Impact of Deformability and Rigidity of Starch Granules on Linear and Non-Linear Rheological Behavior of Waxy Rice Starch Gels and Applicability for Food End Uses.

The objective of this study was to investigate granule size and distribution and deformability of granules and their effect on the rheological properties of waxy starch gels. Native (granular) waxy rice gels (10%) were prepared, and their response in oscillatory shear was investigated in the linear and non-linear viscoelastic regime. The results show the gels were mainly composed of aggregated and deformed swollen granules. Significance of granule size and its distribution, deformability of granules, and the molecular characteristics of amylopectin (AP) on storage modulus of those gels was demonstrated. A low degree of deformability of granules, typical for small granules with a broad size distribution and small molecular size of AP with short external chains, resulted in rigid and brittle gels. Highly deformed granules and high AP leachates, however, yielded soft gels. It was found that the transition of elastic to plastic behavior in the non-linear regime (LAOS) was gradual when AP had long external chains, but an abrupt transition was observed with the gel with short exterior chains of AP. Differences in rheological properties of cohesive waxy starch gels appear to be mainly impacted by the varying degrees of granule deformability and rigidity, which is further attributed to a combination of factors, including granule size, particle size distribution, molecular size, the external chain length of amylopectin (AP), and lipid content. The significance of this study is that it will assist the food industry in selecting suitable waxy rice starches to gain desired textural properties of end products.

Soft gliadin nanoparticles at air/water interfaces: The transition from a particle-laden layer to a thick protein film.

HYPOTHESIS: Protein-based soft particles possess a unique interfacial deformation behavior, which is difficult to capture and characterize. This complicates the analysis of their interfacial properties. Here, we aim to establish how the particle deformation affects their interfacial structural and mechanical properties. EXPERIMENTS: Gliadin nanoparticles (GNPs) were selected as a model particle. We studied their adsorption behavior, the time-evolution of their morphology, and rheological behavior at the air/water interface by combining dilatational rheology and microstructure imaging. The rheology results were analyzed using Lissajous plots and quantified using the recently developed general stress decomposition (GSD) method. FINDING: Three distinct stages were revealed in the adsorption and rearrangement process. First, spherical GNPs (∼105 nm) adsorbed to the interface. Then, these gradually deformed along the interface direction to a flattened shape, and formed a firm viscoelastic 2D solid film. Finally, further stretching and merging of GNPs at the interface resulted in rearrangement of their internal structure to form a thick film with lower stiffness than the initial film. These results demonstrate that the structure of GNPs confined at the interface is controlled by their deformability, and the latter can be used to tune the properties of prolamin particle-based multiphase systems.

Oil-water interface and emulsion stabilising properties of rapeseed proteins napin and cruciferin studied by nonlinear surface rheology.

HYPOTHESIS: Two major protein families are present in rapeseed, namely cruciferins and napins. The structural differences between the two protein families indicate that they might behave differently when their mixture stabilises oil-water interfaces. Therefore, this work focuses on elucidating the role of both proteins in interface and emulsion stabilisation. EXPERIMENTS: Protein molecular properties were evaluated, using SEC, DSC, CD, and hydrophobicity analysis. The oil-water interface mechanical properties were studied using LAOS and LAOD. General stress decomposition (GSD) was used as a novel method to characterise the nonlinear response. Additionally, to evaluate the emulsifying properties of the rapeseed proteins, emulsions were prepared using pure napins or cruciferin and also their mixtures at 1:3, 1:1 and 3:1 (w:w) ratios. FINDINGS: Cruciferins formed stiff viscoelastic solid-like interfacial layers (Gs' = 0.046 mN/m; Ed' = 30.1 mN/m), while napin formed weaker and more stretchable layers at the oil-water interface (Gs' = 0.010 mN/m; Ed' = 26.4 mN/m). As a result, cruciferin-formed oil droplets with much higher stability against coalescence (coalescence index, CI up to 10%) than napin-stabilised ones (CI up to 146%) during two months of storage. Both proteins have a different role in emulsions produced with napin-cruciferin mixtures, where cruciferin provides high coalescence stability, while napin induces flocculation. Our work showed the role of each rapeseed protein in liquid-liquid multiphase systems.

Ion-Induced Reassembly between Protein Nanotubes and Nanospheres.

Proteins used as building blocks to template nanostructures with manifold morphologies have been widely reported. Understanding their self-assembly and reassembly mechanism is important for designing functional biomaterials. Herein, we show that enzyme-hydrolyzed α-lactalbumin (α-lac) can self-assemble into either nanotubes in the presence of Ca2+ ions or nanospheres in the absence of Ca2+ in solution. Remarkably, such assembled α-lac nanotubes can be elongated by adding preassembled α-lac nanospheres and Ca2+ solution, which suggests that the self-assembled α-lac nanospheres undergo disassembly and reassembly processes into existing nanotube nuclei. By performing atomic force microscopy (AFM), transmission electron microscopy (TEM), and confocal laser scanning microscopy (CLSM), it indicates that there is an equilibrium among nanotubes, nanospheres, hydrolyzed α-lac, and Ca2+ in solution. The structural transition between nanotubes and nanospheres is driven from a less stable structure into a more stable structure determined by the conditions. During the transition from nanospheres into nanotubes, the hydrolyzed α-lac in nanospheres transfers into helical ribbon form at both nanotube extremities. Then helical ribbons close into mature nanotubes, extending the length of the initial nuclei. Besides, by dilution or adding ethylene glycol bis(2-aminoethyl ether) tetraacetic acid (EGTA), the decreased Ca2+ concentration in solution drives the Ca2+ dissociating from nanotubes into solution, leading to the transitions from nanotubes into nanospheres. The reversible transformation between nanotubes and nanospheres is achieved by adjusting the pH value from 7.5 to 5.0 and back to 7.5. This is because the stability of nanotubes decreases from pH 7.5 to 5 but increases from 5 to 7.5. Significantly, this approach can be used for the fabrication of various responsive nanomaterials from the same starting material.

The dilatable membrane of oleosomes (lipid droplets) allows their in vitro resizing and triggered release of lipids.

It has been reported that lipid droplets (LDs), called oleosomes, have an inherent ability to inflate or shrink when absorbing or fueling lipids in the cells, showing that their phospholipid/protein membrane is dilatable. This property is not that common for membranes stabilizing oil droplets and when well understood, it could be exploited for the design of responsive and metastable droplets. To investigate the nature of the dilatable properties of the oleosomes, we extracted them from rapeseeds to obtain an oil-in-water emulsion. Initially, we added an excess of rapeseed oil in the dispersion and applied high-pressure homogenization, resulting in a stable oil-in-water emulsion, showing the ability of the molecules on the oleosome membrane to rearrange and reach a new equilibrium when more surface was available. To confirm the rearrangement of the phospholipids on the droplet surface, we used molecular dynamics simulations and showed that the fatty acids of the phospholipids are solubilized in the oil core and are homogeneously spread on the liquid-like membrane, avoiding clustering with neighbouring phospholipids. The weak lateral interactions on the oleosome membrane were also confirmed experimentally, using interfacial rheology. Finally, to investigate whether the weak lateral interactions on the oleosome membrane can be used to have a triggered change of conformation by an external force, we placed the oleosomes on a solid hydrophobic surface and found that they destabilise, allowing the oil to leak out, probably due to a reorganisation of the membrane phospholipids after their interaction with the hydrophobic surface. The weak lateral interactions on the LD membrane and their triggered destabilisation present a unique property that can be used for a targeted release in foods, pharmaceuticals and cosmetics.

The emulsifying ability of oleosomes and their interfacial molecules.

Oleosomes are natural oil droplets, present in all organisms and abundant in oilseeds. After their aqueous extraction from oilseeds, they can be directly utilized as oil droplets in food, cosmetics and all types of oil-in-water emulsion systems. However, to expand the potential uses of oleosomes as green ingredients and to valorize oilseeds as efficient as possible, we explored their emulsifying ability. Oleosomes were extracted from rapeseeds, and 10.0 wt% oil-in-water emulsions were created after homogenization with 0.5-6.0 wt% oleosomes, and the droplet size of the emulsions and their structure was measured by laser diffraction and confocal laser scanning microscopy (CLSM), respectively. The emulsion with an oleosome concentration lower than 1.0 wt% gave unstable emulsions with visible free oil. At oleosome concentrations at 1.5 wt% or higher, we obtained stable emulsions with droplet sizes between 2.0 and 12.0 µm. To investigate the role of the oleosome interfacial molecules in stabilizing emulsions we also studied their emulsifying and interfacial properties (using drop tensiometry) after isolating them from the oleosome structure. Both oleosomes and their isolated interfacial molecules exhibited a similar behavior on the oil-water interfaces, forming predominantly elastic interfacial films, and also showed a similar emulsifying ability. Our results show that oleosomes are not stabilizing the oil-in-water emulsions as intact particles, but they provide their interfacial molecules, which are enough to stabilize an oil-water surface up to about 2 times bigger than the initial oleosome surface. The understanding of the behavior of oleosomes as emulsifiers, opens many possibilities to use oleosomes as alternative to synthetic emulsifiers in food and pharma applications.

Molecular structure and linear-non linear rheology relation of rice starch during milky, dough, and mature stages.

Immature rice has potential to be used as healthy food. The relation between molecular structure and rheological properties was investigated. The lamellar repeating distance (8.42-8.63 nm) and crystalline thickness (4.60-4.72 nm) were not different among stages indicating a complete lamellar structure even at early stage. The relative crystallinity was higher in dough (39.62 %) than milky (36.69 %) and mature starch (35.22 %) caused by molecular structure, amylose, and amylose-lipid complex. The short amylopectin branched chains (A and B1) in dough starch were easily entangled resulted in higher Payne effect and elastic dominant. Dough starch paste exhibited higher G'Max (738 Pa) than milky (685 Pa) and mature (645 Pa) starch. In a non-linear viscoelastic regime, small strain hardening was found in milky and dough starch. Mature starch showed the highest plasticity and shear thinning at high-shear strains as the long-branched chains (B3) microstructure was disrupted, disentangled, followed by chain orientation along shear.

Surface stress decomposition in large amplitude oscillatory interfacial dilatation of complex interfaces.

HYPOTHESIS: Multiphase materials are often subjected to large deformations during processing, but the rheological responses of complex interfaces (e.g. stabilized by proteins) in this nonlinear deformation regime are still poorly understood. We expect nonlinearities in the response to be introduce by changes of the interfacial network and surface density of the emulsifier. EXPERIMENTS: Large amplitude oscillatory dilatation (LAOD) experiments were performed on WPI-, pea albumin-, pea globulin- and rapeseed lecithin-stabilized interfaces and analyzed with a general stress decomposition (GSD). With GSD, the stress response was decomposed into the four stress terms (τ1-τ4). Here, τ1 and τ2 represent, the elastic and viscous contribution of the odd Fourier harmonics, and τ3 and τ4 represent the dissipative and recoverable contribution of the even harmonics. FINDINGS: Analysis of WPI-, pea albumin-, pea globulin- and rapeseed lecithin-stabilized interfaces revealed that higher odd harmonics (k≥3) describe in-plane network responses and that even harmonics describe surface density changes. Analysis of these complex interfaces showed that GSD is a valuable tool for (quantitative) description of interfacial responses in LAOD, providing new insights into the origin of asymmetric nonlinear stress responses.

Pasting and Rheological Properties of Starch Paste/Gels in a Sugar-Acid System.

This study was to investigate the impact of granule size, amylose content, and starch molecular characteristics on pasting and rheological properties of starch paste/gels in neutral (water) and sugar-acid systems. Normal rice starch (RS), waxy rice starch (WRS), normal tapioca starch (TS), and waxy tapioca starch (WTS) representing small-granule starches and intermediate-granule starches respectively, were used in the study. Impacts of granule size, AM content, and their synergistic effects resulted in different starch susceptibility to acid hydrolysis and interactions between starch and sucrose-water, yielding different paste viscosities in both systems. The high molecular weight (Mw¯) and linearity of amylopectin and amylose molecules increased the consistency of starch pastes. RS produced a stronger and more brittle gel than other starch gels in both neutral and sugar-acid systems. The results indicated the impact of the effect of granule size and amylose content on starch gel behaviors. Properties of waxy starch gels were mainly governed by amylopectin molecular characteristics, especially in the sugar-acid system. Adding sugar and acid had minor impacts on starch gel behaviors in the linear viscoelastic (LVE) region but were most evident in the nonlinear response regime of starch gels as shown in the Lissajous curves at large oscillatory strain.

Impact of Particle Sedimentation in Pendant Drop Tensiometry.

Understanding the interface-stabilizing properties of surface-active components is key in designing stable macroscopic multiphase systems, such as emulsions and foams. When poorly soluble materials are used as an interface stabilizer, the insoluble material may sediment and interfere with the analysis of interfacial properties in pendant (or hanging) drop tensiometry. Here, the impact of sedimentation of particles on the interfacial properties determined by pendant drop tensiometry was evaluated using a model system of whey protein isolate and (non surface-active) glass beads (2.2-34.7 µm). Although the glass beads did not adsorb to the air-water interface, a 1% (w/w) glass bead solution appeared to decrease the surface tension by nearly 12 mN/m after 3 h. A similar effect was shown for a mixture of whey proteins and glass beads: the addition of 1% (w/w) of glass beads led to an apparent surface tension decrease of 31 mN/m rather than the 20 mN/m observed for pure whey proteins. These effects are attributed to the sedimentation of particles near the apex of the droplet, leading to droplet shape changes, which are interpreted as a decrease in surface tension using tensiometer software. The droplet density at the apex increases due to sedimentation, and this density increase is not accounted for when fitting the droplet shape with the Young-Laplace equation. The result is the observed apparent decrease in surface tension. In contrast to the significant impact of sedimenting material on the surface tension measurements, the impact on the results of oscillatory deformations was limited. These findings show that the impact of sedimentation should be considered when studying the interface-stabilizing properties of materials with reduced solubility, such as certain plant protein extracts. The presence of such particles should be carefully considered when conducting pendant drop tensiometry.

Interfacial protein-protein displacement at fluid interfaces.

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.

Non-linear rheology reveals the importance of elasticity in meat and meat analogues.

The interest in plant-based meat analogues as an alternative to meat is currently growing. Rheological benchmarking is used to reveal how closely meat analogues resemble the original meat products. Texture maps and dissipation colour schemes were used to reveal similarities in and differences between rheological responses of meat and meat analogues (especially chicken analogues). Under heating, meat analogues differ in terms of their lower elasticity compared with heated meat. The changes caused by heating meat and meat analogues were different as well. Heating of meat resulted in a tougher and more elastic material, while heating has a minor effect on meat analogues. Future developments should therefore focus on routes to create more elasticity and possibly allow heating effects on texture to mimic meat characteristics even better.

Rheological behaviour of attractive emulsions differing in droplet-droplet interaction strength.

HYPOTHESIS: We hypothesise that interaction strength between oil droplets determine the rheological properties of oil-in-water (O/W) emulsions by simultaneous formation and break-up of bonds between droplets. Using small (SAOS) and large (LAOS) amplitude oscillatory shear measurements, we aim to distinguish different classes of emulsions based on the specific microstructural evolution of the emulsions. EXPERIMENTS: Concentrated O/W emulsions differing in droplet-droplet interaction strength were obtained. Different interaction strength was obtained using different types of interactions; (a) electrostatic attraction, (b) salt bridging, or (c) crosslinking. FINDINGS: In line with our hypothesis, different rheological events in emulsions depend on the droplet-droplet interaction strength. Strong interactions lead to monotonous yielding, and droplets undergo jamming or densification to provide strain hardening and gel-like behaviour. Emulsions with weak interactions exhibit two-step yielding (SAOS) and continuous yielding in LAOS; indicating a soft-glassy material. In emulsions above maximum packing, and with weak interactions the rheology is controlled by cluster/cage breaking, and transient formation of new clusters. For medium-strength interactions, two-step yielding was reduced, and apparent stain-hardening occurred. The probability of two distinct time scales of yielding is hindered by stronger interactions and jamming. Overall, in concentrated emulsions, yielding is determined by network rupture and reformation, cluster rearrangement and -breaking, which in turn is influenced by interaction type and strength. We present a more differentiated categorisation of emulsions based on interaction strength.

Air-water interfacial behaviour of whey protein and rapeseed oleosome mixtures.

HYPOTHESIS: Plant seeds store lipids in oleosomes, which are storage organelles with a triacylglycerol (TAG) core surrounded by a phospholipid monolayer and proteins. Due to their membrane components, oleosomes have an affinity for the air/oil-water interface. Therefore, it is expected that oleosomes can stabilise interfaces, and also compete with proteins for the air-water interface. EXPERIMENTS: We mixed rapeseed oleosomes with whey protein isolate (WPI), and evaluated their air-water interfacial properties by interfacial rheology and microstructure imaging. To understand the contribution of the oleosome components to the interfacial properties, oleosome membrane components (phospholipids and membrane proteins) or rapeseed lecithin (phospholipids) were also mixed with WPI. FINDINGS: Oleosomes were found to disrupt after adsorption, and formed TAG/phospholipid-rich regions with membrane fragments at the interface, forming a weak and mobile interfacial layer. Mixing oleosomes with WPI resulted in an interface with TAG/phospholipid-rich regions surrounded by whey protein clusters. Membrane components or lecithin mixed with proteins also resulted in an interface where WPI molecules aggregated into small WPI domains, surrounded by a continuous phase of membrane components or phospholipids. We also observed an increase in stiffness of the interfacial layer, due to the presence of oleosome membrane proteins at the interface.

Large amplitude oscillatory shear (LAOS) for nonlinear rheological behavior of heterogeneous emulsion gels made from natural supramolecular gelators.

The linear and nonlinear rheological behaviors of heterogeneous emulsions gels made from natural glycyrrhizic acid (GA) nanofibrils and sitosterol-oryzanol mixtures (sterols) were investigated using small amplitude oscillatory shear (SAOS) and large amplitude oscillatory shear (LAOS). The nonlinear rheological response was qualitatively analyzed using normalized Lissajous-Bowditch curves. The microstructure of the emulsion gels strongly depended on the concentration of sterols in the oil phase, and showed a percolated segregated network at 10-20 wt% sterols due to the partial coalescence of droplets, and a jamming transition without coalescence at higher sterols concentration of 30 wt%. The microstructure differences led to different linear and nonlinear viscoelastic behaviors of these emulsion gels. SAOS tests showed that the oil phase structuring by the sterols significantly enhance the viscoelasticity of GA nanofibril emulsion gels, and the percolating emulsion gels exhibited higher elasticity than the jammed emulsion gel, as evidenced by a lower damping factor and frequency power-law exponent. The data of crossover strain, phase angle, and the normalized Lissajous-Bowditch curves from LAOS tests further revealed that compared to the samples in a jammed state or without oil phase structuring, the emulsion gels with a percolating segregated network showed higher structural elasticity and thus were more resistant to large deformations, probably due to the slow relaxation of rigid, hydrodynamically interacting clusters of partially coalesced droplets. These findings could potentially aid in the design of novel emulsion gels, based on all-natural and sustainable building blocks, with specific textural and functional properties for foods, cosmetics, and pharmaceutical applications.

Adsorption of rapeseed proteins at oil/water interfaces. Janus-like napins dominate the interface.

Plants offer a vast variety of protein extracts, typically containing multiple species of proteins that can serve as building blocks of soft materials, like emulsions. However, the role of each protein species concerning the formation of emulsions and interfaces with diverse rheological properties is still unknown. Therefore, deciphering the role of the individual proteins in an extract is highly relevant, since it determines the optimal level of purification, and hence the sustainability aspects of the extract. Here, we will show that when oil/water emulsions were prepared with a rapeseed protein extract containing napins and cruciferins (in a mass ratio of 1:1), only napins adsorbed at the interface exhibiting a soft solid-like rheological behavior. The dominance of napins at the interface was ascribed to their small size (radius r = 1.7 nm) and its unique Janus-like structure, as 45% of the amino acids are hydrophobic and primarily located at one side of the protein. Cruciferins with a bigger size (r = 4.4 nm) and a more homogeneous distribution of the hydrophobic domains couldn't reach the interface, but they appear to just weakly interact with the adsorbed layer of napins.

Sequential adsorption and interfacial displacement in emulsions stabilized with plant-dairy protein blends.

HYPOTHESIS: Many traditional or emergent emulsion products contain mixtures of proteins, resulting in complex, non-equilibrated interfacial structures. It is expected that protein displacement at oil-water interfaces depends on the sequence in which proteins are introduced during emulsion preparation, and on its initial interfacial composition. EXPERIMENTS: We produced emulsions with whey, pea or a whey-pea protein blend and added extra protein post-emulsification. The surface load was measured indirectly via the continuous phase, or directly via the creamed phase. The interfacial composition was monitored over a three-day period using SDS-PAGE densitometry. We compared these findings with results obtained using an automated drop tensiometer with bulk-phase exchange to highlight the effect of sequential protein adsorption on interfacial tension and dilatational rheology. FINDINGS: Addition of a second protein increased the surface load; especially pea proteins adsorbed to pre-adsorbed whey proteins, leading to thick interfacial layers. The addition of whey proteins to a pea protein- or whey-pea protein blend-stabilized emulsion led to significant displacement of the pea proteins by ß-lactoglobulin. We determined that protein-protein interactions were the driving force for this displacement, rather than a decrease in interfacial tension. These outcomes could be instrumental in defining new strategies for plant-animal protein hybrid products.

Behavior of plant-dairy protein blends at air-water and oil-water interfaces.

Recent work suggests that using blends of dairy and plant proteins could be a promising way to mitigate sustainability and functionality concerns. Many proteins form viscoelastic layers at fluid interfaces and provide physical stabilization to emulsion droplets; yet, the interfacial behavior of animal-plant protein blends is greatly underexplored. In the present work, we considered pea protein isolate (PPI) as a model legume protein, which was blended with well-studied dairy proteins (whey protein isolate (WPI) or sodium caseinate (SC)). We performed dilatational rheology at the air-water and oil-water interface using an automated drop tensiometer to chart the behavior and structure of the interfacial films, and to highlight differences between films made with either blends, or their constituting components only. The rheological response of the blend-stabilized interfaces deviated from what could be expected from averaging those of the individual proteins and depended on the proteins used; e.g. at the air-water interface, the response of the caseinate-pea protein blend was similar to that of PPI only. At the oil-water interface, the PPI and WPI-PPI interfaces gave comparable responses upon deformation and formed less elastic layers compared to the WPI-stabilized interface. Blending SC with PPI gave stronger interfacial layers compared to SC alone, but the layers were less stiff compared to the layers formed with WPI, PPI and WPI-PPI. In general, higher elastic moduli and more rigid interfacial layers were formed at the air-water interface, compared to the oil-water interface, except for PPI.

Interfacial rheology and relaxation behavior of adsorption layers of the triterpenoid saponin Escin.

HYPOTHESIS: Escin, a monodesmosidic triterpenoid saponin, was shown previously to form viscoelastic interfaces with a very high dilatational and surface shear storage modulus. This is expected to be due to the arrangement of Escin into 2D disordered soft viscoelastic solid interfacial structures, which results in turn in a distribution of relaxation times. EXPERIMENTS: The responses to dilatational and surface shear deformations of Escin-stabilized air-water interfaces were studied, both in the linear viscoelastic (LVE) and non-linear (NLVE) regime. Step relaxation and amplitude sweeps were performed in dilatation experiments. For surface shear, amplitude sweeps and creep recovery experiments were performed. FINDINGS: Escin stabilized-interfaces displayed a highly non-linear behavior in dilatation as seen in the Lissajous plots. In large oscillatory shear the Lissajous curves had a rhomboidal shape, indicating intracycle yielding and recovery, typical of glassy systems. The relaxation of the interface showed stretched exponential behavior, with stretched exponents typical of disordered solids with dynamic heterogeneity. The use of surface rheological measurements beyond the commonly measured LVE regime clearly has provided new insights into the behavior of these interfaces and their microstructure. These results highlight the need to reconsider other complex interfaces as disordered solids and not as 2D homogenous viscoelastic fluids.

Relaxation Behavior and Nonlinear Surface Rheology of PEO-PPO-PEO Triblock Copolymers at the Air-Water Interface.

Surface dilatational viscoelasticity of adsorbed layers of pluronics triblock copolymers at the air-water interface was measured using the oscillating barrier technique. The effect of molecular architecture and concentration on surface viscoelasticity was explored for two different types of pluronics with different degrees of hydrophobicity, Pluronic F-108 (Mw ≈ 14 600 g/mol) and Pluronic P-123 (Mw ≈ 5800 g/mol), the former exhibiting a larger hydrophilic to hydrophobic block length ratio. Frequency sweeps in the linear regime suggested that interfacial films of F-108 have higher surface limiting elasticity and larger in-plane and out-of-plane relaxation times at the same bulk concentration (the former possibly related to in-plane microstructure rearrangements, the latter to surface/bulk diffusion). Increasing the bulk concentration of pluronics from 1 to 100 µM led to a decrease in both in- and out-of-plane relaxation times. Large amplitude oscillatory dilatation (LAOD) tests were performed to capture nonlinear behavior of these interfacial films by means of elastic and viscous Lissajous plots. Nonlinearities in elastic responses were quantified through calculation of the strain-stiffening indices in extension SE and compression SC. Both pluronics exhibited strain softening in extension. In compression, P-123 showed strain-hardening and F-108 displayed a relatively linear response. Apparent strain hardening in extension was observed for the P-123 adsorbed film, at high strain, at a bulk concentration of 100 µM. However, at these strains, the response was dominated by the viscous contribution and calculation of strain rate-thickening factors in extension and compression showed that the overall response was strain rate-thinning in extension and strain rate-thickening in compression.