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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.
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Tensión Superficial , Agua , Proteína de Suero de Leche , Adsorción , Proteína de Suero de Leche/química , Agua/química , Aire , Alcanos/química , Aceites/química , Tamaño de la Partícula , Propiedades de Superficie , Técnicas Analíticas Microfluídicas/instrumentaciónRESUMEN
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.
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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.
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Emulsiones , Oxidación-Reducción , Tamaño de la Partícula , Proteína de Suero de Leche , Proteína de Suero de Leche/química , Emulsiones/química , Compuestos de Boro/química , Cinética , Peróxidos/química , Lípidos/químicaRESUMEN
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.
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Emulsiones , Polisacáridos , Reología , Proteína de Suero de Leche , Concentración de Iones de Hidrógeno , Emulsiones/química , Proteína de Suero de Leche/química , Polisacáridos/química , Emulsionantes/química , Prunus persica/química , Tamaño de la Partícula , Gomas de Plantas/químicaRESUMEN
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.
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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.
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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, â¼ 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.
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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 â¼100 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 â¼103 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.
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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.
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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.
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Plásticos Biodegradables , Nanopartículas , Quitina , Polímeros , Embalaje de AlimentosRESUMEN
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.
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Antioxidantes , Ácidos Grasos Insaturados , Antioxidantes/análisis , Antioxidantes/química , Emulsiones/química , Oxidación-Reducción , Estrés Oxidativo , Agua/química , Polifenoles/análisis , Polifenoles/químicaRESUMEN
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.
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Emulsionantes , Microfluídica , Emulsiones , Proteína de Suero de Leche , Tensión SuperficialRESUMEN
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.
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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.
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Aldehídos , Alimentos , Emulsiones , TriglicéridosRESUMEN
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.
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Microfluídica , Tensoactivos , Emulsiones , Dodecil Sulfato de Sodio , Tensión SuperficialRESUMEN
Lipid oxidation is a longstanding topic within the field of food technology, and is strongly related to loss of product quality and consumer acceptance. Both for bulk oils and emulsions, the chemical phenomena involved in lipid oxidation have been extensively researched, and various reaction pathways have been identified. They are different in bulk oil compared to oil-in-water (O/W) emulsions in which the oil-water interface plays a prominent role. Most probably because of the complexity of the reaction scheme in combination with mass transfer effects, there is no model that describes lipid oxidation in emulsions in a unified fashion, and that is the aim that we have set ourselves to achieve. We use lipid oxidation data previously obtained in O/W emulsions made with 5 different emulsifiers (2 surfactants, and 3 proteins), in well-mixed systems where the oxygen-to-oxidizable lipid ratio is strictly controlled. We use data pertaining to headspace oxygen concentration, and to primary and secondary lipid oxidation products to develop a model based on reaction kinetics, including not only the classical reaction scheme (starting from an unsaturated lipid, LH) but also radical initiation from hydroperoxides, which is thought to be an effect that is overlooked in the classical description of the initiation step. We were able to describe the course of the reactions in these emulsions using the same reaction rate constants for all emulsions, with the exception of the two related to radical-based initiation. In Tween 20- and Tween 80-stabilized emulsions, initiation stems most probably solely from decomposition of hydroperoxides; this implies that lipid oxidation in these emulsions is co-determined by the initial ("pre-existing") hydroperoxide concentration. In protein-stabilized emulsions, on the other hand, lipid radical initiation is probably linked to reactions involving proteins (co-oxidation reactions), whereas initiation through decomposition of hydroperoxides seems less important, if at all. From this, we can conclude that the difference between both types of emulsions with regard to lipid oxidation mechanisms is related to differences in radical initiation. The developed model can serve as a unified basis for understanding lipid oxidation in emulsions, through which additional effects beyond the bare reaction kinetics, such as mass transfer effects, can be identified and used to e.g., quantify antioxidant effects, which is part of follow-up research.
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Emulsionantes , Polisorbatos , Emulsionantes/química , Emulsiones/química , Aceites , Oxígeno , Polisorbatos/química , Agua/químicaRESUMEN
About 1/3rd of produced food goes to waste, and amongst others, advanced packaging concepts need to be developed to prevent this from happening. Here, we target the antioxidative functionality of food packaging to thus address food oxidation without the need for the addition of antioxidants to the food product, which is not desirable from a consumer point of view. Chitin nanocrystals (ChNC) have been shown to be promising bio-fillers for improving the mechanical strength of biodegradable plastics, but their potential as active components in plastic films is rather unexplored. In the current study, we investigate the antioxidant activity of chitin nanocrystals as such and as part of polylactic acid (PLA) films. This investigation was conducted using DPPH (1,1-diphenyl-2-picrylhydrazyl) radical scavenging activity. Chitin nanocrystals produced via acid hydrolysis showed five times higher activity compared to crude chitin powder. When using these crystals as part of a polylactic acid film (either inside or on top), in both scenarios, antioxidant activity was found, but the effect was considerably greater when the particles were at the surface of the film. This is an important proof of the principle that it is possible to create biodegradable plastics with additional functionality through the addition of ChNC.
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Bioplastics may solve environmental issues related to the current linear plastic economy, but they need improvement to be viable alternatives. To achieve this, we aimed to add chitin nanocrystals (ChNC) to polylactic acid (PLA), which is known to alter material properties while maintaining a fully bio-based character. However, ChNC are not particularly compatible with PLA, and surface modification with fatty acids was used to improve this. We used fatty acids that are different in carbon chain length (C4-C18) and degree of saturation (C18:2). We successfully used Steglich esterification and confirmed covalent attachment of fatty acids to the ChNC with FTIR and solid-state 13C NMR. The morphology of the ChNC remained intact after surface modification, as observed by TEM. ChNC modified with C4 and C8 showed higher degrees of substitution compared to fatty acids with a longer aliphatic tail, while particles modified with the longest fatty acid showed the highest hydrophobicity. The addition of ChNC to the PLA matrix resulted in brown color formation that was reduced when using modified particles, leading to higher transparency, most probably as a result of better dispersibility of modified ChNC, as observed by SEM. In general, addition of ChNC provided high UV-protection to the base polymer material, which is an additional feature that can be created through the addition of ChNC, which is not at the expense of the barrier properties, or the mechanical strength.
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Protein blends are used to stabilise many traditional and emerging emulsion products, resulting in complex, non-equilibrated interfacial structures. The interface composition just after emulsification is dependent on the competitive adsorption between proteins. Over time, non-adsorbed proteins are capable of displacing the initially adsorbed ones. Such rearrangements are important to consider, since the integrity of the interfacial film could be compromised after partial displacement, which may result in the physical destabilisation of emulsions. In the present review, we critically describe various experimental techniques to assess the interfacial composition, properties and mechanisms of protein displacement. The type of information that can be obtained from the different techniques is described, from which we comment on their suitability for displacement studies. Comparative studies between model interfaces and emulsions allow for evaluating the impact of minor components and the different fluid dynamics during interface formation. We extensively discuss available mechanistic physical models that describe interfacial properties and the dynamics of complex mixed systems, with a focus on protein in-plane and bulk-interface interactions. The potential of Brownian dynamic simulations to describe the parameters that govern interfacial displacement is also addressed. This review thus provides ample information for characterising the interfacial properties over time in protein blend-stabilised emulsions, based on both experimental and modelling approaches.
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Proteínas , Agua , Adsorción , Emulsiones/química , Proteínas/química , Reología , Agua/químicaRESUMEN
HYPOTHESIS: The interplay of interface evolution and surfactant adsorption determines the formation and stabilization of bubbles, and can be controlled by the liquid phase properties. EXPERIMENTS: We studied bubble formation in an Edge-based Droplet GEneration (EDGE) microfluidic device at relevant length and time scale, allowing investigation of sub-events in a single bubble formation cycle. We vary the properties of the continuous phase that contains whey proteins and study a range of trans-pore pressures (Pd∗). FINDINGS: The shallow pores highlight the crucial role of the Laplace pressure and dynamic adsorption of proteins to the meniscus. Bubble formation is divided into two regimes by the Laplace pressure of the bare meniscus inside the pore. At Pd∗<1400 mbar, pre-adsorption of proteins is required to lower the Laplace pressure; the bubble formation frequency f0 increases with increasing protein concentration and is hardly affected by velocity and viscosity. At Pd∗≥1400 mbar, bubble formation immediately occurs upon applying pressure, and f0 mainly decreases with increasing viscosity. In both regimes, the initial bubble size d0 mainly increases with the viscosity (~η1/3). Bubble coalescence is only observed at Pd∗≥1400 mbar and can be effectively suppressed by raising protein concentration and viscosity within certain boundaries, yet ultimately this is at the cost of higher polydispersity of the bubbles. Our insights into the formation dynamics of micrometer-sized bubbles at time scales down to tens of microseconds can be used for effective control of bubble formation and stabilization in practical applications.