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.

Composite-structure oleogels constructed by glycerol monolaurate and whey protein isolate: Preparation, characterization and in vitro digestion.

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.

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.

Formation, stability, and antimicrobial efficacy of eutectic nanoemulsions containing thymol and glycerin monolaurate.

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.

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.

On the structural and mechanical properties of mixed coconut and olive oil oleogels and bigels.

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.

Effects of different oleogelators on the structural properties and composition of iron walnut-oil oleogels.

In this study, we compared the quality of iron walnut oil (IWO) oleogels prepared with different oleogelators, including γ-oryzanol/ß-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.

Effect of different chain lengths of monoglyceride on the O/W interfacial properties with high-melting and low-melting crystals in low-fat aerated emulsion.

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.

Effect of stearic and oleic acid-based lipophilic emulsifiers on the crystallization of the fat blend and the stability of whipped cream.

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.

Acyl migration of 2-monoacylglycerols rich in DHA: Effect of temperature and solvent medium.

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.

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.

Soy oil and SPI based-oleogels structuring with glycerol monolaurate by emulsion-templated approach: Preparation, characterization and potential application.

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.

Effects of the Distribution Site of Crystallizable Emulsifiers on the Gastrointestinal Digestion Behavior of Double Emulsions.

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.

Double network oleogels co-stabilized by hydroxypropyl methylcellulose and monoglyceride crystals: Baking applications.

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.

Modulation of the spatial distribution of crystallizable emulsifiers in Pickering double emulsions.

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 (t1/2) 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.

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.

Influence of sonocrystallization on lipid crystals multicomponent oleogels structuration and physical properties.

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.

Enhancement of the hydrophilic feruloyl glycerol synthesis using A-35 as a catalyst and its functional characteristics.

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.

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.