Evaluating the Stability of Double Emulsions—A Review of the Measurement Techniques for the Systematic Investigation of Instability Mechanisms

Double emulsions are very promising for various applications in pharmaceutics, cosmetics, and food. Despite lots of published research, only a few products have successfully been marketed due to immense stability problems. This review describes approaches on how to characterize the stability of double emulsions. The measurement methods are used to investigate the influence of the ingredients or the process on the stability, as well as of the environmental conditions during storage. The described techniques are applied either to double emulsions themselves or to model systems. The presented analysis methods are based on microscopy, rheology, light scattering, marker detection, and differential scanning calorimetry. Many methods for the characterization of double emulsions focus only on the release of the inner water phase or of a marker encapsulated therein. Analysis methods for a specific application rarely give information on the actual mechanism, leading to double emulsion breakage. In contrast, model systems such as simple emulsions, microfluidic emulsions, or single-drop experiments allow for a systematic investigation of diffusion and coalescence between the individual phases. They also give information on the order of magnitude in which they contribute to the failure of the overall system. This review gives an overview of various methods for the characterization of double emulsion stability, describing the underlying assumptions and the information gained. With this review, we intend to assist in the development of stable double emulsion-based products

Influence of Hydrophilic Surfactants on the W1–W2 Coalescence in Double Emulsion Systems Investigated by Single Droplet Experiments

Double emulsions are a promising formulation for encapsulation and targeted release in pharmaceutics, cosmetics and food. An inner water phase is dispersed in an oil phase, which is again emulsified in a second water phase. The encapsulated inner water phase can be released via diffusion or via coalescence, neither of which is desired during storage but might be intended during application. The two interfaces in a double emulsion are stabilized by a hydrophilic and a lipophilic surfactant, to prevent the coalescence of the outer and the inner emulsion, respectively. This study focuses on the influence of the hydrophilic surfactant on the release of inner water or actives encapsulated therein via coalescence of the inner water droplet with the outer O–W2 interface. Since coalescence and diffusion are difficult to distinguish in double emulsions, single-droplet experiments were used to quantify differences in the stability of inner droplets. Different lipophilic (PGPH and PEG-30 dipolyhydroxylstearate) and hydrophilic surfactants (ethoxylates, SDS and polymeric) were used and resulted in huge differences in stability. A drastic decrease in stability was found for some combinations, while other combinations resulted in inner droplets that could withstand coalescence longer. The destabilization effect of some hydrophilic surfactants depended on their concentration, but was still present at very low concentrations. A huge spread of the coalescence time for multiple determinations was observed for all formulations and the necessary statistical analysis is discussed in this work. The measured stabilities of single droplets are in good accordance with the stability of double emulsions for similar surfactant combinations found in literature. Therefore, single droplet experiments are suggested for a fast evaluation of potentially suitable surfactant combinations for future studies on double-emulsion stability

Determination of the Dominating Coalescence Pathways in Double Emulsion Formulations by Use of Microfluidic Emulsions

In water-in-oil-in-water (W1/O/W2) double emulsions several irreversible instability phenomena lead to changes. Besides diffusive processes, coalescence of droplets is the main cause of structural changes. In double emulsions, inner droplets can coalesce with each other (W1–W1 coalescence), inner droplets can be released via coalescence (W1–W2 coalescence) and oil droplets can coalesce with each other (O–O coalescence). Which of the coalescence pathways contributes most to the failure of the double emulsion structure cannot be determined by common measurement techniques. With monodisperse double emulsions produced with microfluidic techniques, each coalescence path can be observed and quantified simultaneously. By comparing the occurrence of all possible coalescence events, different hydrophilic surfactants in combination with PGPR are evaluated and discussed with regard to their applicability in double emulsion formulations. When variating the hydrophilic surfactant, the stability against all three coalescence mechanisms changes. This shows that measuring only one of the coalescence mechanisms is not sufficient to describe the stability of a double emulsion. While some surfactants are able to stabilize against all three possible coalescence mechanisms, some display mainly one of the coalescence mechanisms or in some cases all three mechanisms are observed simultaneously

Coalescence of Inner Water Droplets in Double Emulsions Due to Surfactant Transport through Oil

Double emulsions of the water-in-oil-in-water type are promising encapsulation and delivery systems containing at least one hydrophilic and one lipophilic surfactant. Currently, there are still very few implementations on the market, as these systems are subject to extreme stability problems. This study focuses on stability problems induced by the transport of hydrophilic surfactant molecules through the lipophilic phase to the encapsulated inner water droplets. In particular, a model system was developed to quantify surfactant transport and resulting effects on the coalescence of encapsulated water droplets. Changes in stability of the inner water droplets are demonstrated for different surfactants and compared to the stability of the inner water-in-oil emulsions and corresponding double emulsions

Monitoring of Osmotic Swelling Induced Filling Degree Changes in WOW Double Emulsions Using Raman Technologies

Due to their nested structure, double emulsions have the potential to encapsulate value-adding substances until their application, making them of interest to various industries. However, the complex, nested structure negatively affects the stability of double emulsions. Still, there is a lack of suitable measurement technology to fundamentally understand the cause of the instability mechanisms taking place. This study presents a novel measurement method to continuously track filling degree changes due to water diffusion in a water-in-oil-in-water (W1/O/W2) double emulsion droplet. The measurement method is based on the Raman effect and provides both photometric and spectrometric data. No sample preparation is required, and the measurement does not affect the double emulsion droplet

Influence of Rapeseed Oil on Extruded Plant-Based Meat Analogues: Assessing Mechanical and Rheological Properties

Successfully replacing meat with plant-based options will require not only replicating the texture of muscular fibres, but also imitating the taste, aroma, and juiciness of meat as closely and realistically as possible. This study examines the impact of rapeseed oil on the textural properties of meat analogues. Pea protein and soy protein are chosen as model systems to assess the effect of rapeseed oil. Optical, mechanical, and rheological characterisation tests are conducted to investigate the oil droplet distribution, the gel strength, Young’s modulus, and the length of the LVE region. The hypothesis is that oil droplets will act as active fillers in the protein matrix, and thus, diminish the strength of the protein gel network. The results of this study show that rapeseed oil droplets act as inactive fillers, as they are not bound to both examined protein matrices. Soy protein extrudates display minimal changes, while pea protein extrudates are significantly affected by the addition of oil. For example, oil addition decreased the G′ in the LVE region of pea protein meat analogues by 50%, while soy protein samples showed no significant changes. Despite the similar interfacial activities of the investigated proteins, the decreased encapsulation efficiency of pea protein was confirmed by the higher amount of extracted oil from the respective extrudates

The Effect of Gelatin Source on the Synthesis of Gelatin-Methacryloyl and the Production of Hydrogel Microparticles

Gelatin methacryloyl (GelMA) is widely used for the formulation of hydrogels in diverse biotechnological applications. After the derivatization of raw gelatin, the degree of functionalization (DoF) is an attribute of particular interest as the functional residues are necessary for crosslinking. Despite progress in the optimization of the process found in the literature, a comparison of the effect of raw gelatin on the functionalization is challenging as various approaches are employed. In this work, the modification of gelatin was performed at room temperature (RT), and eight different gelatin products were employed. The DoF proved to be affected by the bloom strength and by the species of gelatin at an equal reactant ratio. Furthermore, batch-to-batch variability of the same gelatin source had an effect on the produced GelMA. Moreover, the elasticity of GelMA hydrogels depended on the DoF of the protein as well as on bloom strength and source of the raw material. Additionally, GelMA solutions were used for the microfluidic production of droplets and subsequent crosslinking to hydrogel. This process was developed as a single pipeline at RT using protein concentrations up to 20% (w/v). Droplet size was controlled by the ratio of the continuous to dispersed phase. The swelling behavior of hydrogel particles depended on the GelMA concentration