Guar gum series affect nanostructured lipid carriers via electrostatic assembly or steric hindrance: Improving their oral delivery for phytosterols.

Surface modification of nanostructured lipid carriers (NLCs) can be an effective way to improve their oral delivery for active ingredients. In this study, four type of guar gum series modified NLCs for the delivery of phytosterols (PS) were constructed and the effects of the polysaccharides on their structure and physicochemical properties were studied. DLS and AFM results revealed that positively charged polysaccharides could bind to PS-NLCs through electrostatic attraction and made the complexes finally take positive charges, while negatively charged polysaccharides were more likely to fill in the gaps of NLC systems to achieve a balance between electrostatic repulsion and intermolecular forces. Although all four polysaccharides exhibited good storage stability and controlled release of PS in simulated intestinal digestion, PS-NLCs modified with partially hydrolyzed cationic guar gum (PHCG) at medium or high concentrations exhibited better gastric stability, mucoadhesion, and cellular uptake, which had considerable significance for improving the oral bioavailability of PS. This might be related to the coating structure of PHCG-PS-NLCs confirmed by AFM, FTIR, and Raman characterization. This study provide a reference value for designing suitable PS-NLC complexes without synthetic surfactants.

Chemical conversions of free phytosterols during the bleaching of corn oil.

Phytosterols have health benefits; however, they are partially removed during the bleaching of corn oil. We evaluated the chemical conversion of free phytosterols (FPs) during bleaching. FP degradation accelerated with increased time and temperature, following a first-order kinetic model. In the n-heptane system, air and activated clay promoted the chemical conversion of the FPs. Sterenes formation was analysed under different conditions using a zero-order kinetic model. The apparent activation energies revealed sterene formation decreasing in the following order: campesta-3,5-diene ≈ stigmasta-3,5,22-triene > stigmasta-3,5-diene. Isomers of the above were not detected, indicating that these sterenes were the only primary products of FPs. The desorption test indicated that the FP loss from corn oil was not only due to FPs being adsorbed the activated clay, but also FPs adsorbed at acidic activated sites being degraded. This study presents a vital scientific foundation for retaining FPs to develop healthier and more nutritious oils.

Solid lipid nanoparticles for phytosterols delivery: The acyl chain number of the glyceride matrix affects the arrangement, stability, and release.

The lipid matrix plays a key role in solid lipid nanoparticles (SLNs) embedding active ingredients. To investigate the influence of lipid matrix structure on arrangement, release, and stability of solid lipid nanoparticles, three phytosterols formulations with different carrier glycerides [glycerol monostearate (GMS), glycerol distearate (GDS), and glycerol tristearate (GTS)] were prepared and evaluated. X-ray diffraction and differential scanning calorimetry revealed the lowest crystallinity of phytosterols in the GMS matrix, corresponding to the maximum bioaccessibility (40.2%) in vitro experiments. Sustained release and better stability were observed from GDS and GTS matrices, which could be attributed to strong molecular interactions or a core-rich structure inside the nanoparticles. Molecular dynamics simulations demonstrated that the affinity between phytosterols and glycerides decreased in the order GDS > GTS > GMS, as well as explaining the release and storage capacities of the three nanoparticles. This study would facilitate the rational design of SLNs in functional foods.

NMR Analysis of Lipid Oxidation in Flaxseed Oil-in-Water Emulsions.

The formation of linolenic (Ln) and linoleic (L) acyl oxidation products during storage of flaxseed oil (FO)-in-water emulsions was monitored using proton nuclear magnetic resonance (1H NMR) spectroscopy, as well as chemical analytical methods and gas chromatography. Emulsions containing 10% FO and 1% Tween 60 were prepared by homogenization and then stored at 37 °C in the dark for 21 days under accelerated oxidation conditions (500 µmol ferrous sulfate). The induction time of the emulsions, after which rapid lipid oxidation was first observed, was 5-7 days, as shown by increases in peroxide values and hydroperoxide concentrations determined by NMR spectroscopy. Analysis of the hexanal and propanal concentrations during storage by HS-SPME-GC indicated that the oxidation of Ln and L acyls in the emulsions occurred simultaneously. The oxidation products originating from the Ln and L acyls were monitored using 1H NMR spectroscopy throughout the oxidation process. These results also showed that the Ln and L acyls oxidized simultaneously, and isomers of hydroperoxy-cyclic hydroperoxides (HCPs), Z,E-conjugated dienic hydroperoxides (ZECDHPs), and E,E-conjugated dienic hydroperoxides (EECDHPs) were the major primary oxidation products. Aldehydes were observed after 7 days, which was taken to be the start of the propagation stage, with the formation of a significant amount of oxygenated α, ß-unsaturated aldehydes (OαßUAs). Based on the concentrations of hydroperoxides originating from the Ln and L acyls, our results suggested that the loss rate of L acyls was parallel to that of Ln acyls. This result was consistent with Ln acyls adopting a tighter packing at the oil-water interface in the emulsions than L acyls. This hypothesis was supported by the NMR relaxation time data. A good correlation between the isomer concentrations of ZECDHPs and HCPs in Ln acyls and between ZECDHPs and EECDHPs in L acyls was shown, with the mole ratios between them being 1.2 and 1.1, respectively. Droplet size and microstructure analyses showed that droplet aggregation occurred from 11 days onwards, which was attributed to polar oxidation products located at the oil droplet surfaces promoting coalescence. Zeta-potential measurements indicated that the droplets became more negative during storage, which was attributed to the accumulation of anionic reaction products at the droplet surfaces.

Systematic comparison of structural and lipid oxidation in oil-in-water and water-in-oil biphasic emulgels: effect of emulsion type, oil-phase composition, and oil fraction.

BACKGROUND: Because many common foods are emulsions (mayonnaise, margarine, salad dressing, etc.), a better understanding of lipid oxidation is crucial for the formulation, production, and storage of the relevant consumer products. We prepared oil-in-water (O/W) and water-in-oil (W/O) emulgels, and their architecture was characterized before monitoring lipid oxidation under thermally accelerated conditions to systematically compare the effect of emulsion type, oil composition, and oil fraction on the structure and lipid oxidation in thee biphasic emulgel systems. RESULTS: Higher susceptibility of lipids to oxidation (>2.5 times) was observed in the biphasic O/W and W/O emulgels than in soybean oil owing to an interfacial region. In the heterogeneous emulsion systems, W/O emulgels had oxidation resistance than O/W emulgels did. Compared with the oil-phase composition of high oleic sunflower, soybean, and flaxseed oils, oxidation sensitivity of emulsified lipids was significantly raised as the degree of unsaturation increased from 100.72 to 203.07. Moreover, increasing oil fraction from 75% to 85% led to an obvious increase in total oxidation in O/W emulgels but a decrease in W/O emulgels. In addition to emulsion size and oil unsaturation, viscoelasticity had a remarkable effect on the low-unsaturated oil oxidation (e.g. high oleic sunflower oil). CONCLUSION: Physical and structural phenomena played important roles in lipid oxidation based on a mass transport principle. These findings provide novel information for designing the structures of emulsion gels for controlling lipid oxidation through the cooperation of both formulation and architecture principles. © 2022 Society of Chemical Industry.

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.

Thermal degradation of stigmasterol under the deodorisation temperature exposure alone and in edible corn oil.

Phytosterols are commonly found in vegetable oils and possess health benefits for humans. While investigating the chemical conversion of stigmasterol at deodorisation temperatures, gas chromatography-mass spectrometry (GC-MS) and ultra-high performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS) experiments led to the identification of 5-ethyl-6-methyl-3-heptene-2-one, 3-hydoxy-steroid, 3-ketostigmasterol, and 3,7-diketostigmasterol as by-products. The identification of these compounds assisted in the interpretation of the stigmasterol oligomers characterised by high-pressure size exclusion chromatography (HPSEC). A similar analysis was conducted in stripped corn oil at the deodorisation temperatures. As such, 5-ethyl-6-methyl-3-heptene-2-one, 3-hydoxy-steroid, 3-ketostigmasterol and 3,7-diketostigmasterol were also detected in stripped corn oil, while the contents of 3-hydoxy-steroid and 5-ethyl-6-methyl-3-heptene-2-one were higher than those of 3-ketostigmasterol, as revealed by quantum chemical simulations. In addition, stripped corn oil exhibited the characteristic of preventing stigmasterol degradation below 200 °C, whereas it enhanced the chemical conversion (such as esterification and degradation) of stigmasterol at higher temperatures.

Enzymatic synthesis of hydrophilic phytosterol polyol esters and assessment of their bioaccessibility and uptake using an in vitro digestion/Caco-2 cell model.

A novel enzyme-catalyzed method was developed for the synthesis of phytosterol polyol esters from ß-sitosterol and polyols (sorbitol, mannitol and xylitol) by two-step transesterification using divinyl adipate (DVA) as a link. A high conversion (exceeding 94%) of ß-sitosterol with a vinyl group was achieved, in the presence of Candida rugosa lipase (CRL), at low temperature (35 °C) within 30 min. Subsequently, the maximum conversion of phytosterol polyol esters (>94%) was obtained using alkaline protease from Bacillus subtilis at 65 °C. Phytosterol polyol esters had enhanced thermal stability (up to an above 355 °C) and excellent water solubility (4.6-7.9 mM at 35 °C). Moreover, obvious increases in the bioaccessibility (41.5-63.6%) and intestinal uptake (5.2-6.5%) were observed using a simulated gastrointestinal digestion/Caco-2 cell model. These results highlighted the key role of hydrophilic structural modifications on physicochemical properties and absorption of phytosterols.

One-pot ultrasonic cavitational emulsification of phytosterols oleogel-based flavor emulsions and oil powder stabilized by natural saponin.

Phytosterols oleogel-based flavor emulsions were successfully fabricated for the first time using natural tea saponin as emulsifier and one-pot ultrasonic technique. The effects of ultrasonic time and power, surfactant concentration, and type of flavor oils (e.g., orange, lemon and peppermint) on the emulsion droplet size were investigated. Submicron emulsions with a dispersed phase made by flavor oil (20 wt%) + phytosterol (4 wt%) were stabilized with 3 wt% saponin were obtained by applying an ultrasonic time of 5 min and ultrasonic power of 280 W. The natural tea saponin emulsions exhibited a superior stability and encapsulation efficiency of phytosterol, compared to traditional emulsifiers. Flavor oil-phytosterol enriched powders were prepared by spray-drying and characterized by SEM, XRD and repose angle. The natural saponin encapsulated oil + phytosterol powders had excellent fluidity, redispersion behavior and low phytosterol crystallinity. It was demonstrated that ultrasound is an effective and suitable technique for fabricating fortified flavor emulsions and microcapsules, which may be used for developing functional lipids-based applications in the food, beverage and cosmetic industries.

Comparative Study on Functional Components, Physicochemical Properties and Antioxidant Activity of Amaranthus Caudatus L. Oils Obtained by Different Solvents Extraction.

Functional compositions, physicochemical properties and antioxidant activities of Amaranthus caudatus L. oils (ACO) obtained by different solvents were comparatively investigated. All the resulted ACO were enrich in 75% unsaturated fatty acid and in squalene of about 4 g/100 g. Different solvents showed varying in oil extraction, where acetone results a highest yield of 6.80 g/100 g. ACO extracted by ethanol showed a highest tocopherol (1351.26 mg/kg), polyphenols (211.28 mg/kg) and squalene (42519.13 mg/kg). However, phytosterols in ACO extracted by hexane (27571.20 mg/kg) was higher than that by acetone (19789.91 mg/kg), ethanol (22015.73 mg/kg) and petroleum ether (24763.30 mg/kg). Furthermore, antioxidant activity of ACO was also measured by DPPH, ABTS and FRAP assay. According to principal component and correlation analysis, squalene was correlated with the DPPH scavenging ability, but phytosterols and tocopherols was correlated with the ABTS and ferric reducing ability of the oils, respectively. This study provides a promising excellent source of functional oil for food industries.

Effect of unsaturation of free fatty acids and phytosterols on the formation of esterified phytosterols during deodorization of corn oil.

BACKGROUND: Phytosterols are partly removed during oil refining, and the magnitude of phytosterols loss largely depends on the refining conditions applied and the molecular conformation. The aim of this research was to study the effect of deodorization conditions and molecular unsaturation on the esterification of phytosterols during deodorization of corn oil. RESULTS: In the chemical model, free fatty acids (FFAs) were the major provider of acyl groups during the formation of phytosteryl fatty acid esters (PEs) under deodorization conditions. Among the main parameters of the deodorization, temperature played a role in the formation of PEs with a time-dependent manner. In comparison, saturated palmitic acid had a higher capability of esterifying free phytosterols (FPs) to PEs than unsaturated oleic acid and linoleic acid. Moreover, the influence of FFA unsaturation on the degradation of FPs depended on temperature. Besides, the formation of stigmasteryl ester had a competitive advantage over that of sitosteryl ester by quantum chemistry simulation. CONCLUSION: For laboratory-scale deodorization of corn oil, saturated fatty acids and deodorization process with steam as stripping gas could obviously esterify FPs to PEs. FPs were abundantly enriched in distillate during the deodorization process with nitrogen as stripping gas, whereas FPs and PEs were distilled simultaneously during the deodorization process with steam. © 2020 Society of Chemical Industry.

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.

Molecular reaction mechanism for elimination of zearalenone during simulated alkali neutralization process of corn oil.

Zearalenone (ZEN) is one of the most widely distributed harmful mycotoxins produced by Fusarium species, especially deposited in corn oil. In this study, we systematically tracked the changes of ZEN in the refining of corn oil, and especially during neutralization process. An alkali neutralization process could remove certain amounts of ZEN that was much more than that of others refining steps. In a mimicking condition, ZEN contents decreased continuously and significantly with increasing neutralization temperature. However, when returned to neutral, recoverable ZEN decreased with increasing temperature, which confirmed more degradation of ZEN at high temperature. HPLC-Q/TOF MS and NMR evidence showed that non-reversible hydrolyzate followed decarboxylation was observed in a high-temperature alkali neutralization condition. The results may serve as the scientific basis for the elimination of zearalenone in refined vegetable oils, and provide clues to understanding the oil-safety aspects of elimination of zearalenone.

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 reduced graphene oxide-borate compound-loaded melamine sponge/silicone rubber composite with ultra-high dielectric constant.

Herein, at first, graphene oxide (GO) was prepared by a modified Hummers' method, compounded with borates and then loaded onto a melamine sponge (MS) skeleton by an impregnation-reduction method to obtain a reduced graphene oxide (rGO)-borate compound (rGB)-loaded MS. Then, MS/rGB/silicone rubber (SR) composites were prepared by a vacuum infusion process. Moreover, the microstructures, electrical conductivity, and dielectric properties of the composites were investigated. The results showed that rGO presented a sheet-like structure, compounding with borates produced during the reduction of GO by sodium borohydride. rGB was co-loaded onto the MS skeleton, and a three-dimensional percolation network was successfully constructed in the MS/rGB/SR composite. In addition, there was an efficient synergistic effect between rGO and borates, which significantly improved the dielectric constant of the composites. At the rGO volume fraction of 1.89 vol%, the composite had the volume resistivity of 6.57 × 104 Ω cm, the ultra-high dielectric constant of 2.71 × 104 with the dielectric loss of 1.36 at 1 kHz, and the relatively low percolation threshold of 0.815 vol%. Furthermore, the composite exhibited high compression sensitivity at low compressive strains.