Microemulsions as delivery systems of lemon oil and ß-carotene into beverages: stability test under different light conditions.

BACKGROUND: Microemulsions have been proposed as delivery systems for different lipophilic substances in transparent water-based systems. The chemical stability of the delivered compounds is a key factor to broaden the application of microemulsions in the food sector. The stability of a model beverage containing a microemulsion delivering ß-carotene and lemon oil was tested under increasing light intensity up to 6000 lx at 20 °C. RESULTS: The transparent microemulsion resulted physically stable during storage indicating that no coalescence phenomenon occurred. On the contrary, both colour and flavour of the microemulsion degraded as a consequence of limonene and ß-carotene oxidation. Kinetic data obtained at increasing light intensity were used to estimate the light dependence of beverage spoilage and the mathematical relationship obtained was used to predict spoilage rate under different light conditions. Finally, a shelf life predictive model was proposed. CONCLUSIONS: Transparent microemulsions can be successfully used to deliver flavoured oil and colourants into beverages. However, the photostability of the delivered compounds should be carefully studied to estimate product shelf life. To this aim, the availability of models predicting shelf life as a function of enlightening conditions could largely contribute to speed up the process. © 2019 Society of Chemical Industry.

Improving the Bioaccessibility and Bioavailability of Carotenoids by Means of Nanostructured Delivery Systems: A Comprehensive Review.

Carotenoids are bioactive compounds provided by the diet playing a key role in maintaining human health. Therefore, they should be ingested daily in an adequate amount. However, even a varied and well-balanced diet does not guarantee an adequate intake, as both the bioaccessibility and bioavailability of the compounds significantly affect their absorption. This review summarizes the main results achieved in improving the bioaccessibility and bioavailability of carotenoids by means of nanostructured delivery systems, discussing in detail the available lipid-based and biopolymeric nanocarriers at present, with a focus on their formulation and functional efficiency. Although the toxicity profile of these innovative delivery systems is not fully understood, especially for long-term intake, these systems are an effective and valuable approach to increase the availability of compounds of nutritional interest.

Oleogels and Organogels: A Promising Tool for New Functionalities.

Growing awareness concerning human health and sustainability has been continually driving the need to change consumers' habits and develop new bio-based and environmentally friendly materials that could be used in new product formulations [...].

Addressing criticalities in the INFOGEST static in vitro digestion protocol for oleogel analysis.

The interest on the digestive fate of oleogels, i.e., substitutes for solid fats rich in liquid oil, have pushed researchers to use the widely adopted INFOGEST protocol for static in vitro digestion. However, this protocol was originally designed to simulate the digestibility of conventional foods and to accommodate the large fraction of oil in oleogels, researchers have deliberately modified the INFOGEST protocol, inadvertently leading to results difficult to be compared. In this study, we highlighted possible problems that may arise during oleogel simulated digestion such as under- or overestimation of oleogel lipolysis. The effect of oleogel amount, oleogelator type and concentration, and shear applied during digestion on the rate and extent of oleogel digestion was studied. The release of fatty acids during the application of INFOGEST protocol was monitored using the pH-stat method and compared to those analyzed by HPLC-ELSD. Oleogels' structural information was obtained using brightfield, polarized, and fluorescence microscopy, and DSC. We determined that lipolysis of ethylcellulose oleogels follow the "interaction with enzymes and bile salts" pattern, whereas that of wax oleogels follow the "disintegration of oleogel and interaction with enzymes and bile salts". We also observed that the chemical composition of wax, crystal morphology, and crystal distribution do not alter the lipolysis of oil entrapped inside the wax crystals. We finally recommended a few minimal but fundamental modifications to the INFOGEST protocol to achieve more reliable results from the static in vitro digestion of oleogels and possibly other lipid-based systems.

Practical scale modification of oleogels by ultrasonic standing waves.

Lipid-based materials, such as substitutes for saturated fats (oleogels) structurally modified with ultrasonic standing waves (USW), have been developed by our group. To enable their potential application in food products, pharmaceuticals, and cosmetics, practical and economical production methods are needed. Here, we report scale-up of our procedure of structurally modifying oleogels via the use of USW by a factor of 200 compared to our previous microfluidic chamber. To this end, we compared three different USW chamber prototypes through finite element simulations (FEM) and experimental work. Imaging of the internal structure of USW-treated oleogels was used as feedback for successful development of chambers, i.e., the formation of band-like structures was the guiding factor in chamber development. We then studied the bulk mechanical properties by a uniaxial compression test of the sonicated oleogels obtained with the most promising USW chamber, and sampled local mechanical properties using scanning acoustic microscopy. The results were interpreted using a hyperelastic foam model. The stability of the sonicated oleogels was compared to control samples using automated image analysis oil-release tests. This work enabled the effective mechanical-structural manipulation of oleogels in volumes of 10-100 mL, thus paving the way for USW treatments of large-scale lipid-based materials.

Automated image analysis method for oil-release test of lipid-based materials.

We present an automated method to determine oil release from lipid-based materials. Oil-release tests can provide information regarding the ability to retain oil within the structuring network of lipid-based materials. This test provides a first insight into the stability of these materials and their possible applications in food, cosmetic, and pharmaceutical products. The method presented features a simple setup comprising a camera that automatically captures images of the evolution of the oil stain released from lipid-based materials placed on a filter paper. Image postprocessing is performed with two custom-made scripts developed for the freeware application ImageJ. The scripts allow direct calculation of the oil-stain area from all images stored in a folder returning as output numerical values in a table. This method was shown to be:•inexpensive, as the employed tools and equipment are available in most laboratories both in academia and industry,•self-running, as the method automatically captures images at predefined time intervals for a certain time span,•practical, as manual-image analysis is unnecessary (200 images can be automatically analyzed in 3 min).

Inhibition of lipid autoxidation by vegetable waxes.

This study aims to evaluate the effect of vegetable waxes on the kinetics of lipid oxidation of linseed oil. Apple and orange waxes were obtained using supercritical carbon dioxide. The capacity of waxes to inhibit or retard the oxidation of linseed oil was determined by isothermal calorimetry at 298 K. The results show that waxes were able to slow down linseed oil autoxidation, with apple waxes being more active than orange waxes. However, such activity was visible only at relatively high concentrations (>1% of waxes), greatly higher than the concentration used with radical chain breakers like BHT (0.2%). The inhibition activity was explained by considering three different mechanisms: (1) residual polyphenol content in the wax, (2) high termination rate of the radical chain process, and (3) physical hindrance of the oxidation process by change in viscosity. All these mechanisms were possible, although the latter seemed to be the most important. Finally, the importance of waxes in the inhibition of lipid autoxidation was determined by testing their inhibition activity in combination with primary antioxidants. A mixture of waxes with BHA, ethoxyquin and α-tocopherol showed a higher rate of inhibition than when present individually. This suggested a strong cooperative radical scavenging activity, whose beneficial effect might pave the way to the formulation of novel functional ingredients.

Controlling oleogel crystallization using ultrasonic standing waves.

Oleogels are lipid-based soft materials composed of large fractions of oil (> 85%) developed as saturated and hydrogenated fat substitutes to reduce cardiovascular diseases caused by obesity. Promising oleogels are unstable during storage, and to improve their stability careful control of the crystalline network is necessary. However, this is unattainable with state-of-the-art technologies. We employ ultrasonic standing wave (USSW) fields to modify oleogel structure. During crystallization, the growing crystals move towards the US-SW nodal planes. Homogeneous, dense bands of microcrystals form independently of oleogelator type, concentration, and cooling rate. The thickness of these bands is proportional to the USSW wavelength. These new structures act as physical barriers in reducing the migration kinetics of a liposoluble colorant compared to statically crystallized oleogels. These results may extend beyond oleogels to potentially be used wherever careful control of the crystallization process and final structure of a system is needed, such as in the cosmetics, pharmaceutical, chemical, and food industries.

Lignin-Rich PHWE Hemicellulose Extracts Responsible for Extended Emulsion Stabilization.

Wood hemicelluloses have an excellent capacity to form and stabilize oil-in-water emulsions. Galactoglucomannans (GGM) from spruce and glucuronoxylans (GX) from birch provide multifunctional protection against physical breakdown and lipid oxidation in emulsions. Phenolic residues, coextracted with hemicelluloses using the pressurized hot water (PHWE) process, seem to further enhance emulsion stability. According to hypothesis, phenolic residues associated with hemicelluloses deliver and anchor hemicelluloses at the emulsion interface. This study is the first to characterize the structure of the phenolic residues in both GGM- and GX-rich wood extracts and their role in the stabilization of emulsions. PHWE GGM and GX were fractionated by centrifugation to obtain concentrated phenolic residues as one fraction (GGM-phe and GX-phe) and partially purified hemicelluloses as the other fraction (GGM-pur and GX-pur). To evaluate the role of each fraction in terms of physical and oxidative stabilization, rapeseed oil-in-water emulsions were prepared using GGM, GX, GGM-pur, and GX-pur as stabilizers. Changes in droplet-size distribution and peroxide values were measured during a 3-month accelerated storage test. The results for fresh emulsions indicated that the phenolic-rich fractions in hemicelluloses take part in the formation of emulsions. Furthermore, results from the accelerated storage test indicated that phenolic structures improve the long-term physical stability of emulsions. According to measured peroxide values, all hemicelluloses examined inhibited lipid oxidation in emulsions, GX being the most effective. This indicates that phenolic residues associated with hemicelluloses act as antioxidants in emulsions. According to chemical characterization using complementary methods, the phenolic fractions, GGM-phe and GX-phe, were composed mainly of lignin. Furthermore, the total carbohydrate content of the phenolic fractions was clearly lower compared to the starting hemicelluloses GGM and GX, and the purified fractions GGM-pur and GX-pur. Apparently, the phenolic structures were enriched in the GGM-phe and GX-phe fractions, which was confirmed by NMR spectroscopy as well as by other characterization methods. The frequency of the main bonding pattern in lignins, the ß-O-4 structure, was clearly very high, suggesting that extracted lignin remains in native form. Furthermore, the lignin carbohydrate complex of γ-ester type was found, which could explain the excellent stabilizing properties of PHWE hemicelluloses in emulsions.

Combined high-power ultrasound and high-pressure homogenization nanoemulsification: The effect of energy density, oil content and emulsifier type and content.

Combinations of ultrasound (US) and high-pressure homogenization (HPH) at low-medium energy densities were studied as alternative processes to individual US and HPH to produce Tween 80 and whey protein stabilized nanoemulsions, while reducing the energy input. To this aim, preliminary trials were performed to compare emulsification efficacy of single and combined HPH and US treatments delivering low-medium energy densities. Results highlighted the efficacy of US-HPH combined process in reducing the energy required to produce nanoemulsions stabilized with both Tween 80 and whey protein isolate. Subsequently, the effect of emulsifier content (1-3% w/w), oil amount (10-20% w/w) and energy density (47-175 MJ/m3) on emulsion mean particle diameter was evaluated by means of a central composite design. Particles of 140-190 nm were obtained by delivering 175 MJ/m3 energy density at emulsions containing 3% (w/w) Tween 80 and 10% (w/w) oil. In the case of whey protein isolate stabilized emulsions, a reduced emulsifier amount (1% w/w) and intermediate energy density (120 MJ/m3) allowed a minimum droplet size around 220-250 nm to be achieved. Results showed that, in both cases, at least 50% of the energy density should be delivered by HPH to obtain the minimum particle diameter.

ß-Carotene degradation kinetics as affected by fat crystal network and solid/liquid ratio.

The aim of this research was to study ß-carotene degradation kinetics into lipid systems containing different fat crystal networks in the presence of increasing liquid oil amounts. To this purpose, fat blends containing liquid saturated medium chain triacylglycerols (MCT) with increasing content of saturated monoglycerides (MG), tripalmitin (PPP) and tristearin (SSS) were added with 0.6mg/g ß-carotene. The fat crystal networks formed in the fat blends were characterized by using polarized light microscopy and synchrotron X-ray diffraction (XRD). In addition, ß-carotene degradation was monitored during storage in the dark at 20°C. Results highlighted that fat crystallization could differently affect ß-carotene stability. In bulk SSS and PPP, ß-carotene degradation proceeded at comparable rate, whereas when the saturated liquid oil MCT is included in the fat network, the rate of oxidation slightly decreased. Interestingly, the oxidation rate was not significantly affected by the solid/liquid ratio of the systems. A completely different behavior was observed in MG containing systems: the rate of ß-carotene oxidation was in every case significantly lower than that observed in SSS and PPP containing samples. Also in this case, the MG protective effect was independent on its content in the fat mixtures.

Structural and viscoelastic characterization of ternary mixtures of sunflower oil, saturated monoglycerides and aqueous phases containing different bases.

The structure at different length scales and the viscoelastic properties of ternary mixtures composed of saturated monoglycerides, sunflower oil and aqueous solutions of weak bases (KHCO3, NaHCO3, and NH4HCO3) or strong bases (NaOH and KOH) were investigated. The characteristics of ternary mixtures were studied systematically by using polarized light microscopy, differential scanning calorimetry (DSC), synchrotron X-ray diffraction (XRD) and rheological analysis. Results showed that the base type and concentration greatly affected the structure of the mixtures. The use of strong bases allowed gelled systems to be obtained only at low concentrations (<10mM). On the contrary, the presence of weak bases induced gelling at all concentrations considered (from 1 to 1000mM). The increase of base concentration led to a reduction of the mean droplet diameter and melting temperature. At the same time, the viscoelastic characteristics as a function of base concentration followed a more complex behavior: G' and G″ progressively decreased as the salt concentration increased in a concentration range from 1 to 100mM, while the rheological parameters increased when salt concentration increased from 100 to 1000mM. The structural and viscoelastic behavior of systems prepared with different salts were commonly independent of the cation present in the medium. Results highlight that it is possible to tailor the structure of these gels by using specific bases.