The Bis(monoacylglycero)-phosphate Hypothesis: From Lysosomal Function to Therapeutic Avenues.

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.

Isolation and Structure Determination of cis-OPDA-α-Monoglyceride from Arabidopsis thaliana.

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 1H NMR spectra and ECD measurements. With respect to the absolute configuration of the ß-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 1H 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.

Relationships between the inhibitory efficacy and physicochemical properties of six organic acids and monolaurin against Bacillus weihenstephanensis KBAB4 growth in liquid medium.

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.

Application of Stemphylium lycopersici Extracts Immobilized on MCM-48type Mesoporous Materials as Biocatalysts for Monoacylglycerol Production.

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.

The Impact of Beeswax and Glycerol Monolaurate on Camellia Oil Oleogel's Formulation and Application in Food Products.

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.

Syntheses of Symmetrical and Unsymmetrical Lysobisphosphatidic Acid Derivatives.

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.

An overview of structure engineering to tailor the functionality of monoglyceride oleogels.

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.

Synthesis of the unusual lipid bis(monoacylglycero)phosphate in environmental bacteria.

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.

Pharmacokinetics of Supplemental Omega-3 Fatty Acids Esterified in Monoglycerides, Ethyl Esters, or Triglycerides in Adults in a Randomized Crossover Trial.

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.

Polyurethane derived from castor oil monoacylglyceride (Ricinus communis) for bone defects reconstruction: characterization and in vivo testing.

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.

Regiospecific Positioning of Palmitic Acid in Triacylglycerol Structure of Enzymatically Modified Lipids Affects Physicochemical and In Vitro Digestion Properties.

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.

Glyceric Prodrug of Ursodeoxycholic Acid (UDCA): Novozym 435-Catalyzed Synthesis of UDCA-Monoglyceride.

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 1H-NMR, 13C-NMR, COSY, HSQC, HMBC, IR, and MS spectroscopy.

New Disulfiram Derivatives as MAGL-Selective Inhibitors.

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.

Fabrication and characterization of fast dissolving glycerol monolaurate microemulsion encapsulated gelatin nanofibers with antimicrobial activity.

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.

Chase Dosing of Lipid Formulations to Enhance Oral Bioavailability of Nilotinib in Rats.

PURPOSE: Lipid-based formulations (LBF) have shown oral bioavailability enhancement of lipophilic drugs, but not necessarily in the case of hydrophobic drugs. This study explored the potential of lipid vehicles to improve the bioavailability of the hydrophobic drug nilotinib comparing a chase dosing approach and lipid suspensions. METHODS: Nilotinib in vivo bioavailability in rats was determined after administering an aqueous suspension chase dosed with blank olive oil, Captex 1000, Peceol or Capmul MCM, respectively. Absolute bioavailability was determined (relative to an intravenous formulation). Pharmacokinetic parameters were compared to lipid suspensions. RESULTS: Compared to the lipid suspensions, the chase dosed lipids showed a 2- to 7-fold higher bioavailability. Both long chain chase dosed excipients also significantly increased the bioavailability up to 2-fold compared to the aqueous suspension. Deconvolution of the pharmacokinetic data indicated that chase dosing of nilotinib resulted in prolonged absorption compared to the aqueous suspension. CONCLUSION: Chase dosed LBF enhanced the in vivo bioavailability of nilotinib. Long chain lipids showed superior performance compared to medium chain lipids. Chase dosing appeared to prolong the absorption phase of the drug. Therefore, chase dosing of LBF is favourable compared to lipid suspensions for 'brick dust' molecules such as nilotinib. Graphical Abstract The potential of bio-enabling lipid vehicles, administered via chase dosing and lipid suspensions, has been evaluated as an approach to enhance oral bioavailability of nilotinib.

Safety Assessment of Monoglyceryl Monoesters as Used in Cosmetics.

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.

Sustained delivery of prilocaine and lidocaine using depot microemulsion system: in vitro, ex vivo and in vivo animal studies.

Topical drug delivery for local anesthetics has been an interesting area of research for formulators considering the resistance and barrier properties of skin and high clearance rate of drugs like prilocaine and lidocaine (duration of action < 2.5 h). In this study, efforts have been made to sustain the release of prilocaine and lidocaine by using depot microemulsion system. Drug loaded microemulsions were formulated using Capmul MCM, Pluronic F127, polyethylene glycol 200 (PEG 200) and water from pseudo-ternary diagrams. The Smix at 1:4 ratio showed larger microemulsion area in comparison to 1:2 ratio. The ex-vivo studies indicate sustained release of prilocaine and lidocaine from the microemulsion up to 8 h, in comparison to 4 h with ointments. Skin irritation study on rabbits confirmed the safety of drug loaded microemulsions for local drug delivery. The improved ex vivo data is reflected in the in vivo studies, were radiant heat tail-flick test and sciatic nerve model showed prolong duration of action for both prilocaine and lidocaine microemulsions in comparison to ointment. The in vitro and in vivo efficacy of prilocaine and lidocaine was non-significant. The improved efficacy was due to high penetration of microemulsion and depot effect due to local precipitation (destabilization of microemulsion) of drug in the skin layer. The sustained local anesthetic effect is highly desirable for the treatment of skin irritation due to skin burns and pre- and post-operative pain.

(+)-Limonene 1,2-Epoxide-Loaded SLNs: Evaluation of Drug Release, Antioxidant Activity, and Cytotoxicity in an HaCaT Cell Line.

In this work, we developed a solid lipid nanoparticle (SLN) formulation with (+)-limonene 1,2-epoxide and glycerol monostearate (Lim-SLNs), stabilized with Poloxamer® 188 in aqueous dispersion to modify the release profile of the loaded monoterpene derivative. We also evaluated the role of SLNs in lipid peroxidation and cytotoxicity in a spontaneously transformed aneuploid immortal keratinocyte cell line from adult human skin (the HaCaT cell line). For the cell viability assay, the colorimetric 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay was used. Lim-SLNs with a loading capacity and encapsulation efficiency of 0.39% and 63%, respectively, were produced by high pressure homogenization. A mean particle size of 194 ± 3.4 nm and polydispersity index of 0.244 were recorded for the loaded Lim-SLNs, as compared to 203 ± 1.5 nm (PI 0.213) for the non-loaded (blank) SLNs. The loading of the monoterpene derivative into glycerol monostearate SLNs fitted into the zero-order kinetics, and ameliorated both lipid peroxidation and cytotoxicity in a keratinocyte cell line. A promising formulation for antioxidant and anti-tumoral activities is here proposed.

Structure and Rheological Properties of Glycerol Monolaurate-Induced Organogels: Influence of Hydrocolloids with Different Surface Charge.

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.

Boronic Derivatization of Monoacylglycerol and Monitoring in Biofluids.

Monoacylglycerols (MAGs) are active mediators involved in multiple biological processes closely related to the pathological development of diabetes, obesity, and cancers. Sensitive and unambiguous detection of MAGs is thus essential; however, previous methods are both indirect and labor-intensive. Herein, we developed a straightforward approach by derivatization of MAGs with 3-nitrophenylboronic acid (3-NPB) for sensitive and selective analysis in cell lysates, tissues, and serums by mass spectrometry (MS). Reaction occurring between boronic acid and cis-diol moiety of MAGs blocked the formation of multiple adduct ions and tuned MAGs to negatively charged carrying species. In addition, the characteristic isotopic distribution of boron specialized the presence of modified MAGs in MS and led to distinctive identification. To eliminate endogenous interferences, we further introduced isotopic labeled d4-NPB equivalently premixed with d0-NPB to perform MAG derivatization, which resulted in rapid identification of modified MAGs in biofluids by displaying doublet peak characteristics. A comparative quantification approach was thereafter evoluted to reveal the amount variation of MAGs by d0-NPB and d4-NPB separately derivatized in different pathological tissue and serum samples. The presently developed NPB-based derivatization approach is expected to be essential in the metabolic study of MAG-related diseases.