Decreasing acid value of fatty acid ethyl ester products using complex enzymes.

Recently, enzymatic method has been used to prepare biodiesel using various oils. But the high acid value of the biodiesel product using enzyme as a catalyst has been one issue. In this work, an attempt to reduce the acid value of fatty acid ethyl ester (FAEE) product to satisfy the specified requirement (AV ≤ 0.5 mgKOH/g), a complex enzyme-catalyzed method was used for the ethanolysis of Semen Abutili seed oil (SASO) (AV = 5.5 ± 0.3 mgKOH/g). The effects of various variables (constituents of complex enzyme, type and addition of water removal agent, time, temperature, enzyme addition load, substrate ratio) on the enzymatic reaction were investigated. The optimal reaction conditions were: 1% addition of liquid lipase Eversa® Transform 2.0% and 0.8% of enzyme dry powder CALB, reaction temperature 35°C, alcohol-oil ratio 9:1 (mol/mol), 0.8 g/g of 4A-MS and reaction time 24 h. Under the optimal reaction conditions, the FAEE yield was 90.8% ± 1.5% and its acid value was decreased from 12.0 ± 0.2 mgKOH/g to 0.39 ± 0.10 mgKOH/g. In further evaluating the feasibility of preparing FAEE from SASO, the FAEE products obtained under the optimal reaction conditions were purified and evaluated with reference to the ASTM D6751 standard for the main physicochemical indexes. The results obtained were in accordance with the requirements except for the oxidative stability.

Synthesis of lipophilic antioxidant tyrosol laurate using imidazolium ionic liquid [Bmim]HSO4 as a catalyst.

Tyrosol is a natural phenolic compound with potent antioxidant properties in the field of food manufacturing. However, the low lipophilicity of tyrosol limited its application. Therefore, the construction of tyrosol laurate (Tyr-L) could effectively overcome the limitations of tyrosol. In this work, four ionic liquids (ILs) were applied for TYr-L preparation. Among them, the 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO4) showed the best catalytic performance. The maximum TYr-L yield was achieved (94.24 ± 1.23 %) under the optimal conditions (reaction temperature 119 °C, substrate ratio 1:6.7, IL dosage 9.2 %, and reaction time 12 h). The kinetic and thermodynamic parameters were also evaluated and it was found that Ea, ΔH, ΔS, and ΔG were 80.81 kJ·mol-1, 77.63 kJ·mol-1, -82.08 J·(mol·K)-1, and 109.89 kJ·mol-1, respectively. The acidic [Bmim]HSO4 demonstrated excellent reusability and stability, even after 6 cycles. Furthermore, TYr-L showed superior ABTS radical scavenging ability, which could be further applied in various industrial processes.

Tiger nut (Cyperus esculentus L.) oil: A review of bioactive compounds, extraction technologies, potential hazards and applications.

Tiger nut is a tuber of a plant native in the Mediterranean coastal countries, which is of great interest in food industry due to its richness in carbohydrates, lipids, starches, minerals, etc. Recent studies have focused on the analysis of the phytochemical composition of tiger nut, including six essential nutrients, polyphenols, and the extraction of proteins, starches, and phenolic compounds from the by-products of tiger nut milk 'horchata'. Few works were focused on the possibility of using tiger nut oil, a nutritious oil comparable to olive oil, as an edible oil. Therefore, this review discussed some extraction technologies of tiger nut oil, and their effects on the properties of oil, such as bioactive compounds, oxidative stability and potential hazards. The information on the emerging applications of tiger nut oil was summarized and an outlook on the utilization of tiger nut oil by-products were also reviewed.

Fabrication and characterization of novel thermoresponsive emulsion gels and oleogels stabilizied by assembling nanofibrous from dual natural triterpenoid saponins.

Novel thermoresponsive emulsion gels and oleogels were fabricated by assembling nanofibrous from natural triterpenoid Quillaja saponin (QS) and glycyrrhizic acid (GA). The viscoelasticity of QS-coated emulsion was observed to be remarkably improved by GA and thus obtain the advantages of excellent gelatinous, thermoresponsive and reversible manner due to the viscoelastic texture from GA nanofibrous as scaffolds in continuous phase. In the gelled emulsions, the phase transition of the GA fibrosis network structure upon heating and cooling was attributed to a thermal sensitivity, whereas interface-induced fibrosis assembly of amphiphilic QS endowed the formation of stable emulsion droplets. Then these emulsion gels were further used as an effective template to fabricate soft-solid oleogels with high oil content of 96%. These findings open up new opportunities for the use of all-natural and sustainable ingredients to develop smart soft materials for replace trans and saturated fats in food industry and other fields.

Towards the development of novel bicomponent phytosterol-based oleogels with natural phenolics.

Structuring liquid oils into edible oleogels from natural and abundant plant ingredients has great significance in fields ranging from foods to pharmaceuticals but has proven challenging. Herein, novel bicomponent phytosterol-based oleogels were developed with natural phenolics. Investigating diverse natural phenolics, cinnamic acid (CA) and ethyl ferulate (EF) successfully formed oleogels in combination with phytosterols (PS), where a synergistic effect on the oleogelation and crystallization was observed compared to the corresponding single component formulations. FTIR and UV-vis spectra showed that the gel network was primarily driven by hydrogen bonding and π-π stacking. Furthermore, oscillatory shear demonstrated oleogels featured higher elastic and network structure deformation at molar ratio of 5:5 and 3:7. Moreover, the bicomponent phytosterol-based oleogels displayed partially reversible shear deformation and a reversible solid-liquid transition. Such information was useful for engineering the functional properties of oleogel-based lipidic materials, providing significance for the application in foods, cosmetics and pharmaceuticals industries.

Preparation of a novel healthy tiger nut oil-based margarine fat with low trans and saturated fatty acids.

The present study sought to develop a novel healthy margarine fat with low levels of trans and saturated fatty acids in order to promote healthier alternatives. In this work, tiger nut oil was first used as a raw material to prepare margarine fat. The effects of mass ratio, reaction temperature, catalyst dosage, and time on the interesterification reaction were investigated and optimized. The results showed that, the margarine fat with ≤40% saturated fatty acids was achieved using a 6:4 mass ratio of tiger nut oil to palm stearin. The ideal interesterification parameters were 80 °C, 0.36% (w/w) catalyst dosage, and 32 min. Compared with physical blends, the interesterified oil had lower solid fat content (3.71% at 35 °C), lower slip melting point (33.5 °C), and lower levels of tri-saturated triacylglycerols (1.27%). This investigation provides important information for the utilization of tiger nut oil in healthy margarine formulation.

Color Reversion of Refined Vegetable Oils: A Review.

During the transport, storage, and consumption of edible vegetable oils, the color of some freshly refined oils is gradually darkened, which is known as the color reversion. The oil industry has been plagued by the issue for a long time because the dark color of the oil is related to its poor quality and low acceptability for consumers. Color reversion of refined vegetable oils is primarily related to the processing pigments, especially tocored, which is the oxidation product of γ-tocopherol. However, the underlying molecular action mechanism of tocored is not yet fully understood due to the complex transformations of tocored in oil systems. This paper presents a brief description of oil color, followed by an overview of research progress on the mechanism of color reversion. In particular, the effect of minor components (phospholipids and metal ions) on color reversion is highlighted in an attempt to explain the remaining mysteries of color reversion. Furthermore, the measures to restrain color reversion by quality control of the oilseeds, the adjustment of technical parameters of processing, and the storage conditions of refined oils are summarized to provide some references for the oil industry.

Synthesis of hydrophilic glyceryl monocaffeate with economical catalyst cation-exchange resin Amberlyst-35.

BACKGROUND: Caffeic acid (CA) has anti-oxidation and anti-inflammatory. However, the poor hydrophilicity of CA limits its biological activities. In this work, hydrophilic glyceryl monocaffeate (GMC) was synthesized by esterification using different caffeoyl donors (deep eutectic solvent and solid CA). Cation-exchange resins were used as the catalysts. The effects of reaction conditions were also investigated. RESULTS: The mass transfer limitation of esterification was eliminated using deep eutectic solvent. Compared with the previous catalysts (immobilized lipase Novozym 435), an economic cation-exchange resin, Amberlyst-35 (A-35), showed good catalytic performance for GMC preparation. The activation energies of GMC synthesis and CA conversion were 43.71 kJ mol-1 and 43.07 kJ mol-1 , respectively. The optimal reaction conditions were a temperature reaction of 90 °C, catalyst load of 7%, glycerol/CA molar ratio of 5:1 (mol mol-1 ), and reaction time of 24 h, which resulted in a maximum GMC yield and CA conversion of 69.75 ± 1.03% and 82.23 ± 2.02%, respectively. CONCLUSION: The results of the work showed a promising alternative for the synthesis of GMC. © 2023 Society of Chemical Industry.

Edible HIPE-Gels and oleogels formed by synergistically combining natural triterpenoid saponin and citrus dietary fiber.

High-internal-phase emulsion gels (HIPE-Gels) and oleogels were successfully fabricated through synergistically combination of natural triterpenoid Quillaja saponin (QS) and citrus dietary fiber (CDF). The amphiphilic QS significantly lowered the oil-water interface tension; whereas CDF could form compact structure at the interface as well as in the bulk under a hydrogen-bonding interaction with saponin. The combination endowed the emulsion gels with enhanced performance, such as decreasing droplet size, strengthening gel network structure and better viscoelastic. At a very low QS of 0.045 %, stable HIPE-Gels can be produced with 0.3 % CDF, which mainly attributing to the highly viscoelastic fiber networks in continuous phase and thus actively trap the QS-coated emulsion droplets. Consequently, the robust HIPE-Gels were applied as soft template to fabricate oleogels with controlled by QS and CDF loading. These findings proved an effective strategy towards structuring edible liquid oil into healthy gels for alternating saturated and trans fats in foods.

Co-occurrence of aflatoxins in plant oil products from China.

Aflatoxins have been detected as contaminants of oil crops before harvesting and drying, during storage and manufacturing and could be transferable to plant oils. There are more than 20 different types of aflatoxins, among which the most commonly occurring are the B1, B2, G1 and G2. Concentrations of these four aflatoxins were determined in plant oils from retail shops in China and in crude peanut oil extracted from culled mouldy peanuts by HPLC with fluorescence detection. Overall, aflatoxins were present in 25 of the 63 samples. The four aflatoxins co-existed in vegetable oil, but the content of AFB1 was usually higher than the other aflatoxins. Particularly in the case of highly contaminated oil samples, AFB1 accounted for 68% of the total aflatoxins. According to the health risk assessment, the low margin of exposure values from AFB1 in oils suggests a high level of concern for children.

Lipophilic antioxidant dodecyl caffeate preparation by the esterification of caffeic acid with dodecanol using ionic liquid [Hnmp]HSO4 as a catalyst.

Caffeic acid (CA) is widely found in nature, and has a broad spectrum of biological activities. However, the low hydrophilicity and lipophilicity of CA limited its application. Dodecyl caffeate (DC) is the lipophilic ester of caffeic acid (CA), and also has high antioxidant activity. In this work, CA, used as a substrate, and three ionic liquids with different acidities and H2SO4 were used as economic catalysts for DC preparation. The effects of variables on DC yield were investigated and optimized by response surface methodology (RSM). And the kinetic and thermodynamic parameters of the esterification of CA and dodecanol were evaluated. Results showed that lipophilic DC was successfully synthesized using ionic liquid ([Hnmp]HSO4) as a catalyst. And the optimal conditions by RSM were substrate ratio of 10.2 : 1, IL dosage of 9.8% at 87 °C for 118 min. Under the optional conditions, the maximum DC yield was 94.67 ± 1.32%. The k 0, E a, ΔH, ΔS, and ΔG were 7.18 × 107 mol (L min)-1, 65.77 kJ mol-1, 63.10 kJ (mol K)-1, -103.80 J (mol K)-1, and 99.78 kJ mol-1 at 363 K, respectively. DC prepared in this work showed a good DPPH radical scavenging activity, which indicated that DC can be used as a potential antioxidant in food and cosmetics.

Structuring of Edible Liquid Oil into Smart Thermo-Triggered Soft Matters for Controlled Bioactive Delivery.

Growing interest is being dedicated to smart soft matters because of their potential in controlling bioactives upon exposure to an appropriate stimulus. Herein, structuring of edible liquid oil into oleogels and emulgels as smart thermo-triggered soft vehicles for controllable release of diverse nutrients was developed. Edible liquid oil was trapped inside the crystal network structure of phytosterols and monoglycerides resulting in bicomponent solidlike oleogels. Subsequently, both water-in-oleogel (W/O) emulgels and glycerol-in-oleogel (G/O) emulgels were further fabricated by spatial distribution of the stabilizing interfacial crystals around dispersed droplets as well as the network crystals in the continuous phase. Rheological measurements showed that the gel strength of the oleogel-based emulgels depends on the fraction of the aqueous phase and is greater than that of corresponding oleogels due to a filler effect of dispersed aqueous droplets within the crystal network, offering an additional strategy to tune the structure and rheology. Comparatively, introducing glycerol endowed a higher gel strength for the oleogel-based emulgels than water, particularly at increased filler loads. In addition, these soft matters exhibited interesting thermoresponsive nature, which exhibit the flexibility for programmed release of coencapsulated bioactive components upon exposure to an appropriate thermal triggered switchable. The resulted smart thermo-triggered soft matters have emerging opportunities for application in functional active ingredient delivery by on-demand strategies.

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.

Oil-Water Interfacial-Directed Spontaneous Self-Assembly of Natural Quillaja Saponin for Controlling Interface Permeability in Colloidal Emulsions.

Assembly of amphiphiles at the interface of two immiscible fluids is of great scientific and technological interest in offering efficient routes to smart vehicles for functional deliveries. Natural Quillaja saponin (QS) has gathered widespread interest within the scientific community as a result of its unique interfacial properties. Herein, spontaneously interface-driven self-assembly (SIDSA) of QS at the oil-water interface was systematically studied by morphology and spectroscopy. It was found to self-assemble into a micrometer-scale network in helical fibers by combined intermolecular π-π stacking and hydrogen bonding among saponins at the liquid-liquid interface. From SIDSA, multilayer films on the surfaces of dispersed droplets were formed and enhanced emulsion stability. Interfacial QS-based films on droplet surfaces were also shown to confine interfacial diffusion processes by serving as transport barriers. Furthermore, they can be exploited to control the release of volatiles from the dispersed liquid phase by regulating the interface film, which is shown by molecular dynamics to occur through a hydrogen-bonded mechanism. These results provide new insight into the interfacial assembly structure that can enable unique controllable release in a broad range of applications in food, beverages, pharmaceuticals, and cosmetics.

Synthesis of Lipophilic Caffeoyl Alkyl Ester Using a Novel Natural Deep Eutectic Solvent.

In this work, a novel method for lipophilic caffeoyl alkyl ester production was developed using a natural deep eutectic solvent (DES) consisting of choline chloride and caffeic acid (CA) as the caffeoyl donor. Cation-exchange resins were used as the catalyst to catalyze the esterification of fatty alcohols with the DES. Effects of the caffeoyl donor and reaction variables were investigated. Reaction thermodynamics were also analyzed. The results showed that the lipophilic caffeoyl alkyl ester production can be enhanced using the DES as the caffeoyl donor, and cation-exchange resin A-35 showed the best catalytic activity for the reaction. Under the optimized conditions (85 °C, stearyl alcohol/CA 8:1 (mol/mol), A-35 load 5% and 24 h), the maximum octodecyl caffeate (OC) yield (90.69 ± 2.71%) and CA conversion (95.17 ± 2.76%) were obtained with the DES as the caffeoyl donor, which were much higher than those obtained with solid CA as the caffeoyl donor (OC yield 40.97 ± 2.37% and CA conversion 44.26 ± 1.69%). The activation energy of CA conversion (67.57 kJ/mol) with the DES was lower than that with solid CA (90.19 kJ/mol). In addition, the mass transfer limitation can be decreased with the DES. Compared with solid CA as the caffeoyl donor, a fast reaction rate and low mass transfer limitation were obtained using the DES as the caffeoyl donor.

Hydrophilic Glyceryl Ferulates Preparation Catalyzed by Free Lipase B from Candida antartica.

Ferulic acid (FA), 4-hydroxyl-3-methoxy-2-benzylacrylic acid, has antioxidant, anticancer and ultraviolet absorption activities. However, the low hydrophilicity of FA has limited its application. Glyceryl ferulate (FG), which is an all-natural hydrophilic derivative of FA, can be used as an antioxidant and UV filter in food and cosmetic formulations. However, the applications of FG in these fields are limited due to its low content in nature. In this work, free liquid lipase was firstly used as a catalyst for FG preparation. Several different free liquid lipases (Candida antartica lipase-B, Candida antartica lipase-A, Thermomyces lanuginosus (Lipozyme TL 100L)) were screened and compared. The effects of the transesterification parameters (time, temperature, enzyme load and substrate ratio) were optimized and evaluated by response surface methodology. A reaction thermodynamic investigation was also performed. The results showed that, among the tested free lipases, the maximum FG yield (84.8±1.5%) was achieved using free Candida antartica lipase-B. Under the optimized conditions (an atmospheric system, an enzyme load of 11.1% and a 20:1 molar ratio of glycerol to EF at 70°C for 39.5 h), the FG yield and EF conversion were 84.8±1.5% and 95.7±1.2%, respectively. The activation energies of FG formation and EF conversion were 56.4 and 58.0kJ/mol, respectively.

Biodiesel Production Catalyzed by a Methanol-Tolerant Lipase A from Candida antarctica in the Presence of Excess Water.

In this article, biodiesel was prepared using a novel free liquid lipase A from Candida antarctica (CALA) as a catalyst in the presence of excess water. The methanol tolerance of CALA was investigated. The effect of reaction conditions, including the molar ratio of soybean oil to methanol, water load, CALA load, reaction temperature, and reaction time, was evaluated. Reaction thermodynamics and kinetics were also analyzed. Results showed that free liquid lipase CALA showed excellent methanol tolerance in the reaction system using one-step addition of methanol and can be used to prepare biodiesel with water load of 12-14%. The influence of three transesterification variables on biodiesel yield was water load > temperature > time. The transesterification conditions were optimized by response surface methodology as follows: CALA load 5%, substrate molar ratio (soybean oil/methanol) 1:7, water load 14%, reaction time 26 h, and temperature 38 °C. The maximum biodiesel yield (92.4 ± 0.8%) was obtained under optimal conditions. The activation energy for biodiesel formation was 52.58 kJ/mol. Kinetic parameters K m ' and V max were 4.84 × 10-1 mol/L and 6.85 × 10-2 mol/(L·min), respectively. The mechanism of CALA-catalyzed transesterification was also proposed.

Influence of ionic liquid on Novozym 435-catalyzed the transesterification of castor oil and ethyl caffeate.

Caffeic acid (CA), one kind of phenolic acids widely occurring in the plant kingdom, can be used as potential UV protective ingredient and antioxidant. However, the application of CA was limited because of its unsatisfactory solubility in hydrophilic and lipophilic media. In this work, BMIMPF6, one kind of ionic liquids (ILs), was developed as an environmental friendly reaction media for the enzymatic preparation of CA derivatives by the transesterification of castor oil (CO) and ethyl caffeate (EC). Different series of ILs with BF 4 - , TF 2 - , and PF 6 - were screened and compared, and the effects of transesterification variables [temperature (60-100 °C) enzyme concentration (10-90 mg/mL), substrate molar ratio (CO/EC, 1:1-5:1), water load (0-8%), and reaction pressure] were also investigated. Results showed that, in the IL system, hydrophilic and lipophilic products were formed by two competitive reactions [(i) hydrolysis + transesterification and (ii) transesterification]. The maximum hydrophilic caffeoyl lipids yield (26.10 ± 0.28%) and reaction selectivity for hydrophilic caffeoyl lipids (0.4) was achieved in BMIMPF6 system. The increases of substrate ratio (molar ratio of CO to EC, from 1:1 to 5:1), water load (from 0 to 8%), and enzyme concentration (from 10 to 90 mg/mL) were in favor of hydrophilic caffeoyl lipid formation. However, the vacuum system and high temperature (from 70 to 100 °C) are favorable for lipophilic caffeoyl lipids formation. Under the optimal reaction conditions (90 °C, 75 mg/mL enzyme concentration, substrate ratio 3:1, 60 h, and 10 mmHg vacuum pressures), the maximum EC conversion was 72.48 ± 2.67%. The activation energies of the transesterification, and the selective formations of lipophilic and hydrophilic products were calculated as 44.55, 47.65, and 54.96 kJ/mol, respectively.

Engineering phytosterol-based oleogels for potential application as sustainable petrolatum replacement.

Phytosterol-based oleogels have been engineered in edible oils for potential applications as sustainable replacements for petrolatum. Oleogels have emerged with a crystal network structure with oil molecules trapped inside. In addition, the viscosity of highly thixotropic oleogels could be tuned by manipulating the concentration of phytosterols and monoglycerides, and the type of surface-active small molecules and bulk vegetable oils. Furthermore, viscous soft matter could also be tunably made with 8-20% oleogelators in olive oil with favourable water vapour occlusive and wettability properties, in addition to having good texture, and outstanding thixotropic and thermal reversibility properties. These properties are quite similar to those of commercial petrolatum. This work demonstrates that the natural phytosterol-oleogels in edible oils can be a novel source of sustainable and green replacements for petrolatum.

A novel and rapid method for fatty acid preparation by the lipase-catalyzed hydrolysis of Phoenix tree seeds.

Fatty acids are the precursors for the production of fuels, oleochemicals and special health care products. In this study, a novel rapid method for fatty acid (FA) preparation by the enzymatic hydrolysis of Phoenix tree seed, an undeveloped woody oil seed, was developed. High-temperature GC with flame ionization detector (FID) and the hydrolysis ratio were used to monitor reaction progress. Enzyme screening and the effect of reaction variables on the hydrolysis of seeds were evaluated and optimized by response surface methodology. The results showed that among the tested enzymes, Lipozyme TLIM showed the greatest amount of hydrolysis of Phoenix tree seed. FAs can be rapidly prepared by one-step hydrolysis of Phoenix tree seeds using Lipozyme TLIM as the biocatalyst. Under the optimized conditions (6% enzyme load, 1:8 mass ratio of seed to water, 47.7 °C and 16 min), the maximum hydrolysis ratio (96.4 ± 1.1%) can be achieved. The effect of reaction variables on the hydrolysis decreased in the following order: reaction time > enzyme load > substrate ratio of seed to water > reaction temperature. This work provides a novel and rapid method for FA preparation from oil seeds.