Effect of pH on the emulsifying performance of protein-polysaccharide complexes.

BACKGROUND: Protein-polysaccharide complexes have been successfully used for emulsion stabilization. However, it is unclear how the complex's surface charge influences aggregation stability and coalescence stability of emulsions, and whether a low charged interfacial film can still maintain the coalescence stability of oil droplets. In the present study, the effects of pH (around the pI of protein) on the aggregation and coalescence stability of emulsions were investigated. RESULTS: Whey protein isolate (WPI) and peach gum polysaccharides (PGP) complexes (WPI-PGP complexes) were synthesized at pH 3, 4 and 5. Their sizes were 598, 274 and 183 nm, respectively, and their ζ-potentials were +2.9, -8.6 and -22.8 mV, respectively. Interface rheological experiments showed that WPI-PGP complex at pH 3 had the lowest interfacial tension, and formed the softest film compared to the complexes at pH 4 and 5. Microfluidic experiments showed that all WPI-PGP complexes were able to stabilize droplets against coalescence within short timescales (milliseconds). At pH 3, no coalescence was observed even under conditions where the continuous phase flow influenced the shape of oil droplets (from spheres to ellipsoids). At pH 4 and 5, the model emulsions were stable over 16 days of storage, extensive aggregation and creaming occurred at pH 3 after 8 days. Importantly, no coalescence took place. CONCLUSION: The present study confirmed that the aggregation stability of the emulsions was mainly determined by the surface charge of the complex, whereas the coalescence stability of emulsions is expectedly determined by steric repulsion, providing new insights into how to prepare stable food emulsions. © 2024 Society of Chemical Industry.

Oxidative stability of emulsions fortified with iron: the role of liposomal phospholipids.

BACKGROUND: Interest in supplementing food with iron to counteract dietary deficiencies has been on the rise in recent years. A major challenge is the pro-oxidant activity of soluble iron, which compromises the chemical stability of the enriched food products. This problem could be mitigated by encapsulating iron, to physically keep it separated from oxidizable substrates, such as unsaturated fatty acids. In the present work, the physical and chemical stability of surfactant- or protein-stabilized oil-in-water emulsions fortified with iron was investigated. RESULTS: Iron (ferrous sulfate) was successfully incorporated in liposomes at high encapsulation efficiency (89%). The liposomes obtained were added to emulsions stabilized with either Tween 20 or whey protein isolate (WPI), and its oxidative stability was monitored and compared with emulsions with free iron. Tween 20-stabilized emulsions were more stable against oxidation than WPI-stabilized emulsions, and furthermore lipid oxidation was substantially higher in emulsions containing iron (either free, or encapsulated in liposomes) than in blank emulsions. This shows that liposomal encapsulation did not inhibit the pro-oxidant activity of iron. CONCLUSION: Despite the high encapsulation efficiency of iron in our liposomes, these systems are not suitable to supplement model foods with iron because of the associated deleterious chemical reactivity. This is most probably due to the phospholipids used as encapsulation material being prone to oxidation, which may actively contribute to the oxidative process. These aspects are normally not taken into account but we showed that they are of utmost importance, and should be taken as a starting point in the design of delivery systems. © 2018 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Food-grade micro-encapsulation systems that may induce satiety via delayed lipolysis: A review.

The increasing prevalence of overweight and obesity requires new, effective prevention and treatment strategies. One approach to reduce energy intake is by developing novel foods with increased satiating properties, which may be accomplished by slowing down lipolysis to deliver substrates to the ileum, thereby enhancing natural gut-brain signaling pathways of satiety that are normally induced by meal intake. To develop slow release food additives, their processing in the gastrointestinal tract has to be understood; therefore, we start from a general description of the digestive system and relate that to in vitro modeling, satiety, and lipolytic mechanisms. The effects of physicochemical lipid composition, encapsulation matrix, and interfacial structure on lipolysis are emphasized. We give an overview of techniques and materials used, and discuss partitioning, which may be a key factor for encapsulation performance. Targeted release capsules that delay lipolysis form a real challenge because of the high efficiency of the digestive system; hardly any proof was found that intact orally ingested lipids can be released in the ileum and thereby induce satiety. We expect that this challenge could be tackled with structured o/w-emulsion-based systems that have some protection against lipase, e.g., by hindering bile salt adsorption and/or delaying lipase diffusion.

Tailored microstructure of colloidal lipid particles for Pickering emulsions with tunable properties.

Sub-micron colloidal lipid particles (CLPs) can successfully be used as Pickering stabilizers in oil-in-water (O/W) emulsions, leading to an enhanced physical stability compared to conventional emulsifier-stabilized emulsions. Varying the lipid solid-liquid ratio leads to particles with distinct nanostructure and morphology, resulting in tunable emulsion stabilization performance. Our CLPs are produced by hot high pressure homogenization of high melting point fats in water, and subsequent cooling to induce lipid crystallization. Lath-like tripalmitin and palm stearin CLPs form jammed, cohesive interfacial layers that prevent relaxation of emulsion droplets, and form a three-dimensional network in the continuous aqueous phase. CLPs consisting of a mixture of solid tripalmitin and liquid tricaprylin are polycrystalline platelet-like particles that form O/W emulsions with spherical and bridged droplets covered by a thin particle layer. Our results present a versatile approach to interfacial design that also opens up new perspectives for development of novel delivery systems for active ingredients.

Convective mass transport dominates surfactant adsorption in a microfluidic Y-junction.

Surfactant adsorption during emulsification can be quantified by measuring the acting interfacial tension using a Y-junction microfluidic device. To obtain insight into the surfactant transport mechanism to the interface, the effect of shear force on the acting interfacial tension was assessed by systematically varying the continuous phase viscosity and velocity. Varying the continuous phase viscosity did not affect the acting interfacial tension, indicating that surfactant adsorption during Y-junction emulsification is not diffusion-limited. The acting interfacial tension was inversely dependent on the continuous phase velocity, which indicates that surfactant adsorption is governed by convective mass transfer resulting from the continuous phase velocity. The acting interfacial tension can be measured in the sub-millisecond time scale and under convective transport conditions using the Y-junction. These conditions are relevant to industrial emulsification and cannot be assessed by conventional tensiometry techniques (e.g., drop tensiometers) where surfactant adsorption is mostly driven by diffusion. We believe, therefore, that this method can be used to understand emulsifier adsorption during industrial emulsification, which can, in turn, be used to rationally design emulsion formulations and processes.

Ambient surface analysis of organic monolayers using direct analysis in real time Orbitrap mass spectrometry.

A better characterization of nanometer-thick organic layers (monolayers) as used for engineering surface properties, biosensing, nanomedicine, and smart materials will widen their application. The aim of this study was to develop direct analysis in real time high-resolution mass spectrometry (DART-HRMS) into a new and complementary analytical tool for characterizing organic monolayers. To assess the scope and formulate general interpretation rules, DART-HRMS was used to analyze a diverse set of monolayers having different chemistries (amides, esters, amines, acids, alcohols, alkanes, ethers, thioethers, polymers, sugars) on five different substrates (Si, Si3N4, glass, Al2O3, Au). The substrate did not play a major role except in the case of gold, for which breaking of the weak Au-S bond that tethers the monolayer to the surface, was observed. For monolayers with stronger covalent interfacial bonds, fragmentation around terminal groups was found. For ester and amide-terminated monolayers, in situ hydrolysis during DART resulted in the detection of ions characteristic of the terminal groups (alcohol, amine, carboxylic acid). For ether and thioether-terminated layers, scission of C-O or C-S bonds also led to the release of the terminal part of the monolayer in a predictable manner. Only the spectra of alkane monolayers could not be interpreted. DART-HRMS allowed for the analysis of and distinction between monolayers containing biologically relevant mono or disaccharides. Overall, DART-HRMS is a promising surface analysis technique that combines detailed structural information on nanomaterials and ultrathin films with fast analyses under ambient conditions.

Effect of Nonprotein Components for Lipid Oxidation in Emulsions Stabilized by Plant Protein Extracts.

Plant protein ingredients are rich in non-protein components of which the antioxidant and pro-oxidant effects are expected to be considerable. In this paper, commercial soy and pea protein isolates and concentrates were selected by using their soluble fractions to prepare oil-in-water (O/W) emulsions. Emulsions stabilized with soy protein isolates were more prone to lipid oxidation than those with soy protein concentrate or pea protein isolate. Compositional analysis revealed that the soluble fraction of soy protein isolates contained higher concentrations of phenolic compounds and metals (iron and copper) but lower mineral and ash contents than those of soy protein concentrate and pea protein isolate. Correlating the composition to oxidation in emulsions highlighted the significant role of non-protein components, alongside the protein's oxidative state. These findings are relevant for the use of alternative proteins in food formulation, a practice often promoted as sustainable yet that may come with repercussions for oxidative stability.

From fundamental insights to rational (bio)polymer nanocomposite design - Connecting the nanometer to meter scale.

Nanoparticle addition has the potential to make bioplastic use mainstream, as the resultant nanocomposite shows improved mechanical, barrier, and thermal properties. It is well established that the architecture and dynamics of the nanoparticle-polymer interphasial region, ∼ 1.5-9 nm from the nanoparticle surface, are crucial for nanocomposite characteristics. Yet, how these molecular phenomena translate to the bulk is still largely unknown. A multi-disciplinary and multi-scale vision is required to capture the full picture and improve materials far beyond what is currently possible. In this review, a first step in bridging the apparent gap between fundamental insights toward observed material properties is made. At the molecular scale, the polymer chain density and dynamics at the nanoparticle surface are governed by a complex interplay between enthalpy and entropy. The resultant interphasial properties can only be propagated to the macroscopic scale effectively when the nanoparticles are well-distributed. This makes the dispersion state a key parameter for which thermodynamic and kinetic insights can be used to prevent nanoparticle aggregation. These insights are linked to material properties relevant to packaging. The outlook section elaborates on the remaining challenges and the steps required to further understand and better design nanocomposite systems.

Studying surfactant mass transport through dynamic interfacial tension measurements: A review of the models, experiments, and the contribution of microfluidics.

Surfactant mass transport towards an interface plays a critical role during formation of emulsions, foams and in industrial processes where two immiscible phases coexist. The understanding of these mechanisms as experimentally observed by dynamic interfacial tension measurements, is crucial. In this review, theoretical models describing both equilibrated systems and surfactant kinetics are covered. Experimental results from the literature are analysed based on the nature of surfactants and the tensiometry methods used. The innovative microfluidic techniques that have become available to study both diffusion and adsorption mechanisms during surfactant mass transport are discussed and compared with classical methods. This review focuses on surfactant transport during formation of droplets or bubbles; stabilisation of dispersed systems is not discussed here.

Interfacial protein adsorption behavior can be connected across a wide range of timescales using the microfluidic EDGE (Edge-based droplet GEneration) tensiometer.

HYPOTHESIS: Our hypothesis is that dynamic interfacial tension values as measured by the partitioned-Edge-based Droplet GEneration (EDGE) tensiometry can be connected to those obtained with classical techniques, such as the automated drop tensiometer (ADT), expanding the range of timescales towards very short ones. EXPERIMENTS: Oil-water and air-water interfaces are studied, with whey protein isolate solutions (WPI, 2.5 - 10 wt%) as the continuous phase. The dispersed phase consists of pure hexadecane or air. The EDGE tensiometer and ADT are used to measure the interfacial (surface) tension at various timescales. A comparative assessment is carried out to identify differences between protein concentrations as well as between oil-water and air-water interfaces. FINDINGS: The EDGE tensiometer can measure at timescales down to a few milliseconds and up to around 10 s, while the ADT provides dynamic interfacial tension values after at least one second from droplet injection and typically is used to also cover hours. The interfacial tension values measured with both techniques exhibit overlap, implying that the techniques provide consistent and complementary information. Unlike the ADT, the EDGE tensiometer distinguishes differences in protein adsorption dynamics at protein concentrations as high as 10 wt% (which is the highest concentration tested) at both oil-water and air-water interfaces.

Particle dispersion governs nano to bulk dynamics for tailored nanocomposite design.

Nanoparticle addition can expand bioplastic use, as the resultant nanocomposite features e.g., improved mechanical properties. HYPOTHESIS: It is generally hypothesised that the nanoparticle-polymer interaction strength is pivotal to reduce polymer dynamics within the interphasial region and beyond. EXPERIMENTS: Translating nanoscale phenomena to bulk properties is challenging, as traditional techniques that probe interphasial dynamics are limited to well-dispersed systems. Laser speckle imaging (LSI) enabled us to probe interphasial nanoscale dynamics of samples containing aggregated nanoparticles. We relate these LSI-derived relaxation times to bulk rheological properties at a micro scale. FINDINGS: Nanocomposites with well-dispersed PDMS-coated titanium dioxide nanoparticles of ∼100 nm showed higher viscosities than nanocomposites containing aggregated PVP- and PAA-coated nanoparticles of 200-2000 nm. Within the interphasial region, nanoparticle addition increased relaxation times by a factor 101-102, reaching ultraslow relaxations of ∼103 s. While the viscosity increased upon nanoparticle loading, interphasial relaxation times plateaued at 5 wt% for nanocomposites containing well-dispersed nanoparticles and 10 wt% for nanocomposites containing aggregated nanoparticles. Likely, interphasial regions between nanoparticles interact, which is more prominent in systems with well-dispersed nanoparticles and at higher loadings. Our results highlight that, contrary to general belief, nanoparticle dispersion seems of greater importance for mechanical reinforcement than the interaction between polymer and particle.

Unravelling the effect of droplet size on lipid oxidation in O/W emulsions by using microfluidics.

Lipid oxidation in emulsions is hypothesised to increase with decreasing droplet size, as this increases the specific oil-water interfacial area, where lipid oxidation is expected to be initiated. In literature, however, contradictory results have been reported, which can be caused by confounding factors such as the oil droplet polydispersity and the distribution of components between the available phases. In this work, monodisperse surfactant-stabilised emulsions with highly controlled droplet sizes of 4.7, 9.1, and 26 µm were produced by microfluidic emulsification. We show that lipid oxidation increases with decreasing droplet size, which we ascribe to the increased contact area between lipids and continuous phase prooxidants. Besides, a significant amount of oxygen was consumed by oxidation of the surfactant itself (Tween 20), an effect that also increased with decreasing droplet size. These insights substantiate the importance of controlling droplet size for improving the oxidative stability of emulsions.

Droplet size dependency and spatial heterogeneity of lipid oxidation in whey protein isolate-stabilized emulsions.

Spatiotemporal assessment of lipid and protein oxidation is key for understanding quality deterioration in emulsified food products containing polyunsaturated fatty acids. In this work, we first mechanistically validated the use of the lipid oxidation-sensitive fluorophore BODIPY 665/676 as a semi-quantitative marker for local peroxyl radical formation. Next, we assessed the impact of microfluidic and colloid mill emulsification (respectively producing mono- and polydisperse droplets) on local protein and lipid oxidation kinetics in whey protein isolate (WPI)-stabilized emulsions. We further used BODIPY 581/591 C11 and CAMPO-AFDye 647 as colocalisation markers for lipid and protein oxidation. The polydisperse emulsions showed an inverse relation between droplet size and lipid oxidation rate. Further, we observed less protein and lipid oxidation occurring in similar sized droplets in monodisperse emulsions. This observation was linked to more heterogeneous protein packing at the droplet surface during colloid mill emulsification, resulting in larger inter-droplet heterogeneity in both protein and lipid oxidation. Our findings indicate the critical roles of emulsification methods and droplet sizes in understanding and managing lipid oxidation.

Advances in chitin-based nanoparticle use in biodegradable polymers: A review.

Chitin-based nanoparticles are polysaccharide materials that can be produced from a waste stream of the seafood industry: crustacean shells. These nanoparticles have received exponentially growing attention, especially in the field of medicine and agriculture owing to their renewable origin, biodegradability, facile modification, and functionality adjustment. Due to their exceptional mechanical strength and high surface area, chitin-based nanoparticles are ideal candidates for reinforcing biodegradable plastics to ultimately replace traditional plastics. This review discusses the preparation methods for chitin-based nanoparticles and their applications. Special focus is on biodegradable plastics for food packaging making use of the features that can be created by the chitin-based nanoparticles.

Lipid oxidation products in model food emulsions: do they stay in or leave droplets, that's the question.

Lipid oxidation is a major factor limiting the shelf life of food and other emulsion products. In this work, we explore which lipid oxidation products may transfer between oil droplets in model food emulsions stabilized by excess amounts of surfactant, and whether this affects the overall reaction. No significant differences in concentrations of triglyceride-bound hydroperoxides were found before and after mixing 'clean' oil droplets with pre-oxidized ones. Shorter and more hydrophilic lipid oxidation products, such as 4-hydroperoxy-2-nonenal and 2,4-decadienal, were found to equilibrate between oil droplets within 30 min. Adding exogenous 4-hydroperoxy-2-nonenal to an emulsion led to overall higher lipid oxidation values, although this effect was not systematic nor instantaneous. Therefore, it may be questioned whether transfer and subsequent initiation are always relevant for oxidizing emulsion systems. In future research, this question should be addressed for complex emulsions that are closer to real-life food products.

Comparison of the Degree of Acetylation of Chitin Nanocrystals Measured by Various Analysis Methods.

Chitin and its derivate chitosan have versatile properties and have been used in various applications. One key parameter determining the functionality of chitin-based materials is the degree of acetylation (DA). For DA determination, NMR and FTIR spectroscopy are often considered to be the gold standard, but these techniques may not always be available and are rather time-consuming and costly. The first derivative UV method has been suggested, although accurate measurements can be challenging for materials with high degrees of acetylation, due to hydroxymethylfurfural (HMF) formation and other side reactions occurring. In this paper, we re-evaluated the first derivate UV method for chitin and chitosan powder, chitin nanocrystals, and deacetylated chitin nanocrystals. Our results showed that the first derivative UV method is capable of measuring DA with high accuracy (>0.9), leading to values comparable to those obtained by 1H NMR, 13C NMR, and FTIR. Moreover, by-product formation could either be suppressed by selecting the proper experimental conditions, or be compensated. For chitin nanocrystals, DA calculation deviations up to 20% due to by-product formation can be avoided with the correction that we propose. We conclude that the first derivative UV method is an accessible method for DA quantification, provided that sample solubility is warranted.

Design insights for upscaling spontaneous microfluidic emulsification devices based on behavior of the Upscaled Partitioned EDGE device.

Microfluidic emulsification has the potential to produce emulsions with very controlled droplet sizes in a subtle manner. To support in unleashing this potential, we provide guidelines regarding upscaling based on the performance of Upscale Partitioned EDGE (UPE) devices, using rapeseed oil as the to-be-dispersed phase and whey proteins as the emulsifier. The UPE5x1 device (11,000 droplet formation units (DFUs) of 5 × 1 µm) produced 3.5-µm droplets (CV 3.2 %) at 0.3 mL/h; UPE10x2 (8,000 DFUs of 10 × 2 µm) produced 7-µm droplets (CV 3.2 %) at 0.5 mL/h, and at higher pressures, 32-µm droplets (CV 3-4 %) at 4 mL/h. These productivities are relatively high compared to those of other devices reported in literature (e.g., Microchannel, Tsukuba and Millipede, Harvard). Based on these results, and on others from literature, we conclude that: (1) the continuous phase channel dimensions need to be chosen such that they allow for gradual filling of this channel with droplets without decreasing the pressure over the droplet formation units significantly; (2) the dispersed phase supply channel design should create a wide stable droplet formation pressure range to increase productivity; and (3) higher productivities can be obtained through the choice of the ingredients used; low viscosity dispersed phase and an emulsifier that increases the interfacial tension without negatively affecting device wettability is preferred (e.g., whey protein outperforms Tween 20). These results and design guidelines are expected to contribute to the first food emulsion products prepared with microfluidics.

Physical and Oxidative Stabilization of Oil-In-Water Emulsions by Roasted Coffee Fractions: Interface- and Continuous Phase-Related Effects.

Emulsions fortified with polyunsaturated fatty acids are highly relevant from a nutritional perspective; however, such products are prone to lipid oxidation. In the current work, this is mitigated by the use of natural antioxidants occurring in coffee. Coffee fractions with different molecular weights were extracted from roasted coffee beans. These components were positioned either at the interface or in the continuous phase of emulsions where they contributed to emulsion stability via different pathways. Coffee brew as a whole, and its high-molecular-weight fraction (HMWF), was able to form emulsions with good physical stability and excellent oxidative stability. When added post-homogenization to the continuous phase of dairy protein-stabilized emulsions, all coffee fractions were able to slow down lipid oxidation considerably without altering the physical stability of emulsions, though HMWF was more effective in retarding lipid oxidation than whole coffee brew or low-molecular-weight fraction. This is caused by various effects, such as the antioxidant properties of coffee extracts, the partitioning of components in the emulsions, and the nature of the phenolic compounds. Our research shows that coffee extracts can be used effectively as multifunctional stabilizers in dispersed systems leading to emulsion products with high chemical and physical stability.

Tiny, yet impactful: Detection and oxidative stability of very small oil droplets in surfactant-stabilized emulsions.

HYPOTHESIS: The shelf life of multiphase systems, e.g. oil-in-water (O/W) emulsions, is severely limited by physical and/or chemical instabilities, which degrade their texture, macroscopic appearance, sensory and (for edible systems) nutritional quality. One prominent chemical instability is lipid oxidation, which is notoriously complex. The complexity arises from the involvement of many physical structures present at several scales (1-10,000 nm), of which the smallest ones are often overlooked during characterization. EXPERIMENTS: We used cryogenic transmission electron microscopy (cryo-TEM) to characterize the coexisting colloidal structures at the nanoscale (10-200 nm) in rapeseed oil-based model emulsions stabilized by different concentrations of a nonionic surfactant. We assessed whether the oxidative and physical instabilities of the smallest colloidal structures in such emulsions may be different from those of larger colloidal structures. FINDINGS: By deploying cryo-TEM, we analyzed the size of very small oil droplets and of surfactant micelles, which are typically overlooked by dynamic light scattering when larger structures are concomitantly present. Their size and oil content were shown to be stable over incubation, but lipid oxidation products were overrepresented in these very small droplets. These insights highlight the importance of the fraction of "tiny droplets" for the oxidative stability of O/W emulsions.

Capillary pressure-based measurement of dynamic interfacial tension in a spontaneous microfluidic sensor.

The size of droplets and bubbles, and the properties of emulsions and foams strongly depend on dynamic interfacial tension (γd) - a parameter that is often inaccessible due to the very short time scales for droplet and bubble formation, and the inaccessibility of (e.g., food) production lines. To solve this challenge, we developed a microfluidic tensiometer that can measure γd by monitoring the formation time of both droplets and bubbles. Our tensiometer is a pressure-driven microfluidic device that operates based on the principle of a pressure balance: the formation of a droplet (or a bubble) is initialized when the Laplace pressure of the interface is decreased below the externally applied pressure, and this decrease is caused by a reduction in γd that can be calculated from the applied pressure and the Young-Laplace equation. The decay of γd due to surfactant adsorption can be followed at the characteristic time scale, which is dependent on surfactant type and concentration. For 0.05-1% wt sodium dodecyl sulfate (SDS), we were able to measure γd at time scales down to 1 ms and 0.1 ms for droplet and bubble interfaces, respectively, at increasing applied pressures and SDS concentrations. Our tensiometer proves to be a simple, robust method that inherently allows access to nearly the full range of dynamic interfacial tension at relevant time scales.