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In this study, based on the discovery of thymol/glycerol monolaurate (GML) eutectic solvent, we studied the effect of GML as a multi-functional component (ripening inhibitor and antibacterial agent) on the formation, stability and antibacterial activity of eutectic nanoemulsions, and investigated the preservation of nanoemulsion in fresh pork. These results indicated that the formation of eutectic solvent was due to the hydrogen bonding between thymol and GML in the molten state. And eutectic nanoemulsions prepared with medium GML concentrations (20%, 40%, and 60%) of eutectic solvents as oil phases had small droplet diameters (<150 nm), exhibited sustained-release characteristics, and had excellent physicochemical stability. Moreover, the addition of GML enhanced the antibacterial activity of thymol nanoemulsion against S. aureus. as seen by their ability to inhibit affect formation more effectively. Treatment of fresh pork with optimized eutectic nanoemulsions (40% thymol/60% GML) extended its shelf life during refrigeration, which was mainly attributed to the ability of the encapsulated essential oil to inhibit microbial growth and lipid oxidation. These results provide a novel strategy to control Ostwald ripening and maintain the high antibacterial activity of thymol in nanoemulsion-based delivery systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Lysosomes catabolize and recycle lipids and other biological molecules to maintain cellular homeostasis in diverse nutrient environments. Lysosomal lipid catabolism relies on the stimulatory activity of bis(monoacylglycero)phosphate (BMP), an enigmatic lipid whose levels are altered across myriad lysosome-associated diseases. Here, we review the discovery of BMP over half a century ago and its structural properties that facilitate the activation of lipid hydrolases and recruitment of their coactivators. We further discuss the current, yet incomplete, understanding of BMP catabolism and anabolism. To conclude, we discuss its role in lysosome-associated diseases and the potential for modulating its levels by pharmacologically activating and inhibiting the BMP synthase to therapeutically target lysosomal storage disorders, drug-induced phospholipidosis, Alzheimer's disease, Parkinson's disease, frontotemporal dementia, cancer, and viral infection.

Organic acids are widely used in foodstuffs to inhibit pathogen and spoiler growth. In this study, six organic acids (acetic, lactic, propionic, phenyllactic, caprylic, and lauric acid) and monolaurin were selected based on their physicochemical properties: their molecular structure (carbon chain length), their lipophilicity (logP), and their ability to dissociate in a liquid environment (pKa). The relation between these physicochemical properties and the inhibitory efficacy against B. weihenstephanensis KBAB4 growth was evaluated. After assessing the active form of these compounds against the strain (undissociated, dissociated or both forms), their MIC values were estimated in nutrient broth at pH 6.0 and 5.5 using two models (Lambert & Pearson, 2000; Luong, 1985). The use of two models highlighted the mode of action of an antibacterial compound in its environment, thanks to the additional estimation of the curve shape α or the Non-Inhibitory Concentration (NIC). The undissociated form of the tested acids is responsible for growth inhibition, except for lauric acid and monolaurin. Moreover, long-carbon chain acids have lower estimated MICs, compared to short-chain acids. Thus, the inhibitory efficacy of organic acids is strongly related to their carbon chain length and lipophilicity. Lipophilicity is the main mechanism of action of a membrane-active compound, it can be favored by long chain structure or high pKa in an acid environment like food., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Fatty acid amide hydrolase (FAAH) is a conserved hydrolase in eukaryotes with promiscuous activity toward a range of acylamide substrates. The native substrate repertoire for FAAH has just begun to be explored in plant systems outside the model Arabidopsis thaliana. Here, we used ex vivo lipidomics to identify potential endogenous substrates for Medicago truncatula FAAH1 (MtFAAH1). We incubated recombinant MtFAAH1 with lipid mixtures extracted from M. truncatula and resolved their profiles via gas chromatography-mass spectrometry (GC-MS). Data revealed that besides N-acylethanolamines (NAEs), sn-1 or sn-2 isomers of monoacylglycerols (MAGs) were substrates for MtFAAH1. Combined with in vitro and computational approaches, our data support both amidase and esterase activities for MtFAAH1. MAG-mediated hydrolysis via MtFAAH1 may be linked to biological roles that are yet to be discovered., (© 2024 The Author(s). FEBS Letters published by John Wiley & Sons Ltd on behalf of Federation of European Biochemical Societies.)

Reducing salt intake without affecting the saltiness perception remains a great challenge for the food industry. Herein, the demulsification of water droplets and air bubbles was controlled to modulate the release of sodium from oleogel-stabilized water-in-oil emulsions (OGEs) stabilized by monoglyceride crystals. The effect of monoglycerides with carbon chain length (glycerol monolaurate-GML, glyceryl monostearate-GMS, and glycerol monopalmitate-GMP) and homogenization methods (hand-shaking or high-speed blender) on sodium release and saltiness was investigated by in vitro and in vivo oral processing tests. Milky-white stable emulsions were formed with both water droplets and air bubbles dispersing in the oil phase, regardless of the selected homogenization methods. Air bubbles were more unstable than water droplets during oral digestion. GML OGEs with more and larger air bubbles and the lowest hardness exhibited the highest sodium release rate and the strongest saltiness, independent of homogenization methods. The balance between air bubbles and water droplets in the GMS and GMP OGEs caused slower sodium release and lower saltiness. Overall, the presence of air bubbles in NaCl-loaded W/O oleogel-based emulsions was shown to have important implications for tailoring their sodium release and saltiness.

This study assessed the nutritional profile of camellia oil through its fatty acid composition, highlighting its high oleic acid content (81.4%), followed by linoleic (7.99%) and palmitic acids (7.74%), demonstrating its excellence as an edible oil source. The impact of beeswax (BW) and glycerol monolaurate (GML) on camellia oil oleogels was investigated, revealing that increasing BW or GML concentrations enhanced hardness and springiness, with 10% BW oleogel exhibiting the highest hardness and springiness. FTIR results suggested that the structure of the oleogels was formed by interactions between molecules without altering the chemical composition. In biscuits, 10% BW oleogel provided superior crispness, expansion ratio, texture, and taste, whereas GML imparted a distinct odor. In sausages, no significant differences were observed in color, water retention, and pH between the control and replacement groups; however, the BW group scored higher than the GML group in the sensory evaluation. The findings suggest that the BW oleogel is an effective fat substitute in biscuits and sausages, promoting the application of camellia oil in food products.

Monoacylglycerols are eco-friendly and inexpensive emulsifiers with a range of applications. The traditional synthetic route is not eco-friendly, while enzymatic catalysis offers milder reaction conditions and higher selectivity. However, its application still is limited due to the costs. In this context, endophytic fungi can be source to new biocatalysts with enhanced catalytic activity. Based on this perspective, the aim of this study was perform the synthesis of MAG's through transesterification reactions of solketal and different vinyl esters, using crude and immobilized lipolytic extracts from the endophytic fungi Stemphylium lycopersici, isolated from Humiria balsamifera. The reactions were conducted using 100 mg of biocatalyst, 1 mmol of substrates, 9 : 1 n-heptane/acetone, at 40 °C, 200 rpm for 96 h. In the reactions using the ILE and stearate, laureate and decanoate vinyl esters it was possible to obtain the correspondent products with conversion rates of 52-75 %. Also, according to the structure drivers used in MCM-48 synthesis, different morphologies and conversions rates were observed. Employing [C16MI] Cl, [C14MI] Cl and [C4MI] Cl, the 1-lauroyl- glycerol conversion was 36 %, 79 % and 44 %, respectively. This is the first work involving the immobilization of an endophytic fungi and its utilization as a biocatalyst in the production of MAG's., (© 2024 Wiley-VHCA AG, Zurich, Switzerland.)

Docosahexaenoic acid monoacylglycerol represents a promising lipid constituent in the development of drug nanocarriers owing to its amphiphilicity and the beneficial health effects of this docosahexaenoic acid precursor in various disorders including cancer and inflammatory diseases. Here, we describe the formation and characterization of simple-by-design and stabilizer-free lamellar and non-lamellar crystalline nanoparticles (vesicles and cubosomes, respectively) from binary mixtures of docosahexaenoic acid monoacylglycerol and phosphatidylglycerol, which is a ubiquitous amphiphilic component present in biological systems. At the physiological temperature of 37 °C, these single amphiphilic components tend to exhibit inverse hexagonal and lamellar liquid crystalline phases, respectively, on exposure to excess water. They can also be combined and dispersed in excess water by employing a high-energy emulsification method (by means of ultrasonication) to produce through an electrostatic stabilization mechanism colloidally stable nanodispersions. A colloidal transformation from vesicles to cubosomes was detected with increasing MAG-DHA content. Through use of synchrotron small-angle X-ray scattering, cryo-transmission electron microscopy, and nanoparticle tracking analysis, we report on the structural and morphological features, and size characteristics of these nanodispersions. Depending on the lipid composition, their internal liquid crystalline architectures were spanning from a lamellar (L α ) phase to biphasic features of coexisting inverse bicontinuous (Q 2 ) cubic Pn3m and Im3m phases. Thus, a direct colloidal vesicle-cubosome transformation was detected by augmenting the concentration of docosahexaenoic acid monoacylglycerol. The produced cubosomes were thermally stable within the investigated temperature range of 5-60 °C. Collectively, our findings contribute to understanding of the imperative steps for production of stabilizer-free cubosomes from biocompatible lipids through a simple-by-design approach. We also discuss the potential therapeutic use and future implications for development of next-generation of multifunctional vesicles and cubosomes for co-delivery of docosahexaenoic acid and drugs in treatment of diseases., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

To improve nutritional health, a low-salt (0.5 %) silver carp (Hypophthalmichthys molitrix) surimi gel with α-tocopherol, soybean oil, and glyceryl monostearate oleogel was fabricated and evaluated for textural qualities, lipid oxidation, and in-vitro digestion analysis. Based on the texture profile analysis, gel strength, water holding capacity (WHC), rheological, protein secondary structure, and microstructural examination, 5 % oleogel addition to low-salt surimi exhibited similar physicochemical properties to regular-salt surimi gels. By crosslinking myosin and filling protein network voids, the oleogel increased surimi gel density. Increasing oleogel content improved the physicochemical qualities of heat-induced surimi, causing protein aggregation during digestion and reducing digestibility. The presence of oleogel altered protein secondary structure, reducing α-helix content and increasing β-sheet and other structures, enhancing WHC and gel strength of low salt surimi. Adding oleogel improved the antioxidant activity of digestive solutions. This study will help understand myosin-oleogel interaction and the development of sustainable and nutritious surimi-based foods., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The inclusion complex (IC) was successfully obtained by encapsulating glycerol monolaurate (GML) into the cavity of hydroxypropyl-β-cyclodextrin (HP-β-CD). Compared with solubility of pure GML <80 μg/mL in water, and the water-solubility of encapsulated GML was significantly improved and reached to 270,000 μg/mL. IC can form nanoparticles by self-assembly, probably assigned to its strong capability to form micellar-type aggregates. A Higuchi's A L -type phase-solubility diagram indicated the strong interaction between host and guest molecules with the formation of 1:1 GML/HP-β-CD complex and the stability constant at 6248 L/mol. Compared with pure GML, encapsulated GML at the same concentration can also show good antibacterial capabilities against S. aureus and E. coli in sterile water, and the effective preservative capabilities towards beef meatballs. The boosted enhancement in water-solubility of GML and the effective antibacterial capabilities endowed IC with potential in the application of food decontamination., Competing Interests: Declaration of competing interest The authors declared that they have no conflicts of interest to this work., (Copyright © 2023. Published by Elsevier Ltd.)

The Glycerol monolaurate (GML) oleogel was induced using Camellia oil by slowly raising the temp to the melting point (MP) of GML. Whey protein isolate (WPI) solution with different ratios was composited with GML oleogel by emulsion template methods, forming dense spines and honeycomb-like networks and impressed with an adjustable composite structure. Textural results showed that compared with single GML-based oleogels, the GML/WPI composite oleogels had the advantages of high hardness and molding, and structural stability. The composite oleogels had moderate thermal stability and maximal oil binding (96.36%). In particular, as up to 6 wt% GML/WPI, its modulus apparent viscosity was significantly increased in rheology and similar to commercial fats. Moreover, it achieved the highest release of FFA (64.07%) and the synergy provided a lipase substrate and reduced the body's burden. The resulting composite oleogel also showed intermolecular hydrogen bonding and van der Waals force interactions. These findings further enlarge the application in the plant and animal-based combined of fat substitutes, delivery of bioactive molecules, etc., with the desired physical and functional properties according to different proportions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

cis -12-oxo-Phytodieneoic acid-α-monoglyceride ( 1 ) was isolated from Arabidopsis thaliana . The chemical structure of 1 was elucidated based on exhaustive 1D and 2D NMR spectroscopic measurements and supported by FDMS and HRFDMS data. The absolute configuration of the cis -OPDA moiety in 1 was determined by comparison of 1 H NMR spectra and ECD measurements. With respect to the absolute configuration of the β-position of the glycerol backbone, the 2:3 ratio of ( S ) to ( R ) was determined by making ester-bonded derivatives with ( R )-(+)-α-methoxy-α-trifluoromethylphenylacetyl chloride and comparing 1 H NMR spectra. Wounding stress did not increase endogenous levels of 1 , and it was revealed 1 had an inhibitory effect of A. thaliana post germination growth. Notably, the endogenous amount of 1 was higher than the amounts of (+)-7- iso -jasmonic acid and (+)- cis -OPDA in intact plants. 1 also showed antimicrobial activity against Gram-positive bacteria, but jasmonic acid did not. It was also found that α-linolenic acid-α-monoglyceride was converted into 1 in the A. thaliana plant, which implied α-linolenic acid-α-monoglyceride was a biosynthetic intermediate of 1 .

The interaction of monoglycerides and phytosterols in olive- and coconut oil on the structuring of oleogels was analyzed. Specifically, bigels with gelatin hydrogel in different ratios (40:60 and 60:40 w/w) were formed. The physicochemical and microstructural attributes of these systems were assessed. The olive oil to coconut oil ratio (0-100 w/w) and the added oleogelators affected the crystal structure and the mechanical properties of the oleogels. Polarized light microscopy revealed that the addition of coconut oil created a denser triglycerides crystal network and the presence of phytosterols created more needle-like crystals, enhancing the textural properties of the oleogels and of the resulting bigels. The hardness of the oleogels ranged from 0.50 N to 1.24 N and for bigels was 5.96-36.75 N. Bigels hardness decreased as the oleogel ratio in the bigel increased. Microscopy and FTIR revealed that the addition of coconut oil in oleogels hampered the formation of a distinct crystalline monoglycerides network. Also, the absence of new peaks in the bigels indicated that the two structured phases interact with each other mostly physically, without the formation of new chemical bonds. Consequently, the oleogels and bigels developed, comprise a promising hard fat substitute with improved nutritional profile., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Eugenios Katsanidis reports financial support was provided by Hellenic Foundation for Research and Innovation., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In this study, we compared the quality of iron walnut oil (IWO) oleogels prepared with different oleogelators, including γ-oryzanol/β-sitosterol (OZ-PS), γ-oryzanol/triglyceride (OZ-TC), monoglycerides (MGS), beeswax (BW), beeswax-monoglycerides (BW-MGS), and carnauba wax (CW). The physicochemical and component properties, rheological and textural parameters, macroscopic morphologies, and antioxidant capacities of the resulting oleogels were analyzed. In addition, their microscopic properties were analyzed using Fourier-transform infrared (FTIR), X-ray powder diffraction (XRD) spectroscopy, and polarized light microscopy (PLM). The results showed that the gel structures produced by different oleogelators did not change the fatty acid composition of IWO. In addition, the IWO oleogel prepared with OZ-PS had a more stable network structure, excellent hardness at 4℃ (1116.51 g), better antioxidant capacity (766.50 μmol TE/kg) and higher total phenolic content (14.98 mg/kg) than any other experimental IWO oleogels. Moreover, comprehensive ranking by principal component analysis of numerous characteristics showed that the OZ-PS oleogel (2.533) ranked first among the six oleogels studied. Therefore, the IWO oleogel prepared with OZ-PS is a promising product, and our results provide guidance for the preparation of IWO oleogels, such as to increase their applications in the food industry., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Effect of stearic acid-based lipophilic emulsifiers (sorbitan monostearate (Span-60), sucrose ester S-170, and lactic acid esters of monoglycerides (LACTEM)) and oleic acid-based lipophilic emulsifiers (sorbitan monooleate (Span-80) and sucrose ester O-170) on the crystallization of fat blend and the stability of whipped cream were studied. Span-60 and S-170 possessed strong nucleation inducing ability and good emulsifying properties. Thus, tiny and uniform crystals were formed in fat blends, small and ordered fat globules were distributed in emulsions, and air bubbles were effectively wrapped in firmly foam structures. The crystallization of the fat blend and the stability of whipped cream were slightly modified by LACTEM due to its poor nucleation inducing ability and moderate emulsifying characteristic. Span-80 and O-170 had weak nucleation inducing ability and poor emulsifying properties, therefore, loose crystals were formed in fat blends and some big fat globules were separated in emulsions, thereby decreasing the stability of whipped creams., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The effect of different types of monoglycerides, including monopalmitin, capryl monoglyceride (GMB), and succinylated monoglyceride (GMSA) in combination with palm kernel stearin (PKS) and beeswax (BW), on the formation, crystal network structure, and partial coalescence properties of aerated emulsions (20 % w/w fat) was investigated. The stability of BW and PKS crystals with a 1 % concentration of GMSA and GMB, respectively, in the oil phase was lower than the other crystals. BW-GMSA and PKS-GMB crystals exhibited a lower crystallization rate, higher contact angles and no significant peak shift in the small-angle X-ray scattering results. The BW-GMSA and PKS-GMB emulsions had a lower nucleation rate in the bulk and a higher nucleation rate at the interface, resulting in a higher fraction of crystals adsorbed at the oil/water interface. This reduced the number of interfacial proteins and led to a high degree of partial coalescence and the formation of stable aerated networks., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Aquatic products are highly susceptible to spoilage, and preparing composite edible film with essential oil is an effective solution. In this study, composite edible films were prepared using perilla essential oil (PEO)-glycerol monolaurate emulsions incorporated with chitosan and nisin, and the film formulation was optimized by response surface methodology. These films were applied to ready-to-eat fish balls and evaluated over a period of 12 days. The films with the highest inhibition rate against Staphylococcus aureus were acquired using a polymer composition of 6 μL/mL PEO, 18.4 μg/mL glycerol monolaurate, 14.2 mg/mL chitosan, and 11.0 μg/mL nisin. The fish balls coated with the optimal edible film showed minimal changes in appearance during storage and significantly reduced total bacterial counts and total volatile basic nitrogen compared to the control groups. This work indicated that the composite edible films containing essential oils possess ideal properties as antimicrobial packaging materials for aquatic foods., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Acyl migration of 2-monoacylglycerols (2-MAGs) rich in DHA is a universal reaction occurring during storage and structural lipid synthesis, and affects their nutritional value. In this study, their acyl migration was investigated under different systems and temperatures. The enhanced temperature promoted acyl migration, leading to a 5.6-fold increase from 20 °C to 50 °C. The kinetic study indicated rate constants followed the order: hexane > solvent-free > dichloromethane > ethanol ≈ acetone ≈ acetonitrile > t-butanol, and positively correlated with log P of solvent. During acyl migration in ethanol, acetone, acetonitrile and t-butanol at 40 °C, DHA content in 2-MAGs was higher than in 1-MAGs, indicating slow acyl migration of DHA; while at 50 °C, the difference of DHA distribution was small, due to increasing acyl migration rate. The results suggest that acyl migration of different fatty acids can be regulated by changing conditions to enrich DHA at sn-2 position., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

In this study, soybean oil-based oleogels were prepared using soy-protein isolate (SPI) and glycerol monolaurate (GML) in an emulsion-template approach. The rheological, texture, microstructure, and oil-retention properties of the obtained oleogels were analyzed. Results showed that the soy oil-based oleogel prepared with 6 wt% GML exhibited high oil loss, low-hardness, and needle-like morphology compared to the soy-oil/SPI-based oleogel. On the other hand, soy oil-based /SPI-based oleogels structured by 3 or 6 wt% GML presented moderate thermal-stability and lowest oil loss than those prepared without GML. Furthermore, SPI-based oleogel containing 6 wt% GML showed highest free fatty acids release (62.07%) with significantly improved elastic modulus and apparent viscosity. Additionally, the obtained oleogels displayed the occurrence of van der Waals interactions and intermolecular hydrogen bonds, presenting enhanced thermal stability. These results contribute to a better understanding of oleogelation-based emulsions for formulating trans-free and low-saturated foodstuffs with desired physical and functional properties., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Recent years have witnessed significant achievements in the field of organic chemistry, which have led to new drugs and the discovery of new and biologically interesting molecules. Herein, we describe a practical and efficient approach to the synthesis of enantiomerically pure and diverse lysobisphosphatidic acid analogues. The key feature of the synthesis is a one-pot, sequential phosphorylation of a protected sn -2- O -oleoyl glycerol or sn -3- O -oleoyl glycerol with 2-cyanoethyl N , N -diisopropylchlorophosphoramidite, followed by oxidation.

The unique role of the spatial distribution of crystallizable emulsifiers in regulating the structure and properties of double emulsions has been gradually recognized. Herein, we utilized crystallizable monoglycerides of different carbon chain length (GMS/GMP/GML) to "structuring" the intermediate oil phase of double emulsions during a two-stage emulsification process followed by a cooling treatment. A ternary eigenvector (I, M, E) based on the numerical processing of polarization images was invented to quantitatively characterize the distribution pattern of monoglycerides. Crystallization kinetics analysis and dissipative particle dynamic simulation were then employed to reveal the regulatory mechanism for the site-specific interface distribution behavior. Results suggested that the distribution pattern of monoglycerides could be pricesly tuned as the internal interface-, external interface- or oil-phase dominated one in double emulsions. The surface activity as well as crystallization rates of monoglycerides dominated the interfacial distribution kinetics, and the cooling gradient along the interface region further regulated their interfacial distribution potential. Specificly, shorter crystallization time (t 1/2 ) made GMP molecules rapidly solidified in oil phase, leading to the oil phase domninate crystallization (0, M, 0), whereas, slow crystallization rate rendered GML and GMS with sufficient time to diffuse to the interface, thus forming interfacial crystals ((I, 0, 0) and (0, 0, E)). The sensitivity of GML to cooling gradient along the interface region led to its preferential external interface distribution under cooling treatment. The presented study explored novel strategies that can be used in characterizing and manipulating the distribution pattern of crystallizable emulsifiers in multi-interface emulsion systems., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Edible double network oleogels were prepared by hydroxypropyl methylcellulose (HPMC) and glyceryl monostearate (GMS) by the cryogel-templated method. Hot GMS soybean oil solutions were absorbed by HPMC cryogels, which were further homogenized and cooled to form oleogels containing both the HPMC network and GMS network. The crystal network constructed by GMS crystal clusters significantly enhanced the mechanical and rheological attributes of oleogels. Both the HPMC network and the GMS network were built up due to hydrogen bonds. According to the normalization analysis of FTIR and the deepening of the shift of the absorption peak, hydrogen bonds could also be formed between HPMC and GMS to connect the two independent networks. Double network oleogels were further used to fabricate cookies and cakes, assessed by the texture profile analysis. The combination of the HPMC network and GMS network in preparing oleogels will promote the application of oleogels as the fat replacer., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Monoglyceride (MG)-based oleogelation is an effective strategy to create soft matter structures with the functionality of fats, but with a nutritional profile similar to edible oils. MG oleogels are mainly studied to replace or reduce trans and saturated fats as well as to develop novel products with improved physical and organoleptic properties. The process consists of direct dispersion of MGs into the oil at temperatures above the melting point. This is followed by a cooling period in which the gelator network is formed, entrapping the oil in a crystalline structure. MG composition and concentration, oil type, process temperatures, stirring speed, shear rate during cooling, and storage time play a role in the kinetics of MG crystallization within an MG-oil system, which leads to the formation of lipid materials with different properties. A deep understanding of MG oleogelation processing parameters allows for the tailoring of oleogel properties to meet desirable characteristics as solid fat replacers. This review provides insight regarding manipulating physical process parameters to engineer structures with specific functionality. Furthermore, ultrasound technologies and optimization methodologies are discussed as tools for the production of oleogels with specific properties based on their potential use as well as the development of bi- and multi-gelators oleogels using MGs. Finally, the food applications in which MG oleogels have been tested are summarized in addition to the identified gaps that require further research., (© 2022 Institute of Food Technologists®.)

Double emulsions (DEs) are promising delivery vehicles for the protective and programmed release of bioactive compounds. Herein, DEs with monoglycerides crystallized at the internal- or external interface or oil phase were fabricated. The results suggested that the crystallization site of monoglycerides exerts a significant role in retarding the structural degradation and lipid digestion of DEs by affecting the available contact area of lipase. At the initial stage of intestinal digestion, compared with noncrystalline DEs (82.1%, 3.7 min), the burst release of internal markers in the internal interface crystallized emulsions was decreased by 42.4% and the lag time of free fatty acid (FFA) release was delayed by 5.8 min in the external interface crystallized emulsions. The structural integrity and digestion kinetics of the external interface crystallized DEs were synchronized with the retention time of the interfacial crystals. Therefore, crystallizable emulsifiers exhibit unique and fine regulatory effects on the digestive properties of emulsions.

The use of multicomponent oleogels combined with a physical process such as high-intensity ultrasound (HIU) has become an interesting alternative to overcome nutritional and technological issues in fat-based foods. This is because the combination can add technological properties without changing the total amount of gelators, improving sensory acceptance and clean label claim. In this context, the study aims to evaluate the structuration power and physical properties of oleogels formed by monoglycerides (MG), fully hydrogenated rapessed oil (FHRO), and lecithin (LE) in rapeseed oil, with and without HIU. All samples were analyzed according to their microstructure, melting behavior, rheology, texture, polymorphism, and oil binding capacity. In mono-structured oleogels, only MG was able to form gels that did not flow. Three synergic combinations that produced 99% oil binding capacity oleogels were found: MG: FHRO, FHRO:LE, and MG:FHRO:LE. These combinations showed improved physical properties like hardness, elastic modulus, and oil loss when sonicated, which was attributed to the induced secondary crystallization of the FHRO promoted by HIU., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The bacterial membrane is constantly remodelled in response to environmental conditions and the external supply of precursor molecules. Some bacteria are able to acquire exogenous lyso-phospholipids and convert them to the corresponding phospholipids. Here, we report that some soil-dwelling bacteria have alternative options to metabolize lyso-phosphatidylglycerol (L-PG). We find that the plant-pathogen Agrobacterium tumefaciens takes up this mono-acylated phospholipid and converts it to two distinct isoforms of the non-canonical lipid bis(monoacylglycero)phosphate (BMP). Chromatographic separation and quadrupole-time-of-flight MS/MS analysis revealed the presence of two possible BMP stereo configurations acylated at either of the free hydroxyl groups of the glycerol head group. BMP accumulated in the inner membrane and did not visibly alter cell morphology and growth behaviour. The plant-associated bacterium Sinorhizobium meliloti was also able to convert externally provided L-PG to BMP. Other bacteria like Pseudomonas fluorescens and Escherichia coli metabolized L-PG after cell disruption, suggesting that BMP production in the natural habitat relies both on dedicated uptake systems and on head-group acylation enzymes. Overall, our study adds two previously overlooked phospholipids to the repertoire of bacterial membrane lipids and provides evidence for the remarkable condition-responsive adaptation of bacterial membranes., (© 2021 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.)

Feruloyl glycerol (FG) is the hydrophilic ester of ferulic acid (FA), which has a high solubility in water and a strong ability to resist ultraviolet (UV) radiation. In this work, several solid acids were used as novel economical catalysts and FA was used as a cheap substrate for FG preparation. The effects of reaction variables on the esterification of FA with glycerol were investigated and optimized by response surface methodology (RSM). Results showed that a cheap solid acid cation exchange resin A-35 showed the best performance for esterification. The reaction conditions were optimized by RSM as follows: 15 : 1 (glycerol/FA) substrate molar ratio and 14% catalyst loading at 90 °C for 7 h. The maximum FG yield (98.50 ± 0.58%) was achieved under the optimized conditions. The activation energy of the esterification was 53.71 kJ mol -1 . The results of UV absorbance showed that FG had good anti-UV activity and photostability, which can be used as a potential antioxidant and UV absorber in food and sunscreen products.

Bile acids (BAs) are a family of steroids synthesized from cholesterol in the liver. Among bile acids, ursodeoxycholic acid (UDCA) is the drug of choice for treating primary biliary cirrhosis and dissolving cholesterol gallstones. The clinical effectiveness of UDCA includes its choleretic activity, the capability to inhibit hydrophobic bile acid absorption by the intestine under cholestatic conditions, reducing cholangiocyte injury, stimulation of impaired biliary output, and inhibition of hepatocyte apoptosis. Despite its clinical effectiveness, UDCA is poorly soluble in the gastro-duodeno-jejunal contents, and pharmacological doses of UDCA are not readily soluble in the stomach and intestine, resulting in incomplete absorption. Indeed, the solubility of 20 mg/L greatly limits the bioavailability of UDCA. Since the bioavailability of drug products plays a critical role in the design of oral administration dosages, we investigated the enzymatic esterification of UDCA as a strategy of hydrophilization. Therefore, we decided to enzymatically synthesize a glyceric ester of UDCA bile acid to produce a more water-soluble molecule. The esterification reactions between UDCA and glycerol were performed with an immobilized lipase B from Candida antarctica (Novozym 435) in solvent-free and solvent-assisted systems. The characterization of the UDCA-monoglyceride, enzymatically synthesized, has been performed by 1 H-NMR, 13 C-NMR, COSY, HSQC, HMBC, IR, and MS spectroscopy.

Background: Electrospun fibers are a good candidate for the delivery of bioactive compounds in the food industry because of their advantages that include a tunable diameter, high porosity and a high specific surface area. In the present study, we fabricated gelatin/glycerol monolaurate (GML) microemulsion nanofibers by solubilizing GML in Tween-80 followed by mixing with gelatin solution for electrospinning. We hypothesized that the addition of GML microemulsions affects the properties of the gelatin solution and modifies the physical and antimicrobial properties of the resulting nanofibers., Results: Both pure gelatin solution and gelatin/GML microemulsions showed shear-thinning behavior. However, electrospinnability was not affected by the addition of GML microemulsions. A significantly higher average diameter of nanofibers (1147 nm) with 5% GML was observed compared to the gelatin fiber diameter of 560 nm. Fourier transform infrared spectroscopy showed hydrogen bonding between gelatin molecules and GML microemulsions. Thermal analysis and X-ray diffraction indicated an amorphous structure of gelatin/GML microemulsion nanofibers, although a small amount of crystalline GML existed in the nanofibers with high GML content. Gelatin/GML microemulsion nanofibers showed high thermal stability and improved hydrophilicity. Nanofibers with 5% GML (weight with respect to nanofiber) (D64 nanofibers) showed effective antimicrobial activity against Escherichia coli and Staphylococcus aureus., Conclusion: Gelatin/GML microemulsion nanofibrous films demonstrate superhydrophilicity and fast dissolution properties as a result of the high surface-to-volume ratio, amorphous structure and improved hydrophilicity of the nanofiber surface. The results indicate the potential application of gelatin/GML microemulsion nanofibrous films as edible antimicrobial food packaging. © 2021 Society of Chemical Industry., (© 2021 Society of Chemical Industry.)

In this paper, different types of oleogels were prepared by five gelators including hydroxypropyl methyl cellulose (HPMC), monoacylglycerol (MAG), sodium stearyl lactate (SSL), rice bran wax (RBW) and beeswax (BW), and their applications in cookies were compared. Texture, microstructure, and colour results showed that MAG, RBW and shortening based cookies had similar hardness, porous structure, and L*, a*, b*. MAG and RBW exhibited excellent rheological properties similar to shortening. Regarding the consumer sensory evaluation of cookies, RBW, MAG and shortening had similar scores of 3.9, 4.3 and 4.1, respectively. For wax-based oleogels, the higher the content of β' crystal and solid fat content (SFC), the lower the hardness of cookies, but the cookies hardness of emulsifier based oleogels do not depend on β' content and SFC. This paper confirmed the best gelators for cookies, and provided a reference for developing the oleogels to match the quality of shortening in cookies., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The efficiency of filtration membranes is substantially lowered by bacterial attachments and potential fouling processes, which reduce their durability and lifecycle. The antibacterial and antifouling properties exhibited by the added materials play a substantial role in their application. We tested a material poly(vinylidene fluoride)- co -hexafluoropropylene (PDVF- co -HFP) based on an electrospun copolymer, where an agent was incorporated with a small amount of ester of glycerol consecutively with caprylic, capric, and lauric acids. Each of these three materials differing in the esters (1-monoacylglycerol, 1-MAG) used was prepared with three weighted concentrations of 1-MAG (1, 2, and 3 wt %). The presence of 1-MAG with an amphiphilic structure resulted in the hydrophilic character of the prepared materials that contributed to the filtration performance. The tested materials (membranes) were characterized with rheological, optical (scanning electron microscopy, SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and other methods to evaluate antibacterial and antifouling activities. The pure water flux was 6 times higher than that of the neat PVDF- co -HFP membrane when the added 1-MAG attained only 1 wt %. It was experimentally shown that the PVDF- co -HFP/1-MAG membrane with high wettability improved antibacterial activity and antifouling ability. This membrane is highly promising for water treatment due to the safety of antibacterial 1-MAG additives.

Here, we developed an efficient strategy for the production of lauric acid-enriched monoacylglycerol (MAG) via enzymatic glycerolysis using black soldier fly (Hermetia illucens) larvae (BSFL) oil. The effects of the substrate molar ratio, reaction temperature, type of immobilized lipase, and organic solvent on the MAG content and conversion degree of BSFL oil were optimized. The maximum substrate conversion rate (97.88%) and MAG content (70.84%) were obtained in a tert-butanol system at 50 °C with a glycerol/BSFL oil molar ratio of 4:1 by using immobilized MAS1 lipase as a catalyst. The MAG content in the purified product reached 97.7%, with lauric acid accounting for 50.2%. Improved oxidation stability was observed after glycerolysis. Overall, this study provides a new strategy for the preparation of lauric acid-enriched MAG from BSFL oil., (© 2021. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

The effect of using highly unsaturated 2-monoglycerides as oleogelators on the properties of soybean oil oleogels designed to eliminate saturated and trans fatty acids was investigated in this study. We adopted a novel two-step synthesis aiming to increase the yield of the 2-monoglycerides. The optimal synthesis conditions were a substrate weight ratio of 2:1 (w/w), 10% Lipozyme 435 (w/w total reactants), and 4 h of reaction time at room temperature. Under these conditions, the 2-monoglyceride yield (40.69%) increased by 10% compared to that of the conventional synthesis route. Additionally, soybean oil oleogels prepared using 10% 2-monoglycerides with or without rice bran wax were systematically characterized by polarized light microscopy, a texture analyzer, XRD spectroscopy, and rheometry. Comparative studies indicated that a combination of rice bran wax and 2-monoglycerides had synergistic effects on gel properties. A mixture of 4% rice bran wax and 6% 2-monoglycerides was found to provide better oleogels., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Vitamin C (VC)-loaded oleogel (VCOG) with corn oil and monoglyceride stearate was used to replace lipid phase of margarine completely. The oxidative stability of VCOG was evaluated at 60±1°C in a lightproof oven for 18 days and the result showed that VCOG peroxide (> 6 days) and p-anisidine value (> 4 days) was significantly lower than that of bulk oil and VC-free oleogel (p < 0.05). Then, the margarine containing 79.70% VCOG (VCOGM) was in comparison with four commercial butter in sensory and physical characteristic. Results showed that firmness, solid fat content and trans fatty acid of VCOGM were in the lowest values while unsaturated fatty acid and adhesiveness of VCOGM was in the highest values. Furthermore, VCOGM presented the similar springiness, cohesiveness, gumminess, score appearance, texture, taste and overall impression to some/all commercial butters selected in this research (p > 0.05). These results implied that VC-loaded oleogel was an excellent alternative of lipid phase in margarine which confirmed by 55% "definitely buy" and 25% "try once-then decide".

Glucuronic acid containing diacylglycerols (3-(O-α-d-glucuronopyranosyl)-1,2-diacyl- sn -glycerols, GlcA-DAG) are glycolipids of plant membranes especially formed under phosphate-depletion conditions. An analytical approach for the structural characterization of GlcA-DAG in red ripe tomato ( Solanum lycopersicum L. ) extracts, based on reversed-phase liquid chromatography (RPLC) coupled with electrospray ionization (ESI) and tandem mass spectrometry (MS/MS) using a linear ion trap, is described in this paper. At least 14 GlcA-DAG (R 1 /R 2 ) species, including four regioisomers, containing three predominant fatty acyl chains C16:0, C18:2, and C18:3, were identified for the first time. Moreover, 29 GlcA-DAG acylated on the glucuronosyl ring (acyl-R 3 GlcA-DAG) were discovered, alongside 15 acylated lyso -forms, i.e., acylated 3-( O -α-d-glucuronosyl)monoacylglycerols, abbreviated as acyl-R 3 GlcA-MAG (R 1 /0) or (0/R 2 ). Although many of these acylated lyso -forms were isomeric with GlcA-DAG (i.e., acyl chains with equivalent sum composition), they were successfully separated by reversed-phase liquid chromatography (RPLC) using a solid-core C18 column packed with 2.6 μm particle size. Tandem MS (and eventually MS 3 ) data obtained from sodium adducts ([M + Na] + ) and deprotonated molecules ([M - H] - ) were fundamental to detect diagnostic product ions related to the glucuronosyl ring and then determine the identity of all investigated glycolipids, especially to recognize the acyl chain linked to the ring. A classification of GlcA-MAG, GlcA-DAG, and acylated GlcA-DAG and GlcA-MAG was generated by an in house-built database. The discovery of acylated derivatives emphasized the already surprising heterogeneity of glucuronic acid-containing mono- and diacylglycerols in tomato plants, stimulating interesting questions on the role played by these glycolipids.

Tripalmitin-(PPP, 81.2%), 1,3-dipalmitoyl-2-oleoylglycerol-(POP, 64.4%), 1,2-dipalmitoyl-3-oleoylglycerol-(PPO, 86.5%), and 1,3-dioleoyl-2-palmitoylglycerol-(OPO, 50.2%)-rich lipids with different regiospecific positions of palmitic acid (P) were synthesized via acetone fractionation and lipase-catalyzed acidolysis, and their physicochemical and hydrolytic characteristics were compared. Triacylglycerols (TAGs) with higher content of P, wherein P was at the sn -1 (or 3) position, had higher melting points, crystallization temperatures, and packing densities of fat crystals compared to those with a lower content of P, and with P at the sn -2 position. The in vitro digestion degree calculated as released fatty acid (FA) (%) at 30, 60, and 120 min was in the following order: OPO-rich > PPO-rich > POP-rich lipids. At 120 min, in vitro digestion of the OPO-rich lipid released 92.6% of fatty acids, resulting in the highest digestibility, while 89.7% and 87.2% of fatty acids were released from the OPO-rich and PPO-rich lipids, respectively. Over the digestion period, the TAG and monoacylglycerol (MAG) contents decreased, while the diacylglycerol (DAG) content initially increased and then decreased, and the 1,2-DAG content exceeded the 1,3-DAG content. Therefore, the content and stereospecific position of P attached to a specific TAG affected the physicochemical and in vitro digestion characteristics of the lipids.

Monoacylglycerol lipase (MAGL) is a key enzyme in the human endocannabinoid system. It is also the main enzyme responsible for the conversion of 2-arachidonoyl glycerol (2-AG) to arachidonic acid (AA), a precursor of prostaglandin synthesis. The inhibition of MAGL activity would be beneficial for the treatment of a wide range of diseases, such as inflammation, neurodegeneration, metabolic disorders and cancer. Here, the author reports the pharmacological evaluation of new disulfiram derivatives as potent inhibitors of MAGL. These analogues displayed high inhibition selectivity over fatty acid amide hydrolase (FAAH), another endocannabinoid-hydrolyzing enzyme. In particular, compound 2i inhibited MAGL in the low micromolar range. However, it did not show any inhibitory activity against FAAH.

Background: Omega-3 (n-3) fatty acid (FA) supplements increase blood concentrations of EPA and DHA. Most of the supplements on the market are esterified in triglycerides (TGs) or ethyl esters (EEs), which limits their absorption and may cause gastrointestinal side effects., Objective: The objective of this study was to compare the 24-h AUC of the plasma concentrations of EPA, DHA, and EPA+DHA when provided esterified in monoglycerides (MAGs), EEs, or TGs, (primary outcomes) and evaluate their side effects over 24 h (secondary outcome)., Methods: This was a randomized, triple-blind, crossover, controlled clinical trial. Eleven women and 11 men between 18 and 50 y of age ingested, in random order, a single oral dose of ∼1.2 g of EPA and DHA esterified in MAGs, EEs, and TGs with low-fat meals provided during the 24-h follow-up. Eleven blood samples over 24 h were collected from each participant, and the plasma n-3 FAs were quantified. Friedman's paired ANOVA statistical rank test was used for the pharmacokinetic parameters and a chi-square statistical test was used for the side effects., Results: The 24-h AUC of plasma EPA was ∼2 times and ∼1 time higher after the MAG compared with the EE and TG forms of n-3 FAs, respectively (P ≤ 0.0027). Effects of the EE and TG treatments did not differ. The 3 supplements had similar eructation, dysgeusia, abdominal discomfort, nausea, and bloating side effects., Conclusions: The plasma n-3 FA concentration in adults is greater after acute supplementation with n-3 FAs esterified in MAGs rather than in EEs or TGs, suggesting that with a lower dose of MAG n-3 FAs, the plasma n-3 FA concentrations attained are similar to those after higher doses of n-3 FAs esterified in EEs or TGs. This trial is registered at www.clinicaltrials.gov as NCT03897660., (© The Author(s) 2021. Published by Oxford University Press on behalf of the American Society for Nutrition.)

Biomaterials used in tissue regeneration processes represent a promising option for the versatility of its physical and chemical characteristics, allowing for assisting or speeding up the repair process stages. This research has characterized a polyurethane produced from castor oil monoacylglyceride (Ricinus communis L) and tested its effect on reconstructing bone defects in rat calvaria, comparing it with commercial castor oil polyurethane. The characterizations of the synthesized polyurethane have been performed by spectroscopy in the infrared region with Fourier transform (FTIR); thermogravimetric analysis (TG/DTG); X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). For the in vivo test, 24 animals have been used, divided into 3 groups: untreated group (UG); control group treated with Poliquil® castor polyurethane (PCP) and another group treated with castor polyurethane from the Federal University of Piauí - UFPI (CPU). Sixteen weeks after surgery, samples of the defects were collected for histological and histomorphometric analysis. FTIR analysis has shown the formation of monoacylglyceride and polyurethane. TG and DTG have indicated thermal stability of around 125 °C. XRD has determined the semi-crystallinity of the material. The polyurethane SEM has shown a smooth morphology with areas of recesses. Histological and histomorphometric analyzes have indicated that neither CPU nor PCP induced a significant inflammatory process, and CPU has shown, statistically, better performance in bone formation. The data obtained shows that CPU can be used in the future for bone reconstruction in the medical field.

Oleogels and oleogelation routes have been extensively studied in the past decade; however, the industry has not yet implemented this technique due to price, availability, and clean label. The objective of this study was to evaluate the synergism of binary oleogels structured by monoglycerides (MG) and high melting point triacylglycerols (HF) with and without high-intensity ultrasound (HIU) according to their physical properties. MG:HF (0:6, 1:5, 2:4, 3:3, 4:2, 5:1, and 6:0) oleogels were produced by mixing at 70 °C with a stirring of 350 rpm for 5 min, followed by a cooling and storage at 20 °C for 24 hr. A 20-kHz HIU was applied for 10s, 30s, or 10s using three pulses (10sON/10sOFF) during the cooling step via a macro tip (12.7 mm) and 50% amplitude (56 W) in the presence of few -crystals. Samples were evaluated according to their hardness, oil-binding capacity (OBC), microstructure, melting behavior, viscoelasticity, and flow behavior. The best physical properties were found in the MG6:HF0 oleogel, with a hardness of 1.2 N, elasticity of 5.5 kPa, viscosity of 99 Pa⋅s and 99% OBC. These properties were reduced with the decrease of MG in the blend. The sonication did not improve the MG6:HF0, instead it affected its properties negatively. However, sonication showed a positive effect on the blends of MG and HF. The hardness was improved at least threefold and OBC around 20%, these effects were already observed using only 10s sonication. Sonocrystallization induced secondary nucleation and changed the crystalline material only in blends containing HF indicating the better effect of the sonocrystallization on oleogels in the presence of high-melting points triacylglycerols. PRACTICAL APPLICATION: Oleogels are a valuable alternative in food industry to replace trans and reduce saturated fatty acids content in many food products. The combination of a binary structuration and use of high-intensity ultrasound that is a physical green technology will give the food industry information on how to improve the physical properties of oleogels without increasing the amount of oleogelators, giving a future alternative to clean label and sensory claims of oleogels applications., (© 2021 Institute of Food Technologists®.)

This research was conducted to evaluate the potential use of saturated monoglyceride (MG)-based gels in the protection of probiotics upon in vitro digestion. For this purpose, a Lactobacillus rhamnosus strain was inoculated into binary and ternary systems, containing MGs, a water phase composed of an aqueous solution at controlled pH or UHT skimmed milk, and in ternary gels, sunflower oil. Gel structure characterization was initially performed just after preparation and after 14 days of storage at 4 °C by rheological, mechanical, thermal, and microscopy analyses. Afterwards, probiotic viability upon in vitro digestion was evaluated. The results highlighted that all freshly prepared samples showed good capability to protect L. rhamnosus with the exception of the binary system containing milk. However, the digestion of samples after 14 days of storage showed that the ternary system containing skimmed milk exhibited the best protection performance ensuring a L. rhamnosus viability of almost 10 6 CFU g -1 at the end of the gastrointestinal passage. Confocal microscopy results demonstrated that bacterial cells were located prevalently within the aqueous domain near the monoglycerides and protein aggregates. Under these conditions, they can simultaneously achieve physical protection and find nutrients to survive environmental stresses. These findings suggest that MG-based gels can be proposed as efficient carriers of probiotic bacteria not only during food processing and storage but also upon digestion.

Phospholipids play important roles in biological process even at a very low level. For example, bis(monoacylglycerol)phosphate (BMP) is involved in the pathogenesis of lysosomal storage diseases, and polyphosphoinositides (PPI) play critical roles in cellular signaling and functions. Phosphatidylglycerol (PG), a structural isomer of BMP, mediates lipid-protein and lipid-lipid interactions, and inhibits platelet activating factor and phosphatidylcholine transferring. However, due to their low abundance, the analysis of these phospholipids from biological samples is technically challenging. Therefore, the cellular function and metabolism of these phospholipids are still elusive. This chapter overviews a novel method of shotgun lipidomics after methylation with trimethylsilyl-diazomethane (TMS-D) for accurate and comprehensive analysis of these phospholipid species in biological samples. Firstly, a modified Bligh and Dyer procedure is performed to extract tissue lipids for PPI analysis, whereas modified methyl-tert-butylether (MTBE) extraction and modified Folch extraction methods are described to extract tissue lipids for PPI analysis. Secondly, TMS-D methylation is performed to derivatize PG/BMP and PPI, respectively. Then, we described the shotgun lipidomics strategies that can be used as cost-effective and relatively high-throughput methods to determine BMP, PG, and PPI species and isomers with different phosphate position(s) and fatty acyl chains. The described method of shotgun lipidomics after methylation achieves feasible and reliable quantitative analysis of low-abundance lipid classes. The application of this novel method should enable us to reveal the metabolism and functions of these phospholipids in healthy and disease states.

Present in the small intestine, cellular retinol binding protein 2 (CRBP2) plays an important role in the uptake, transport, and metabolism of dietary retinoids. However, the recent discovery of the interactions of CRBP2 with 2-arachidonoylglycerol and other monoacylglycerols (MAGs) suggests the broader involvement of this protein in lipid metabolism and signaling. To better understand the physiological role of CRBP2, we determined its protein-lipid interactome using a fluorescence-based retinol replacement assay adapted for a high-throughput screening format. By examining chemical libraries of bioactive lipids, we provided evidence for the selective interaction of CRBP2 with a subset of nonretinoid ligands with the highest affinity for sn-1 and sn-2 MAGs that contain polyunsaturated C18-C20 acyl chains. We also elucidated the structure-affinity relationship for nonretinoid ligands of this protein. We further dissect the molecular basis for this ligand's specificity by analyzing high-resolution crystal structures of CRBP2 in complex with selected derivatives of MAGs. Finally, we identify T51 and V62 as key amino acids that enable the broadening of ligand selectivity to MAGs in CRBP2 as compared with retinoid-specific CRBP1. Thus, our study provides the molecular framework for understanding the lipid selectivity and diverse functions of CRBPs in controlling lipid homeostasis., Competing Interests: Conflict of interest The authors declare that they have no conflicts of interest with the contents of this article., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

In this study, Candida antarctica lipase B (CALB), Rhizomucor miehei lipase (RML) and Lecitase ® Ultra (LU) were immobilized onto the mesoporous silica SBA-15. The glycerolysis performance of the obtained supported lipases (lipase@SBA-15) in solvent systems was carefully investigated. LU@SBA-15 exhibited good glycerolysis performance in solvent-free system, with diacylglycerols (DAG) content and triacylglycerols (TAG) conversion at 52.4 and 98.6% respectively obtained after 12 h reaction at 60°C. CALB@SBA-15 showed good glycerolysis activity in tert-pentanol and tert-butanol systems, with TAG conversion over 90% obtained. In addition, the present CALB@SBA-15 exhibited selectivity for monoacylglycerols (MAG) production, with glycerol to TAG molar ratio increased to 3:1, MAG content over 80% and TAG conversion over 99% could be obtained from both tert-pentanol and tert-butanol systems. However, RML@SBA-15 showed low glycerolysis activity neither in solvent nor in solvent-free systems. The present results favor the practical enzymatic design for MAG and DAG production.

Objectives: The aim of this study was to use Ligand-based pharmacophore modelling approach for four established antiviral drugs, namely remdesivir, lopinavir, ritonavir and hydroxychloroquine for COVID-19 inhibitors as training sets. In this study Twenty vanillin derivatives together with monolaurin and tetrodotoxin were used as test sets to evaluate as potential SARS-CoV-2 inhibitors. The Structure-based pharmacophore modelling approach was also performed using 5RE6, 5REX and 5RFZ in order to analyse the binding site and ligand-protein complex interactions., Results: The pharmacophore modelling mode of 5RE6 displayed two Hydrogen Bond Acceptors (HBA) and one Hydrophobic (HY) interaction. Besides, the pharmacophore model of 5REX showed two HBA and two HY interactions. Finally, the pharmacophore model of 5RFZ showed three HBA and one HY interaction. Based on ligand-based approach, 20 Schiff-based vanillin derivatives, showed strong M Pro inhibition activity. This was due to their good alignment and common features to PDB-5RE6. Similarly, monolaurin and tetrodotoxin displayed some significant activity against SARS-CoV-2. From structure-based approach, vanillin derivatives (1) to (12) displayed some potent M Pro inhibition against SARS-CoV-2. Favipiravir, chloroquine and hydroxychloroquine also showed some significant M Pro inhibition.

In meso crystallization of membrane proteins relies on the use of lipids capable of forming a lipidic cubic phase (LCP). However, almost all previous crystallization trials have used monoacylglycerols, with 1-(cis-9-octadecanoyl)-rac-glycerol (MO) being the most widely used lipid. We now report that EROCOC 17+4 mixed with 10% (w/w) cholesterol (Fig. 1) serves as a new matrix for crystallization and a crystal delivery medium in the serial femtosecond crystallography of Adenosine A 2A receptor (A 2A R). The structures of EROCOC 17+4 -matrix grown A 2A R crystals were determined at 2.0 Å resolution by serial synchrotron rotation crystallography at a cryogenic temperature, and at 1.8 Å by LCP-serial femtosecond crystallography, using an X-ray free-electron laser at 4 and 20 °C sample temperatures, and are comparable to the structure of the MO-matrix grown A 2A R crystal (PDB ID: 4EIY). Moreover, X-ray scattering measurements indicated that the EROCOC 17+4 /water system did not form the crystalline L C phase at least down to - 20 °C, in marked contrast to the equilibrium MO/water system, which transforms into the crystalline L C phase below about 17 °C. As the L C phase formation within the LCP-matrix causes difficulties in protein crystallography experiments in meso, this feature of EROCOC 17+4 will expand the utility of the in meso method.

Organogel (OG) is a class of semi-solid gel, entrapping organic solvent within a three-dimensional network, which is formed via the self-assembly of organogelators. In the present study, OG was produced by glycerol monolaurate (GML) as organogelator. The influence of hydrocolloids with different surface charges (chitosan (CS), konjac glucomannan (KGM) and sodium alginate (SA)) on the physiochemical properties of OG was investigated. Rheological studies demonstrated that OG and pure hydrocolloid solution showed shear-thinning behavior. After incorporation of the hydrocolloid, the initial viscosity of OG was lowered from ~100 Pa·s to <10 Pa·s, and then the viscosity increased to more than 100 Pa·s at a low shear rate of 0.1-0.2 s -1 , which subsequently decreased with a higher shear rate. OGs in the presence of hydrocolloids still kept the thermo-sensitivity, while the melting point of the OG decreased with the incorporation of hydrocolloids. Hydrocolloid addition greatly shortened the gelling time of the OG from 21 min to less than 2 min. The presence of hydrocolloids increased the particle size of oil droplets in the molten OG. Some aggregation and coalescence of oil droplets occurred in the presence of positive-charged CS and negative-charged SA, respectively. After gelling, the gel structure converted into a biphasic-like network. Hydrocolloids improved the hardness, stickiness and the oil-holding stability of OGs by 18.8~33.9%. Overall, hydrocolloid incorporation could modulate the properties of OGs through their different surface charge properties. These novel OGs have potential as nutrient carriers or low-fat margarine alternatives and avoid the trans-fatty acid intake.

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.

The Expert Panel for Cosmetic Ingredient Safety (Panel) assessed the safety of 44 monoglyceryl monoesters that are structurally constituted as the esterification products of glycerin and carboxylic acids (the majority of which are fatty acids); 36 of these monoesters were previously reviewed by the Panel, and 8 are reviewed herein for the first time. Most of the monoglyceryl monoesters have several reported functions in cosmetics, but the most common function among the ingredients is skin conditioning agent; a few are reported to function only as surfactant-emulsifying agents. The Panel reviewed relevant new data, including frequency and concentration of use and considered the data from previous Cosmetic Ingredient Review reports. The Panel concluded that these ingredients are safe in cosmetics in the present practices of use and concentration described in this safety assessment.

Bis(monoacylglycero)phosphate (BMP), also known as lysobisphosphatidic acid (LBPA), is a phospholipid specifically enriched in the late endosome-lysosome compartment playing a crucial role for the fate of endocytosed components. Due to its presence in extracellular fluids during diseases associated with endolysosomal dysfunction, it is considered as a possible biomarker of disorders such as genetic lysosomal storage diseases and cationic amphiphilic drug-induced phospholipidosis. However, there is no true validation of this biomarker in human studies, nor a clear identification of the carrier of this endolysosome-specific lipid in biofluids. The present study demonstrates that in absence of any sign of renal failure, BMP, especially all docosahexaenoyl containing species, are significantly increased in the urine of patients treated with the antiarrhythmic drug amiodarone. Such urinary BMP increase could reflect a generalized drug-induced perturbation of the endolysosome compartment as observed in vitro with amiodarone-treated human macrophages. Noteworthy, BMP was associated with extracellular vesicles (EVs) isolated from human urines and extracellular medium of human embryonic kidney HEK293 cells and co-localizing with classical EV protein markers CD63 and ALIX. In the context of drug-induced endolysosomal dysfunction, increased BMP-rich EV release could be useful to remove excess of undigested material. This first human pilot study not only reveals BMP as a urinary biomarker of amiodarone-induced endolysosomal dysfunction, but also highlights its utility to prove the endosomal origin of EVs, also named as exosomes. This peculiar lipid already known as a canonical late endosome-lysosome marker, may be thus considered as a new lipid marker of urinary exosomes., Competing Interests: Declaration of competing interest The authors declared no competing financial interest., (Copyright © 2020 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.)