Stabilisation of oleofoams by lauric acid and its glycerol esters.

Four types of pure lipid, namely lauric acid (LA), glycerol monolaurate (MAG), diglycerol laurate (DAG) and triglyceride laurate (TAG) were used to prepare oleofoams. The relationship between crystal profiles and their performance in oleofoams was established. DAG formed small needle-like crystals while MAG formed large flake-like crystals in oleogels, and crystal shells around air bubbles were observed in LA-, MAG- and DAG-based oleofoams. LA and DAG displayed higher over-run whereas DAG-stabilised foam possessed smaller bubbles and higher physical stability due to the presence of small ß and ß' crystals. Upon heating, DAG and TAG-based foams showed varying extents of oil drainage indicating the crystals were distributed in a different manner. Therefore, DAG was shown to be an excellent gelator in the fabrication of ultra-stable oleofoams. This work extends the lipid varieties with nutritional features and allows a better understanding on the stabilization mechanisms of lauric acid lipids in oleofoams.

W/O high internal phase emulsion featuring by interfacial crystallization of diacylglycerol and different internal compositions.

High internal phase emulsions (HIPEs) show promising application in food and cosmetic industries. In this work, diacylglycerol (DAG) was applied to fabricate water-in-oil (W/O) HIPEs. DAG-based emulsion can hold 60% water and the emulsion rigidity increased with water content, indicating the water droplets acted as "active fillers". Stable HIPE with 80% water fraction was formed through the combination of 6 wt% DAG with 1 wt% polyglycerol polyricinoleate (PGPR). The addition of 1 w% kappa (κ)-carrageenan and 0.5 M NaCl greatly reduced the droplet size and enhanced emulsion rigidity, and the interfacial tension of the internal phase was reduced. Benefiting from the Pickering crystals-stabilized interface by DAG as revealed by the microscopy and enhanced elastic modulus of emulsions with the gelation agents, the HIPEs demonstrated good retaining ability for anthocyanin and ß-carotene. This study provides insights for the development of W/O HIPEs to fabricate low-calories margarines, spread or cosmetic creams.

The effects of interesterification on the physicochemical properties of Pangasius bocourti oil and its fractions.

Soft and solid fats which were fractionated from Pangasius bocourti oil (PBO), namely, Pangasius bocourti olein (PBOL) and Pangasius bocourti stearin (PBST), respectively, were introduced as new base oils for plastic fats. The physicochemical properties of PBO and its fractions were modified after interesterification. Enzymatic interesterification (EIE) reduced the sn-2 palmitic acid content attributed to the occurrence of acyl migration. The PBO solid fat content (SFC) at 20-40 °C increased after chemical interesterification whereas under similar range of temperature, the SFC of PBST decreased after EIE and a steep melting curve was obtained. The effect of interesterification on the crystal polymorphisms was less prominent whereby the initial and interesterified samples exhibited similar crystal forms. The solid state of PBOL was improved after interesterification but post-hardening was observed. Free fatty acids were produced via partial hydrolysis during EIE which contributed to the reduced oxidative stability in the EIE fats.

Tailored rigidity of W/O Pickering emulsions using diacylglycerol-based surface-active solid lipid nanoparticles.

Pickering water-in-oil (W/O) emulsions were fabricated by using medium-long chain diacylglycerol (MLCD)-based solid lipid nanoparticles (SLNs) and the connection between the characteristics of the SLNs and the colloidal stability of the emulsions was established. Via melt-emulsification and ultrasonication, MLCD-based SLNs with particle sizes of 120-300 nm were obtained with or without other surfactants. The particle size of the SLNs was influenced by the chemical properties of the surfactants, and surfactants decreased the contact angle of SLNs at the oil-water interface. Gelation was observed in SLNs modified by sodium stearoyl lactylate and lecithin, whereas the addition of Tween 20 resulted in a homogeneous SLN solution. The adsorption of surfactants onto SLN surfaces caused the production of higher amounts of α crystals accompanied by delayed crystallization onset which contributed to the reduction of particle size, interfacial tension and oil wetting ability. The W/O emulsions with higher rigidity and physical stability can be obtained by varying surfactant types and by increasing SLN mass ratios to 60%, whereby more SLNs are adsorbed at the droplet surface as a Pickering stabilizer. This study provides useful insights for the development of diacylglycerol-based SLNs and Pickering W/O emulsions which have great potential for food, cosmetic and pharmaceutical applications.

A practical and fast isolation of 12 cyclolinopeptides (linusorbs) from flaxseed oil via preparative HPLC with phenyl-hexyl column.

Linusorbs, known as cyclolinopeptides, are a group of cyclic hydrophobic peptides derived from flaxseed oil with various health benefits. However, the current research efforts on both the biological activities and antioxidant capacities of linusorbs are limited because of existing issues with their purification and characterization. A practical method based on preparative HPLC for isolating 12 linusorbs simultaneously was developed and factors such as the solvent selection, gradient elution program, flow rate, loaded mass, and loading concentration, were optimized. The optimum conditions were an initial acetonitrile (ACN) to water ratio of 40%, final ACN ratio of 80%, eluting time of 21 min, a flow rate of 16 mL/min, sample load of 12.5 mg, and concentration of 80 mg/mL (in methanol). The 12 linusorbs obtained were verified using off-line MS/MS, recording purities of above 95.5%. The method could serve as a practical and fast isolation method enabling further investigation of minor linusorbs.

Fabrication and characterization of stable oleofoam based on medium-long chain diacylglycerol and ß-sitosterol.

Oleofoams have emerged as attractive low-calorie aeration systems, but saturated lipids or large amount of surfactants are commonly required. Herein, an innovative strategy was proposed to create oleofoams using medium-long chain diacylglycerol (MLCD) and ß-sitosterol (St). The oleofoams prepared using MLCD and St in ratios of 15:5 and 12:8 exhibited smaller bubble size and much higher stability. MLCD crystals formed rigid Pickering shell, whereby air bubbles acted as "active fillers" leading to enhanced rigidity. Both Pickering and network stabilization for the MLCD-St oleofoam provided a steric hindrance against coalescence. The gelators interacted via hydrogen bonding, causing a condensing effect in improving the gel elasticity. The oleofoams and foam-based emulsions exhibited a favorable capacity in controlling volatile release where the maximum headspace concentrations and partition coefficients showed a significantly decrease. Overall, the oleofoams have shown great potential for development of low-calorie foods and delivery systems with enhanced textural and nutritional features.

Modification of palm-based oil blend via interesterification: Physicochemical properties, crystallization behaviors and oxidative stabilities.

Interesterification is widely employed as an effective technique to modify oils and fats. This study utilizes palm-based oil (palm olein: palm kernel oil: palm stearin, 5:3:2, w/w/w) as the raw material for the interesterification process performed in a pilot-scale packed bed reactor. Enzymatic interesterification (EIE) was catalyzed by Lipozyme TL IM (813.0 g) at 60℃ with reaction flow rate of 100 mL/min. Chemical interesterification (CIE) was catalyzed using sodium methoxide (0.3 wt%) as catalyst at 105 °C for 30 min. The results showed that the EIE fats had lower solid fat content tendency compared to that of CIE fats. The crystallization onset temperature was higher in EIE fats (23.09℃) compared to that of CIE (19.08℃). The results were consistent with the crystallization kinetics whereby the Avrami K constants of EIE fats were higher than that of CIE fats at various temperatures, indicating rapid crystallization and instant nucleation. Linear growth mechanism was dominant and the crystals formed were smaller in size as observed using polarized light microscope. The interesterified fats exhibited the presence of ß and ß'-crystals. While most of the tocopherol content was retained after EIE (386.18 ug/g), the molecular distillation process reduced the tocopherol concentration (110.01 ug/g) which consequently affected the oxidative stability. The findings in this work contribute to the fundamental understanding on the differences between CIE and EIE fats and provides data to support the preparation of modified fats via EIE that shows great potential as a controllable technique for industrialization.

Enzymatic Interesterification of Palm Stearin and Palm Olein Blend Catalyzed by sn-1,3-Specific Lipase: Interesterification Degree, Acyl Migration, and Physical Properties.

Acyl migration of fatty acid at sn-2 is often observed alongside enzymatic interesterification (EIE), causing the loss of lipase selectivity toward the acyl group at sn-1,3. In this study, an oil blend consisting of palm stearin (PST) and palm olein (POL) was interesterified via a chemical interesterification (CIE) and enzymatic method using a packed bed reactor. Characterization in terms of the triacylglycerol (TAG) compositions, sn-2 fatty acid distributions, and solid fat content profiles was performed. In comparison to that of CIE fats, EIE fats showed different modification effects on the solid fat content. Under similar reaction conditions, different interesterification degrees (IDs) were obtained according to the various blend ratios. Using the same mass ratio of substrates (POL/PST of 9:1), the EIE reaction time and temperature affected the ID and the change in the fatty acyl group at the sn-2 position. Under the reaction time of 46 min, an ID of 94.41% was acquired, while at 80 °C, the degree of acyl migration at sn-2 was 92.87%. EIE with high acyl migration exhibited a lower crystallization rate than that of EIE with low acyl migration. However, the effect of acyl migration on crystal polymorphism and oxidative stability was insignificant. Outcomes from this study are meaningful for the establishment of a theoretical basis for a controlled positional-specific EIE that is catalyzed by sn-1,3-specific lipase.

Evaluation of enzymatic interesterification in structured triacylglycerols preparation: a concise review and prospect.

Enzymatic interesterification (EIE) is one of the emerging technologies in the specialty fats industry. EIE has several advantages over the conventional chemical interesterification method, such that the process has higher flexibility and efficiency, is environmentally friendly and the immobilized enzyme can be recycled besides of the lower requirement for substrate's acid value. The physical properties and nutritional qualities of the fats and oils are modified after EIE, depending on the change in the position of fatty acids on the triacylglycerol (TAG) molecules. Evaluation of the interesterification reaction are important and useful in terms of its technological applications. This paper summarizes the conventional methods and the advancement for evaluating EIE processes, e.g., determination of the change in slip melting points, solid fat contents, TAG with equivalent carbon numbers, and sn-2 fatty acid compositions of the end product. Nonetheless, these methods are not comprehensive because during the EIE process, acyl migration occurs. A novel and convenient evaluation model which is based on the fatty acid distribution on the glycerol-backbone is proposed as a perspective. This model can be employed to monitor the interesterification degree and acyl migration during a regiospecific EIE process, which serves as a reaction rule that can be employed to control and optimize the EIE process, thereby producing structured TAG with desired properties.

Comparison between synthetic and rosemary-based antioxidants for the deep frying of French fries in refined soybean oils evaluated by chemical and non-destructive rapid methods.

Using natural antioxidants instead of synthetics ones has been the tendency for retarding the oil deterioration during repeated deep frying process. Concerning this, the comparison between synthetic tertiarybutyl hydroquinone (TBHQ) and rosemary-based antioxidants in frying French fries was hereby evaluated. The quality and stability of frying oils with rosemary-based antioxidants showed higher efficiency than TBHQ regarding oxidation parameters (i.e., chemical indices, sensory, etc.), where rosmarinic acid (RA) was the most effective, followed by rosemary extracts (RE) and carnosic acid (CA). LF-NMR results were highly correlated (R2 = 0.909-0.998) to the change in physicochemical properties tested, where RA could effectively regulate the relaxation spectrum (T2) change and decrease single component relaxation time (T2W). The PCA graph of NIRS also revealed the dynamic change of antioxidant effectiveness in accordance with that obtained by chemical methods. Hence, both LF-NMR and NIRS can be expected as rapid and efficient methods for future monitoring the frying process.

Immobilized Lipase in the Synthesis of High Purity Medium Chain Diacylglycerols Using a Bubble Column Reactor: Characterization and Application.

Novozym® 435, an immobilized lipase from Candida antarctica B. (CALB), was used as a biocatalyst for the synthesis of high purity medium chain diacylglycerol (MCD) in a bubble column reactor. In this work, the properties of the MCD produced were characterized followed by determining its practical application as an emulsifier in water-in-oil (W/O) emulsion. Two types of MCDs, namely, dicaprylin (C8-DAG) and dicaprin (C10-DAG), were prepared through enzymatic esterification using the following conditions: 5% Novozym® 435, 2.5% deionized water, 60°C for 30 min followed by purification. A single-step molecular distillation (MD) (100-140°C, 0.1 Pa, 300 rpm) was performed and comparison was made to that of a double-step purification with MD followed by silica gel column chromatography technique (MD + SGCC). Crude C8-DAG and C10-DAG with DAG concentration of 41 and 44%, respectively, were obtained via the immobilized enzyme catalyzing reaction. Post-purification via MD, the concentrations of C8-DAG and C10-DAG were increased to 80 and 83%, respectively. Both MCDs had purity of 99% after the MD + SGCC purification step. Although Novozym® 435 is a non-specific lipase, higher ratios of 1,3-DAG to 1,2-DAG were acquired. Via MD, the ratios of 1,3-DAG to 1,2-DAG in C8-DAG and C10-DAG were 5.8:1 and 7.3:1, respectively. MCDs that were purified using MD + SGCC were found to contain 1,3-DAG to 1,2-DAG ratios of 8.8:1 and 9.8:1 in C8-DAG and C10-DAG, respectively. The crystallization and melting peaks were shifted to higher temperature regions as the purity of the MCD was increased. Dense needle-like crystals were observed in MCDs with high purities. Addition of 5% C8-DAG and C10-DAG as emulsifier together in the presence of 9% of hydrogenated soybean oil produced stable W/O emulsion with particle size of 18 and 10 µm, respectively.

Effect of Purification Methods on the Physicochemical and Thermodynamic Properties and Crystallization Kinetics of Medium-Chain, Medium-Long-Chain, and Long-Chain Diacylglycerols.

Medium-chain diacylglycerol (MCD), medium-long-chain diacylglycerol (MLCD), and long-chain diacylglycerol (LCD) were prepared through enzymatic esterification using different conditions at temperatures of 55-70 °C and reaction times of 1.5-5 h and in the presence of 5-6% Novozym 435. Subsequently, purification was performed using three different techniques, namely, molecular distillation (MD), deodorization (DO), and silica gel column chromatography (SGCC). Variations in terms of the physicochemical and thermodynamic properties, crystallization properties, and kinetics of the diacylglycerols (DAGs) before and after purification were determined. Irrespective of the DAG chain lengths, SGCC was able to produce samples with high DAG purity (96-99 wt %), followed by MD (58-79 wt %) and DO (39-59 wt %). A higher 1,3-DAG/1,2-DAG ratio was recorded for all samples, with the highest ratio recorded for SGCC purified samples. Regardless of the purification techniques used, the solid fat content (SFC) profiles of crude samples with steep curves were altered post-purification, showing a gradual increment in SFC along with increasing temperature. Modification of the Avrami constant and coefficient suggested the modification of the crystal growth mechanism post-purification. Crystallization and melting temperatures of products with a higher DAG purity were shifted to a higher temperature region. Variations were also reflected in terms of the crystal polymorphism, whereby the α and ß' crystals transitioned into the more stable ß form in purified samples accompanied by modification in the microstructures and crystal sizes. However, there was insignificant change in the morphology of MLCD crystal after purification, except for the decrease in crystal sizes. In conclusion, synthesis of MCD, MLCD, and LCD comprising different DAG purities had distinctive SFC profiles, thermodynamic properties, crystallization kinetics, and crystal morphologies, which can be further incorporated into the preparation of a variety of fat products to obtain end products with desired characteristics.

Effect of diacylglycerol interfacial crystallization on the physical stability of water-in-oil emulsions.

The influence of diacylglycerol (DAG) combined with polyglycerol polyricinoleate (PGPR) on the stability of water-in-oil (W/O) emulsions containing hydrogenated palm oil (HPO) was studied. Polarized light microscope revealed that DAG promoted HPO to crystallize at the water-oil interface, providing the combination of Pickering and network stabilization effects. It was proposed that the molecular compatibility of fatty acids in DAG with HPO accounted for the promotional effect. The interfacial crystallization of DAG together with the surface activity of PGPR led to the formation of emulsions with uniform small droplets and high freeze-thaw stability. Further exploration of physical properties indicated that the combination of DAG and PGPR dramatically improved the emulsion's viscoelasticity and obtained a larger deformation yield. Water droplets in DAG-based emulsions acted as active fillers to improve the network rigidity. Therefore, DAG is a promising material to be used as emulsifier to enhance the physical stability of W/O emulsions.

Characterization of enzymatically interesterified palm oil-based fats and its potential application as cocoa butter substitute.

Cocoa butter substitutes (CBS) used for chocolate preparation was produced using a mixture of palm kernel oil (PKO) and enzymatically interesterified fats. The interesterified fats consisted of palm olein (POL), fully hydrogenated palm oil (FHPO) and PKO that were catalyzed using Lipozyme TL IM at 65 °C in a solvent-free packed bed reactor. An interesterification degree of 97.10% was obtained using feed flow rate of 70 mL/min and the interesterified fats showed steep solid fat content (SFC) curve characteristics with low SFC at high temperature. In the binary system, PKO and the interesterified fats showed good compatibility at 5-10 °C, while eutectic effects were observed at 15-35 °C. CBS produced from PKO and the interesterified fats in a mass ratio of 4:6 (CBS-46) and 3:7 (CBS-37) had crystals formed prominently in the ß' form. Without the need of a tempering process, chocolate made using CBS-46 as the base oil exhibited the desired properties in terms of hardness and fracturability.

Storage stability and degradation kinetics of bioactive compounds in red palm oil microcapsules produced with solution-enhanced dispersion by supercritical carbon dioxide: A comparison with the spray-drying method.

Solution-enhanced dispersion by supercritical carbon dioxide (SEDS) and spray drying (SD) were used to microencapsulate red palm oil (RPO) to prolong the functionality of carotenes and vitamin E. The protective effects provided by SEDS and SD were evaluated in terms of the oxidative stability (65 °C for 35 days), fatty acid compositions, color change and degradation kinetics of carotenes and vitamin E (25 °C, 45 °C, 65 °C, and 85 °C for up to 198 days). SEDS microcapsules (SEDS-M) were the most oxidatively stable (total oxidation (Totox): 26.5), followed by SD microcapsules (SD-M) (34.9) and RPO (56.7). Degradation of carotenes and vitamin E fitted well a first-order kinetic model (average absolute relative deviation = 2-16%). SEDS-M offered better protection to vitamin E (Ea = 36 kJ/mol), whereas SD-M provided better protection for α +â€¯ß carotene (Ea = 29 kJ/mol). Overall, encapsulation protected RPO during storage, with SEDS-microencapsulated RPO performing better than SD-microencapsulated RPO.

Non-aqueous foams formed by whipping diacylglycerol stabilized oleogel.

Formation of foams is critical for tailoring the texture and mouthfeel of fat-based products. Diacylglycerol (DAG) is regarded as a preferable alternative structurant to hydrogenated lipid. Effect of DAG concentration (2-10 wt%) on the characteristics of oleogels and foams including crystal polymorphisms, size and distribution, rheological and thermodynamic properties was investigated. Oleogel prepared with 10 wt% DAG had comparable whipping and foaming stability to that of 6 wt% fully hydrogenated palm oil (FHPO). DAG formed small plate-crystals which tend to occur at the bubble surface, whereas FHPO showed needle-like crystals that were formed mainly in the continuous phase. For the 2 wt% FHPO-8 wt% DAG-based oil foams, interfacial templating crystallization effect contributed to the smaller bubble size and improved rheological properties whereby less oil drainage and foam breakdown occurred. Hence, the non-aqueous foam formed by DAG has broad application prospect because of the thermoresponsive properties and the desirable health benefits.

Effects of chemical interesterification on the triacylglycerols, solid fat contents and crystallization kinetics of palm oil-based fats.

The effects of chemical interesterification (CIE) on the physicochemical properties and crystallization kinetics of oil blends containing palm oil (PO) in combination with six other types of oils were studied. The CIE reaction was performed at a reaction temperature of 105 °C for 30 min, catalyzed by 0.3% sodium methoxide. The results showed that the formation of ß' crystals was prominent and the crystallization rate increased significantly when PO was interesterified with beef tallow (BT). The presence of soybean oil (SBO) in the oil blend significantly increased the triacylglycerol (TAG) S/U/U content after CIE. For the sample consisting of a pure vegetable oil base, a gradual change in the crystallization rate was observed and the formation of ß crystals was dominant. The S/U/U content in the oil blends that contained palm kernel oil (PKO) decreased after CIE. Together in the presence of SBO, PKO had stronger ability to stabilize S/U/U, enriched the TAG composition (particularly by increasing the C44 TAG content), accelerated the crystallization rate and formed ß' crystals. The addition of a sufficient amount of palm mid fraction (PMF) could improve the high-temperature solid fat content and expand the plasticity range. Changes in the Avrami constant K and n values derived from solid fat content and heat enthalpy also suggested the modification of the crystal growth mechanism through the CIE process.