Emulsion gels: The structuring of soft solids with protein-stabilized oil droplets

Many food products can be categorized as emulsion gels. This is especially the case for protein-based oil-in-water emulsions which can be converted into soft-solid-like materials by common food processing operations such as heating, acidification, and enzyme action. This review article outlines how the rheological and structural properties of protein-stabilized emulsion gels are influenced by the dispersed oil volume fraction, the oil–water interfacial composition, and the colloidal interactions of the constituent emulsion droplets. For model systems of variable oil content and containing different food proteins, some general trends of rheological behaviour at small and large deformations are identified. Experimental rigidity data are considered in relation to: (i) material science theories of the reinforcement of solid materials by active and inactive filler particles, and (ii) Brownian dynamics simulations of aggregated particle networks containing bonded and non-bonded particles. Influences of interfacial composition and particle–matrix interactions on microstructure and rheology are explained with particular reference to the role of small-molecule surfactants. Compositional and structural factors affecting the large-deformation rheology and fracture properties are described. Finally, the practical relevance of the model system studies to the behaviour of real food products is critically assessed.     

Interfacial design of protein-stabilized emulsions for optimal delivery of nutrients

Proteins are often used as ingredients in food emulsions, as their amphiphilic structures provide electrostatic and steric stabilization. Significant attention has recently been directed at understanding how the composition and structure of oil-water interfaces change during digestion and how these can be manipulated to enhance the delivery of nutrients contained within the oil droplets. These efforts have necessitated the development of more sophisticated in vitro digestion models of greater physiological relevance and increased efforts in research to identify the role of the various digestive parameters on interfacial dynamics. The changes occurring at the oil-water interface will affect the adsorption of gastro-intestinal lipases and, ultimately, affect lipid digestion. The composition of a protein-stabilized oil droplet changes continuously during digestion, because of proteolysis and the formation of peptides with different affinities for the interface. In addition, natural bio-surfactants such as phospholipids and bile salts, other surface- active molecules present in foods, and the products of lipolysis (i.e. mono and diglycerides, lysophospholipids), all compete for access to the interface, and contribute to the dynamic changes occurring on the surface of the oil droplets. A better understanding of how to tailor the composition of oil droplet surfaces in food emulsions will aid in optimizing lipid digestion and, as a result, delivery of lipophilic nutrients. This review focuses on the physico-chemical changes occurring in protein-stabilized oil-in-water emulsions during gastric and small intestine digestion, and on how interfacial engineering could lead to differences in fatty acid release and the potential bioavailability of lipophilic molecules.     

Investigation of food microstructure and texture using atomic force microscopy: A review

We review recent applications of atomic force microscopy (AFM) to characterize microstructural and textural properties of food materials. Based on interaction between probe and sample, AFM can image in three dimensions with nanoscale resolution especially in the vertical orientation. When the scanning probe is used as an indenter, mechanical features such as stiffness and elasticity can be analyzed. The linkage between structure and texture can thus be elucidated, providing the basis for many further future applications of AFM. Microstructure of simple systems such as polysaccharides, proteins, or lipids separately, as characterized by AFM, is discussed. Interaction of component mixtures gives rise to novel properties in complex food systems due to development of structure. AFM has been used to explore the morphological characteristics of such complexes and to investigate the effect of such characteristics on properties. Based on insights from such investigations, development of food products and manufacturing can be facilitated. Mechanical analysis is often carried out to evaluate the suitability of natural or artificial materials in food formulations. The textural properties of cellular tissues, food colloids, and biodegradable films can all be explored at nanometer scale, leading to the potential to connect texture to this fine structural level. More profound understanding of natural food materials will enable new classes of fabricated food products to be developed.     

Atomic force microscopy of starch systems

Atomic force microscopy (AFM) generates information on topography, adhesion, and elasticity of sample surface by touching with a tip. Under suitable experimental settings, AFM can image biopolymers of few nanometers. Starch is a major food and industrial component. AFM has been used to probe the morphology, properties, modifications, and interactions of starches from diverse botanical origins at both micro- and nano-structural levels. The structural information obtained by AFM supports the blocklet structure of the granules, and provides qualitative and quantitative basis for some physicochemical properties of diverse starch systems. It becomes evident that AFM can complement other microscopic techniques to provide novel structural insights for starch systems.     

A review of the rheological properties of dilute and concentrated food emulsions

Rheology is a powerful and versatile analytical tool for providing information about changes in the composition, structure, and interactions of food emulsions. Moreover, an understanding of emulsion rheology is essential for designing efficient food processing operations and emulsion-based foods with the desired physicochemical, sensory, and nutritional attributes, such as appearance, texture, flavor, shelf life, and bioavailability. This article provides a brief overview of the current understanding of food emulsions, with a focus on how their viscosity is related to the properties of the emulsion droplets present.     

In vitro β‐Carotene Bioaccessibility and Lipid Digestion in Emulsions: Influence of Pectin Type and Degree of Methyl‐Esterification

Citrus pectin (CP) and sugar beet pectin (SBP) were demethoxylated and fully characterized in terms of pectin properties in order to investigate the influence of the pectin degree of methyl‐esterification (DM) and the pectin type on the in vitro β‐carotene bioaccessibility and lipid digestion in emulsions. For the CP based emulsions containing β‐carotene enriched oil, water and pectin, the β‐carotene bioaccessibility, and lipid digestion were higher in the emulsions with pectin with a higher DM (57%; “CP57 emulsion”) compared to the emulsions with pectin with a lower DM (30%; “CP30 emulsion”) showing that the DM plays an important role. In contrast, in SBP‐based emulsions, nor β‐carotene bioaccessibility nor lipid digestion were dependent on pectin DM. Probably here, other pectin properties are more important factors. It was observed that β‐carotene bioaccessibility and lipid digestion were lower in the CP30 emulsion in comparison with the CP57, SBP32, and SBP58 emulsions. However, the β‐carotene bioaccessibility of CP57 emulsion was similar to that of the SBP emulsions, whereas the lipid digestion was not. It seems that pectin type and pectin DM (in case of CP) are determining which components can be incorporated into micelles. Because carotenoids and lipids have different structures and polarities, their incorporation may be different. This knowledge can be used to engineer targeted (digestive) functionalities in food products. If both high β‐carotene bioaccessibility and high lipid digestion are targeted, SBP emulsions are the best options. The CP57 emulsion can be chosen if high β‐carotene bioaccessibility but lower lipid digestion is desired.     

Rheological behaviour of aerated palm kernel oil/water emulsions

The interactions between emulsion droplets containing solid fat are important for the rheology and functionality of the emulsion as a whole, particularly for aerated emulsion systems where partial coalescence plays a role in the overall structure of the product. In this study, the interactions between emulsion droplets appeared to be sensitive to the relative amounts of solid fat and liquid oil, thus changing the rheology of the whole system. Incorporation of air had a major effect on these interactions as it appeared to force the emulsion to adopt a stronger structure by encouraging partial coalescence. The rheological behaviour of a non-aerated emulsion and an aerated emulsion was compared. Non-aerated samples did not show major changes in viscosity with increasing temperature. In contrast, the aerated emulsion seemed to be considerably more temperature sensitive, showing a dramatic increase of viscosity as the temperature was increased above a critical value. The effect of temperature ramp rates was investigated. Higher temperature ramp rates resulted in delayed changes in viscosity. The phase behaviour of the fat is both time and temperature dependent; therefore, a faster temperature ramp means that a higher temperature could be reached before critical phase changes in the fat could take place. The rheological behaviour of the emulsions was also dependent on the shear rate applied during the experiment.     

植物油体消化特性研究的进展

油体是植物种子储存甘油三酯的天然细胞器,其内部是甘油三酯、外部由单层磷脂和结构蛋白组成的生物膜所覆盖,油体在食品中有广泛的应用前景。本文综述影响油体界面层的因素及界面层对油体消化特性的影响。油体界面层主要通过油体来源、提取条件和外源添加等方式进行调控,并将界面层分为天然界面层和复合界面层。天然界面层由磷脂和结构蛋白组成,油体在胃消化时会融合成大尺寸液滴,比表面的增加影响了肠阶段的游离脂肪酸释放;复合界面层是由外源性蛋白质、多糖或酚类物质与油体的天然界面层组成,消化过程中外源性蛋白质水解不彻底会产生多重乳液和胶束,多糖在油体表面形成了紧密的界面膜,酚类与油体表面的蛋白络合,这些变化影响了油脂的消化。本文为油体作为膳食脂质、功能营养素运载及产品开发提供了参考。     

Importance of bacterial surface properties to control the stability of emulsions

In colloidal media such as emulsions or food matrixes, the stability results from physicochemical interactions. The same type of interaction is involved in the attachment processes of microorganisms, through their surface properties, to interfaces. When bacteria are present in a food matrix, it is probable that their surface interacts with the other constituents. In this paper, the involvement of bacterial surface properties of Lactococcus lactis subsp lactis biovar diacetylactis (LLD) on the stability of model emulsions has been studied. The hydrophobic and electrostatic cell-surface properties were characterized by the MATH method and by microelectrophoresis, respectively. The oil-in-water emulsions were stabilized by various surface-active compounds, CTAB, SDS or Tween 20, giving differently charged droplets. Two strains with different surface characteristics were added to the emulsion. Contrasting with emulsions made with the non-ionic surfactant, for which the stability was not modified by the addition of bacteria, the emulsions made with ionic surface-active compounds were unstable in the presence of bacteria when the bacterial surface charge was opposite to the one of the emulsion droplets. Moreover, aggregation and flocculation phenomena were observed for emulsions stabilized with the cationic surfactant, particularly for more negatively charged bacteria. The effect of bacteria on the emulsion stability depended on the strain which shows the importance of the choice of the microorganism according to of the characteristics of the colloidal media to obtain a stable system. In addition, these results suggest that the interactions between bacteria and other food components can influence the position of bacteria in food matrixes.     

Characterisation of emulsion properties and of interface composition in O/W emulsions prepared with hen egg yolk, plasma and granules

Comprehension of hen egg yolk emulsifying properties remains incomplete because competition between its various emulsifiers (proteins and lipoproteins containing phospholipids) has not been clearly elucidated and colloidal interactions between yolk-stabilised oil droplets have not been documented. Recent studies emphasised the interest of the fractionation of yolk into plasma and granules to improve this comprehension. In the present study, we characterised, concurrently, emulsion properties (oil droplet size and stability against creaming) and interface attributes (interfacial concentrations of proteins and phospholipids, SDS-PAGE profiles of adsorbed proteins and zeta potential) in oil-in-water (O/W) emulsions prepared with yolk, plasma and granules. We observed these features at four physicochemical conditions (pH 3.0 or 7.0 and at 0.15 or 0.55 M NaCl). Emulsion properties in emulsions made with yolk or plasma varied similarly as a function of pH and NaCl concentration whereas granules emulsions exhibited distinct properties. Therefore the main contributors to yolk emulsifying properties are to be sought for among plasma constituents (proteinaceous or phospholipids). Since, in plasma emulsions, variations of emulsion stability against creaming correlated exclusively to variations of protein interfacial concentration, a driving contribution of the proteinaceous part of plasma, namely apo-LDL, was hypothesised. In the pH and ionic strength ranges studied, zeta potentials of the interfaces were low, excluding extended electrostatic repulsion between oil droplets. We deduced that steric repulsion is the main interaction opposing to droplet aggregation in food emulsions made with yolk.     

Structure and stability of heat-treated concentrated dairy-protein-stabilised oil-in-water emulsions: A stability map characterisation approach

Emulsion instabilities such as depletion flocculation, coalescence, aggregation and heat-induced protein aggregation may be detrimental to the production of sterilised food emulsions. The type and the amount of protein present in the continuous phase and at the oil–water interface are crucial in the design of emulsions with appropriate stability. In this study, four oil-in-water model emulsion systems (pH 6.8–7.0) were formulated, characterised and categorised according to the potential interactions between protein-coated or surfactant-coated emulsion droplets and non-adsorbed proteins present in the continuous phase. The heat stability, the creaming behaviour and the flow behaviour of the model emulsions were influenced by both the emulsifier type and the type of protein in the continuous phase. The results suggest that this stability map approach of predicting droplet–droplet, droplet–protein and protein–protein interactions will be useful for the future design of heat-stable emulsion-based beverages with good creaming stability at high protein concentrations.     

Effects of long chain fatty acid unsaturation on the structure and controlled release properties of amylose complexes

The addition of functional long chain (LC) unsaturated fatty acids to foods is often hampered by their instability. This study aimed to probe the possibility of using molecular inclusion complexes formed by amylose, termed V-amylose, as a possible solution for the delivery of long chain (LC) fatty acids to the consumer. X-ray diffraction, light scattering and atomic force microscopy (AFM) were employed to study the micro- and nano-structure of V-amylose hosting LC fatty acids with different degrees of unsaturation. Additionally, enzymatic digestion tests were conducted to assess the release of the fatty acids from the complexes. X-ray diffraction confirmed the formation of V-amylose while light scattering measurements, and the AFM images revealed that increased fatty acid unsaturation lead to the formation of bigger and more disperse particle populations. Enzymatic digestion tests with mammalian pancreatin illustrated the control over guest release which is induced by enzymatic hydrolysis. In conclusion, this study demonstrates that guest chemistry affects some of the functional properties of V-amylose for the delivery of LC fatty acids.     

小麦醇溶蛋白纳米颗粒稳定皮克林乳液的研究

目的 构建负载丁香酚的小麦醇溶蛋白/果胶纳米颗粒稳定皮克林乳液,提高丁香酚生物利用率。方法 通过反溶剂法制备复合纳米颗粒,以乳液粒径、乳析指数为指标,考察复合纳米颗粒对皮克林乳液稳定性影响;以抑菌率为指标,考察皮克林乳液中丁香酚的生物利用率。结果 当负载丁香酚的小麦醇溶蛋白/果胶纳米颗粒浓度达5.00%,油相比例不超过60%,盐离子浓度低于250 mmol/L,储藏时间60 d以内时:皮克林乳液液滴颗粒分散,体系较为稳定。与此同时,当皮克林乳液最小抑菌浓度为1.00 mg/mL时,可有效抑制大肠杆菌的生长。结论 负载丁香酚的小麦醇溶蛋白/果胶纳米颗粒可在油水两相间形成界面膜以稳定皮克林乳液,其抑菌性能通过延长食品货架期的形式应用于食品保鲜领域中。     

蛋白界面膜及其评价方法研究进展

食品中乳化类产品的稳定性决定了其价值和顾客满意度,天然蛋白的乳化特性多年来受到食品胶体和界面科学领域广泛关注。蛋白吸附到水油界面形成的黏弹性薄膜具有降低界面张力、维持乳液稳定的特性。研究蛋白界面膜的物化性质有助于了解蛋白大分子在水油界面的吸附规律,能够用于评价、表征和预测蛋白乳液稳定性,并为优化蛋白乳液稳定性提供理论基础。基于此,该文对水包油乳液蛋白界面膜结构和影响因素进行探讨,系统综述了目前用于评价蛋白质界面特性的手段和方法,包括微观成像技术、热力学技术、光谱技术和界面流变学技术等,以研究蛋白类乳化液性能在宏观和微观层面的联系,为蛋白质界面膜在乳化食品中的应用提供参考。     

Surface Characterization of Caramel at the Micrometer Scale

ABSTRACT: The surface of caramel has been imaged using pulsed force atomic force microscopy (AFM) and scanning thermal microscopy, revealing shallow depressions in the surface of 1 to 10μm in dia that have a higher adhesion to the silicon AFM probe and a lower stiffness and different thermal character than the surrounding sample. This is consistent with the view of caramel as fat droplets within a matrix of sugars. As confirmation, the depressed regions were identified by infrared microscopy as consisting mainly of fat in a matrix of sugar. AFM also reveals that regions surrounding the depressions are decorated with thin (about 6nm) plate-like features that display a higher stiffness than the rest of the matrix. We propose that these are of crystalline origin and most probably consist of fat.     

Towards a nanoscale view of fungal surfaces

In the past years, atomic force microscopy (AFM) has offered novel possibilities for exploring the nanoscale surface properties of fungal cells. For the first time, AFM imaging enables investigators to visualize fine surface structures, such as rodlets, directly on native hydrated cells. Moreover, real-time imaging can be used to follow cell surface dynamics during cell growth and to monitor the effect of molecules such as enzymes and drugs. In fact, AFM is much more than a microscope in that when used in the force spectroscopy mode, it allows measurement of physicochemical properties such as surface energy and surface charge, to probe the elasticity of cell wall components and macromolecules, and to analyse the force and localization of molecular recognition events.     

Interfacial properties of deamidated wheat protein in relation to its ability to stabilise oil-in-water emulsions

Isolated wheat protein (IWP) is an acidic deamidated wheat protein. The deamidation process enhances the protein solubility at pHs greater than 6, and therefore its potential ability to act as a food emulsifier. The interfacial properties and the mechanism by which this protein stabilises oil-in-water emulsions were investigated by measuring the protein's absorbed layer thickness on latex particles, its interfacial rheology, and the colloidal and thermal stability of IWP stabilised emulsions. IWP forms a relatively thick interfacial layer of 18 nm upon adsorption onto latex beads, suggesting that the protein adsorbed with the long axis perpendicular to the surface, i.e. end-on, at a full protein coverage. The interfacial rheology measurement showed that IWP formed a relatively weak fluid-like interface. Similar to other protein emulsifiers, the colloidal stability of IWP emulsions is provided largely through electrostatic repulsion. Although IWP emulsions were sensitive to salt induced flocculation, the presence of excess protein in the aqueous phase (e.g. 4 wt%) was able to reduce the effect of salt screening (50 mM CaCl₂) on a 25 wt% oil-in-water emulsion completely. The emulsions underwent minimal coalescence when droplets were in close contact, e.g. flocculated, because the interfacial layer of IWP provides a barrier to droplet coalescence, even in high salt environments. IWP emulsions were resistant to thermal treatment with no changes in particle size observed when the emulsions were heated (up to 90 °C for 20 min) in the absence or the presence of 150 mM NaCl. The heat stability of IWP emulsions is thought to arise from the structure of IWP at the interface. A lack of free cysteines combined with few hydrophobic regions meant that there were minimal interactions between protein molecules adsorbed onto the same droplet or on neighbouring droplets. The unique interfacial properties of IWP, e.g. its physical layer thickness and the structure provide enhanced stability for emulsions against coalescence and heating.     

Food protein functionality: A comprehensive approach

Food protein functionality has classically been viewed from the perspective of how single molecules or protein ingredients function in solutions and form simple colloidal structures. Based on this approach, tests on protein solutions are used to produce values for solubility, thermal stability, gelation, emulsifying, foaming, fat binding and water binding to name a few. While this approach is beneficial in understanding the properties of specific proteins and ingredients, it is somewhat restricted in predicting performance in real foods where the complexities of ingredients and processing operations have a significant affect on the colloidal structures and therefore overall properties of the final food product. In addition, focusing on proteins as just biopolymers used to create food structures ignores the biological functions of proteins in the diet. These can be beneficial, as in providing amino acids for protein synthesis or bioactive peptides, or these can be detrimental, as in causing a food allergic response. This review will focus on integrating the colloidal/polymer and biological aspects of protein functionality. This will be done using foams and gels to illustrate colloidal/polymer aspects and bioactive peptides and allergenicity to demonstrate biological function.     

高内相Pickering乳液荷载生物活性物质的构建

目的 构建稳定荷载生物活性物质的高内相Pickering乳液。方法 通过简单的反溶剂纳米沉淀法制备玉米醇溶蛋白/果胶复合颗粒,再通过均质乳化技术,成功构建荷载姜黄素的高内相Pickering乳液,研究在不同pH条件下该乳液体系的储藏稳定性、外观、粒径和流变学特性。结果 该荷载姜黄素的高内相Pickering乳液（油相占比高达80%）能稳定储藏两个月以上不变质,乳液粒径较小,基本在100~200 μm之间,其流变学行为表明该乳液具有较好的粘弹性和凝胶特性,并且随着pH值的降低,胶体颗粒的三相接触角越接近90°,乳液的凝胶性越强,乳液越稳定。结论 本方法制备简单,操作方法,成功的构建了荷载姜黄素的高内相Pickering乳液,为高内相Pickering乳液在食品、药品和化妆品等领域的应用提供了一个方向。     

Aspects of milk-protein-stabilised emulsions

Milk proteins are widely used as ingredients in prepared foods, in which they perform a wide range of key functions, including emulsification, thickening, gelling and foaming. An important functionality of milk proteins in food colloids is their ability to facilitate the formation and stabilisation of oil droplets in emulsions. The ability of milk proteins to adsorb at the oil–water interface and to stabilise emulsions has been exploited by the food industry in the manufacture of nutritional products, specialised medical foods, dietary formulations, cream liqueurs and dairy desserts. This article provides an overview of the properties and functionalities of food emulsions formed with milk proteins, focusing on the structure and composition of adsorbed protein layers, competition between proteins and the physical and chemical stability of emulsion droplets. Of particular importance is the understanding of the behaviour of milk-protein-based emulsions under the conditions relevant to digestion in the human gastrointestinal tract. Recent relevant research in this area is reviewed and discussed.