obtained by chemically, enzymatically, or genetically modifying the composition and/or distribution of fatty acids in the glycerol backbone. Due to the unique physicochemical characteristics and health benefits of SLs (for example, calorie reduction, immune function improvement, and reduction in serum triacylglycerols), there is increasing interest in the research and application of novel SLs in the food industry. The chemical structures and molecular architectures of SLs define mainly their physicochemical properties and nutritional values, which are also affected by the processing conditions. In this regard, this holistic review provides coverage of the latest developments and applications of SLs in terms of synthesis strategies, physicochemical properties, health aspects, and potential food applications. Enzymatic synthesis of SLs particularly with immobilized lipases is presented with a short introduction to the genetic engineering approach. Some physical features such as solid fat content, crystallization and melting behavior, rheology and interfacial properties, as well as oxidative stability are discussed as influenced by chemical structures and processing conditions. Health-related considerations of SLs including their metabolic characteristics, biopolymer-based lipid digestion modulation, and oleogelation of liquid oils are also explored. Finally, potential food applications of SLs are shortly introduced. Major challenges and future trends in the industrial production of SLs, physicochemical properties, and digestion behavior of SLs in complex food systems, as well as further exploration of SL-based oleogels and their food application are also discussed.