Thermoresponsive oil-continuous gels based on double-interpenetrating colloidal-particle networks.

Gels composed of multicomponent building blocks offer promising opportunities for the development of novel soft materials with unique and useful structures. While interpenetrating polymer networks have been extensively studied and applied in the creation of these gels, equivalent strategies utilizing colloidal particles have received limited scientific and technological attention. This study presents a novel class of thermo-responsive apolar double gels from interpenetrating networks of attractive colloidal silica and lipid particles. These double gels are easily assembled and suitable for the fabrication of 3D-printed edible soft constructs. Emphasis is focused on the rheological properties and structure emerging on the dilute regime (ϕ ≲ 0.1). Rheological investigations demonstrate that double gels exhibit greater stiffness and resilience to yielding compared to their single lipid gel counterparts. The scaling behavior of the oscillatory linear shear moduli and the critical strain for yielding with volume fraction remain comparable between single and double gels. Creep yielding in double gels exhibits two exponential decay regimes, suggesting the presence of thicker gel strands undergoing flow. Visualization and quantification of the quiescent microstructure confirms the existence of such denser aggregates devoid of larger clusters due to steric hindrance of interpenetrating networks in double gels. This is in stark contrast to lipid single gels where aggregates grow unrestrictedly into larger clusters. Our study constitutes the first demonstration on the assembly of apolar double gel networks as a promising avenue for the design of novel soft materials and foods with tailored structure and mechanics.

Is there a difference between surfactant-stabilised and Pickering emulsions?

What measurable physical properties allow one to distinguish surfactant-stabilised from Pickering emulsions? Whereas surfactants influence oil/water interfaces by lowering the oil/water interfacial tension, particles are assumed to have little effect on the interfacial tension. Here we perform interfacial tension (IFT) measurements on three different systems: (1) soybean oil and water with ethyl cellulose nanoparticles (ECNPs), (2) silicone oil and water with the globular protein bovine serum albumin (BSA), and (3) sodium dodecyl sulfate (SDS) solutions and air. The first two systems contain particles, while the third system contains surfactant molecules. We observe a significant decrease in interfacial tension with increasing particle/molecule concentration in all three systems. We analyse the surface tension data using the Gibbs adsorption isotherm and the Langmuir equation of state for the surface, resulting in surprisingly high adsorption densities for the particle-based systems. These seem to behave very much like the surfactant system: the decrease in tension is due to the presence of many particles at the interface, each with an adsorption energy of a few kBT. Dynamic interfacial tension measurements show that the systems are in equilibrium, and that the characteristic time scale for adsorption is much longer for particle-based systems than for surfactants, in line with their size difference. In addition, the particle-based emulsion is shown to be less stable against coalescence than the surfactant-stabilised emulsion. This leaves us with the conclusion that we are not able to make a clear distinction between the surfactant-stabilised and Pickering emulsions.

Edible mechanical metamaterials with designed fracture for mouthfeel control.

Metamaterials can display unusual and superior properties that come from their carefully designed structure rather than their composition. Metamaterials have permeated large swatches of science, including electromagnetics and mechanics. Although metamaterials hold the promise for realizing technological advances, their potential to enhance interactions between humans and materials has largely remained unexplored. Here, we devise a class edible mechanical metamaterials with tailored fracture properties to control mouthfeel sensory experience. Using chocolate as a model material, we first demonstrate how to create and control the fracture anisotropy, and the number of cracks, and demonstrate that these properties are captured in mouthfeel experience. We further use topology optimization to rationally design edible metamaterials with maximally anisotropic fracture strength. Our work opens avenues for the use of metamaterials to control fracture and to enhance human-matter interactions.

Water reorientation dynamics in colloidal water-oil emulsions.

We study the molecular-scale properties of colloidal water-oil emulsions consisting of 120-290 nm oil droplets embedded in water. This type of emulsion can be prepared with low concentrations of surfactants and is usually kinetically stable. Even though colloidal water-oil emulsions are used ubiquitously, their molecular properties are still poorly understood. Here we study the orientational dynamics of water molecules in these emulsions using polarization resolved pump-probe infrared spectroscopy, for varying surfactant concentrations, droplet sizes, and temperatures. We find that the majority of the water molecules reorients with the same time constant as in bulk water, while a small fraction of the water molecules reorients on a much longer time scale. These slowly reorienting water molecules are interacting with the surface of the oil droplets. The fraction of slowly orienting water molecules is proportional to the oil volume fraction, and shows a negligible dependence on the average droplet size. This finding indicates that the total surface area of the oil droplets is quite independent of the average droplet size, which indicates that the larger oil droplets are quite corrugated, showing large protrusions into the water phase.

Stringiness of hyaluronic acid emulsions.

OBJECTIVE: Cosmetic emulsions containing hyaluronic acid are ubiquitous in the cosmetic industry. However, the addition of (different molecular weight) hyaluronic acid can affect the filament stretching properties of concentrated emulsions. This property is often related to the "stringiness" of an emulsion, which can affect the consumer's choice for a product. It is thus very important to investigate and predict the effect of hyaluronic acid on the filament stretching properties of cosmetic emulsions. METHODS: Model emulsions and emulsions with low and high molecular weights are prepared and their filament stretching properties are studied by the use of an extensional rheometer. Two different stretching speeds are employed during the stretching of the emulsions, a low speed at 10 µm/s and a high speed at 10 mm/s. The shear rheology of the samples is measured by rotational rheology. RESULTS: We find that filament formation only occurs at high stretching speeds when the emulsion contains high molecular weight hyaluronic acid. The formation of this filament, which happens at intermediate states of the break-up, coincides with an exponential decay in the break-up dynamics. The beginning and end of the break-up of high molecular weight hyaluronic acid emulsions show a power law behaviour, where the exponent depends on the initial stretching rate. At a lower stretching speed, no filament is observed for both high molecular weight and low molecular weight hyaluronic acid emulsions and the model emulsion. The emulsions show a power law behaviour over the whole break-up range, where the exponent also depends on the stretching rate. No significant difference is observed between the shear flow properties of the emulsions containing different molecular weights hyaluronic acid. CONCLUSION: In this work, we underline the importance of the molecular weight of hyaluronic acid on the elongational properties of concentrated emulsions. The filament formation properties, for example the stringiness, of an emulsion is a key determinant of a product liking and repeat purchase. Here, we find that high molecular weight hyaluronic acid and a high stretching speed are the control parameters affecting the filament formation of an emulsion.

OBJECTIF: Les émulsions contenant de l'acide hyaluronique sont omniprésentes dans l'industrie cosmétique. En particulier, l'ajout d'acide hyaluronique (de poids moléculaires différents) peut affecter les propriétés extensionnelles d'un filament d'émulsion concentrée. Cette propriété importante est souvent assimilée à la perception organo-sensorielle "filante/cohésive" d'une émulsion et peut influer sur le choix final du consommateur pour un produit. Il est donc important d'étudier, mais aussi de pouvoir prédire, l'effet de l'acide hyaluronique sur les propriétés d'étirement de filaments d'émulsions cosmétiques. MÉTHODES: Nous avons préparé des émulsions modèles à faible et grands poids moléculaires et étudié leurs propriétés extensionnelles à l'aide d'un rhéomètre extensionnel. Deux vitesses d'étirement différentes sont utilisées, une vitesse faible à 10 µm/s et une vitesse élevée à 10 mm/s. La rhéologie de cisaillement des échantillons est mesurée par rhéologie rotationnelle. RÉSULTATS: Nous constatons que la formation de filaments ne se produit que pour des vitesses d'étirement élevées et lorsque l'émulsion contient de l'acide hyaluronique à grands poids moléculaire. La formation de ce filament, qui se produit à des temps intermédiaires de la rupture, coïncide avec une décroissance exponentielle de la dynamique de rupture. Le début et la fin de la rupture des émulsions d'acide hyaluronique de grands poids moléculaire montrent un comportement en loi de puissance, où l'exposant dépend de la vitesse d'étirement initiale. À une vitesse d'étirement inférieure, aucun filament n'est observé, à la fois pour les émulsions d'acide hyaluronique à grands et faibles poids moléculaires, mais aussi pour l'émulsion modèle ne contenant pas d'acide hyaluronique. Les émulsions présentent un comportement en loi de puissance sur tout le régime de rupture, où l'exposant dépend également de la vitesse d'étirement. Aucune différence significative n'est observée quant aux propriétés d'écoulement de cisaillement des émulsions contenant différents poids moléculaires d'acide hyaluronique. CONCLUSION: Dans cette étude, nous soulignons l'importance du poids moléculaire de l'acide hyaluronique sur les propriétés extensionnelles d'émulsions concentrées. Les propriétés de formation de filaments, ou la perception filante/cohésive d'une émulsion, sont un facteur clé dans l'appréciation d'un produit afin d'assurer un achat répété. Nous démontrons que la présence d'acide hyaluronique à grands poids moléculaires ainsi qu'une vitesse d'étirement élevée, sont les paramètres de contrôle affectant la formation de filaments dans une émulsion.

Emulsion Destabilization by Squeeze Flow.

There is a large debate on the destabilization mechanism of emulsions. We present a simple technique using mechanical compression to destabilize oil-in-water emulsions. Upon compression of the emulsion, the continuous aqueous phase is squeezed out, while the dispersed oil phase progressively deforms from circular to honeycomb-like shapes. The films that separate the oil droplets are observed to thin and break at a critical oil/water ratio, leading to coalescence events. Electrostatic interactions and local droplet rearrangements do not determine film rupture. Instead, the destabilization occurs like an avalanche propagating through the system, starting at areas where the film thickness is smallest.

Seeded-Growth of Silica Rods from Silica-Coated Particles.

Seeded growth of silica rods from colloidal particles has emerged as a facile method to develop novel complex particle structures with hybrid compositions and asymmetrical shapes. However, this seeded-growth technique has been so far limited to colloidal particles of only a few materials. Here, we first develop a general synthesis for the seeded-growth of silica rods from silica particles. We then demonstrate the growth of silica rods from silica-coated particles with three different cores which highlight the generality of this synthesis: fluorescently labeled organo-silica (fluorescein), metallic (Ag), and organic (PS latex). We also demonstrate the assembly of these particles into supraparticles. This general synthesis method can be extended to the growth of silica rods from any colloidal particle which can be coated with silica.

Inelastic behaviour of cellulose microfibril networks.

Cellulose microfibrils (CMF) are a unique class of shape anisotropic bio-nanomaterials, already finding many applications in diverse fields owing to their advantageous material properties and abundant availability. The rich non-linear mechanical behaviour of CMF networks has been under-studied due to the complex nature of this system, being influenced by many factors such as strong inter-fibril interactions, a heterogeneous microstructure, and process conditions. In this work, we systematically explore the non-linear rheological behaviour of these networks using a CMF model system with controlled process conditions and fibril interactions. The microfibrils were dispersed in dimethyl sulfoxide to minimise the attractive van der Waals interactions and thereby also the network heterogeneity. We show that the networks exhibit a transition with increasing shear stress from a predominantly elastic to a plastic deformation where they undergo softening. We find that the network stiffness and plasticity are dependent on the loading rate. Finally, we observed that the networks regain their original viscoelastic moduli on cessation of shear. These findings form a basis towards understanding and ultimately modelling the mechanics of CMF networks, which is a prerequisite for the rational design of novel bio-based materials.

Yielding and flow of cellulose microfibril dispersions in the presence of a charged polymer.

The shear flow of microfibrillated cellulose dispersions is still not wholly understood as a consequence of their multi-length-scale heterogeneity. We added carboxymethyl cellulose, a charged polymer, that makes cellulose microfibril dispersions more homogeneous at the submicron and macro scales. We then compared the yielding and flow behavior of these dispersions to that of typical thixotropic yield-stress fluids. Despite the apparent homogeneity of the dispersions, their flow velocity profiles in cone-plate geometry, as measured by rheo-MRI velocimetry, differ strongly from those observed for typical thixotropic model systems: the viscosity across the gap is not uniform, despite a flat stress field across the gap. We describe these velocity profiles with a nonlocal model, and attribute the non-locality to persistent micron-scale structural heterogeneity.

Structure and dynamics of water molecules confined in triglyceride oils.

Though it is commonly known that a small amount of water can be present in triglyceride oil, a molecular picture of how water molecules organize in the oil phase is lacking. We investigate the hydrogen-bond configuration and dynamics of water in triacetin, tributyrin and trioctanoin using linear infrared and time-resolved two-dimensional infrared (2DIR) spectroscopy of the water hydroxyl stretch vibration. We identify water molecules with a single strong hydrogen bond to the triglyceride, water molecules with two weaker hydrogen bonds to the triglycerides, and water clusters. These species do not interconvert on the 20 ps timescale of the experiment, as evidenced by the absence of cross-peaks in the 2DIR spectrum. The vibrational response of water molecules with a single strong hydrogen bond to the triglyceride depends strongly on the excitation frequency, revealing the presence of different subspecies of singly-bound water molecules that correspond to different hydrogen-bond locations. In contrast, the water molecules with two weaker hydrogen bonds to the triglyceride correspond to a single, specific hydrogen-bond configuration; these molecules likely bridge the carbonyl groups of adjacent triglyceride molecules, which can have considerable influence on liquid triglyceride properties.

Nanoscale Heterogeneity of the Molecular Structure of Individual hIAPP Amyloid Fibrils Revealed with Tip-Enhanced Raman Spectroscopy.

Type 2 diabetes mellitus is characterized by the pathological deposition of fibrillized protein, known as amyloids. It is thought that oligomers and/or amyloid fibrils formed from human islet amyloid polypeptide (hIAPP or amylin) cause cell death by membrane damage. The molecular structure of hIAPP amyloid fibrils is dominated by ß-sheet structure, as probed with conventional infrared and Raman vibrational spectroscopy. However, with these techniques it is not possible to distinguish between the core and the surface structure of the fibrils. Since the fibril surface crucially affects amyloid toxicity, it is essential to know its structure. Here the surface molecular structure and amino acid residue composition of hIAPP fibrils are specifically probed with nanoscale resolution using tip-enhanced Raman spectroscopy (TERS). The fibril surface mainly contains unordered or α-helical structures, in contrast to the ß-sheet-rich core. This experimentally validates recent models of hIAPP amyloids based on NMR measurements. Spatial mapping of the surface structure reveals a highly heterogeneous surface structure. Finally, TERS can probe fibrils formed on a lipid interface, which is more representative of amyloids in vivo.

Microstructure and rheology of microfibril-polymer networks.

By using an adsorbing polymer in combination with mechanical de-agglomeration, the microstructure and rheological properties of networks of microfibrils could be controlled. By the addition of sodium carboxymethyl cellulose during de-agglomeration of networks of bacterial cellulose, the microstructure could be changed from an inhomogeneous network with bundles of microfibrils and voids to a more homogeneous spread and alignment of the particles. As a result the macroscopic rheological properties were altered. Although still elastic and gel-like in nature, the elasticity and viscous behavior of the network as a function of microfibril concentration is altered. The microstructure is thus changed by changing the surface properties of the building blocks leading to a direct influence on the materials macroscopic behavior.

Phase transitions in cellulose microfibril dispersions by high-energy mechanical deagglomeration.

It is shown that dispersions of cellulose microfibrils display gel-sol and direct gel-colloidal liquid crystalline structure transitions. This is achieved by applying high-energy mechanical deagglomeration to bacterial cellulose (BC) networks in the presence of sodium carboxymethyl cellulose (CMC). At high CMC content adsorption of the polymer leads to a significant increase in the ζ potential. The resulting apparent phase diagram shows transitions from aggregates to single microfibril dispersions with increasing the CMC/BC weight ratio at low microfibril concentrations. At higher concentrations, liquid crystalline ordering was observed and the microstructure becomes more homogeneous with increasing the CMC content. The observed liquid crystalline ordering was found to be reminiscent of nematic gels. Applying deagglomeration in the presence of CMC, thus, transitions the system from aggregates and gels to dispersions of single microfibrils and nematic gel-type structures.

The effect of submicron fat droplets in a drink on satiety, food intake, and cholecystokinin in healthy volunteers.

PURPOSE: Small fat droplets infused into the gut reduce food intake and hunger more than bigger ones, at levels as low as 6 g, and these effects are hypothesized to occur via satiety hormones such as cholecystokinin. It is, however, unknown whether the effect of droplet size would persist after oral consumption. It is also unknown whether an even smaller droplet size can affect hunger and food intake and at what minimum amount of fat. Therefore, the aim of the study was to test the effect of very fine fat droplets on satiety and food intake in two different quantities. METHODS: In a balanced-order 4-way crossover design, 24 volunteers consumed a fat-free meal replacement drink with either 5 or 9 g oil (rapeseed) and either 3 or 0.1 µm droplet size. Appetite scores and plasma cholecystokinin levels (in n = 12 subset) were measured for 180 min, when food intake was assessed during an ad libitum meal. Data were analyzed by ANCOVA, followed by Dunnett's test and paired t test. The behavior of the emulsions was also characterized in a simulated gastrointestinal model. RESULTS: Despite faster in vitro lipolysis of the smallest droplets, neither droplet size nor fat amount affected satiety or food intake. From t = 45-150 min, cholecystokinin response was 50% higher (P < 0.05) after the 0.1 versus 3 µm, but only with 9 g fat. CONCLUSION: When this particular fat at these amounts is delivered in a meal replacement drink, droplet size does not influence appetite or food intake. This effect is independent of the amount of fat or plasma cholecystokinin changes.

Ferrous Pyrophosphate and Mixed Divalent Pyrophosphates as Delivery Systems for Essential Minerals.

Poorly water-soluble iron-containing compounds are promising iron fortificants. However, ensuring high bioaccessibility and low reactivity of iron is challenging. We present the potential application of ferrous pyrophosphate (Fe(II)PP) and Fe(II)-containing M2(1-x)Fe2x P2O7 salts (0 < x < 1, M = Ca, Zn, or Mn) for delivery of iron and a second essential mineral (M). After preparation by a facile and environment-friendly coprecipitation method, the salts were investigated for their composition, pH-dependent dissolution, iron-mediated discoloration of a black tea solution, and oxidation of vitamin C. Our results suggest that these salts are possible dual-fortificants with tunable composition that compared to Fe(II)PP (i) show lower (<0.5 mM) and enhanced (to 5 mM) iron dissolution in moderate and gastric pH, respectively, (ii) exhibit less discoloration and dissolved iron in tea when x = 0.470 for M = Ca or Zn and x = 0.086 for M = Mn, and (iii) do not increase the oxidation extent of vitamin C over 48 h when x = 0.06, 0.086, or 0.053 for M = Ca, Zn, or Mn, respectively.

Transparency-changing elastomers by controlling of the refractive index of liquid inclusions.

Complex materials that change their optical properties in response to changes in environmental conditions can find applications in displays, smart windows, and optical sensors. Here a class of biphasic composites with stimuli-adaptive optical transmittance is introduced. The biphasic composites comprise aqueous droplets (a mixture of water, glycerol, and surfactant) embedded in an elastomeric matrix. The biphasic composites are tuned to be optically transparent through a careful match of the refractive indices between the aqueous droplets and the elastomeric matrix. We demonstrate that stimuli (e.g., salinity and temperature change) can trigger variations in the optical transmittance of the biphasic composite. The introduction of such transparency-changing soft matter with liquid inclusions offers a novel approach to designing advanced optical devices, optical sensors, and metamaterials.

Pickering stabilization mechanism revealed through direct imaging of particles with tuneable contact angle in a phase-separated binary solvent.

Pickering emulsions have attracted increasing attention from multiple fields, including food, cosmetics, healthcare, pharmaceutical, and agriculture. Their stability relies on the presence of colloidal particles instead of surfactant at the droplet interface, providing steric stabilization. Here, we demonstrate the microscopic attachment and detachment of particles with tunable contact angle at the interface underlying the Pickering emulsion stability. We vary the interfacial tension continuously by varying the temperature offset of a phase-separated binary liquid from its critical point, and employ confocal microscopy to directly observe the particles at the interface to determine their coverage and contact angle as a function of the varying interfacial tension. When the interfacial tension decreases upon approaching the binary liquid's critical point, the contact angle and detachment energy (ΔE) drop, and the particles move out of the interface. Microscopic imaging suggests necking and capillary interactions lead to clustering of the particles, before they eventually desorb from the interface. Macroscopic measurements show that concomitantly, coalescence takes place, and the emulsion loses its stability. These results reveal the interplay of interfacial energies, contact angle and surface coverage that underlies the Pickering emulsion stability, opening up ways to manipulate and design the stability through the microscopic behavior of the adsorbed particles.

Novel low-molecular-weight-gelator-based microcapsules with controllable morphology and temperature responsiveness.

A new type of microcapsules with controllable morphology is presented. They are based on a low-molecular-weight gelator and can be switched from temperature-stable to temperature-responsive by simply modifying the preparation method.

Stability and viscoelasticity of magneto-Pickering foams.

We have developed a new class of bistable Pickering foams, which can remain intact for weeks at room temperature but can be destroyed rapidly and on-demand with the use of a magnetic field. Such responsive foam systems can find application in various industrial and environmental processes that require controlled defoaming. These foams are stabilized by particles of hypromellose phthalate (HP-55) and contain oleic acid-coated carbonyl iron particles embedded in the HP-55 matrix. The complex behavior of these foams arises from several factors: a robust anisotropic particle matrix, the capacity to retain a high amount of water, as well as an age-dependent response to an external field. We report how the structure and viscoelastic properties of the foams change with time and affect their collapse characteristics. The evolution of foam properties is quantified by measuring the rate of liquid drainage from the foam as well as the rate of bubble growth in the foam with respect to time elapsed (in the absence of a magnetic field). We also evaluate the time necessary for foam collapse in magnetic fields as a function of magnetic particle content. A decreasing liquid volume fraction in the foam during aging leads to an increase in the elasticity and rigidity of the foam structure. These data allow us to identify a transition time separating two distinct stages of foam development in the absence of field. We propose different mechanisms which control foam collapse for each stage in a magnetic field. The stiffening of foam films between air bubbles with age plays a key role in distinguishing between the two destabilization regimes.

Dispersions of attractive semiflexible fiberlike colloidal particles from bacterial cellulose microfibrils.

We prepared dispersions from bacterial cellulose microfibrils (CMF) of a commercial Nata de Coco source. We used an ultra-high-energy mechanical deagglomeration process that is able to disperse the CMFs from the pellicle in which they are organized in an irregular network. Because of the strong attractions between the CMFs, the dispersion remained highly heterogeneous, consisting of fiber bundles, flocs, and voids spanning tens to hundreds of micrometers depending on concentration. The size of these flocs increased with CMF concentration, the size of the bundles stayed constant, and the size of the voids decreased. The observed percolation threshold in MFC dispersions is lower than the theoretical prediction, which is accounted for by the attractive interactions in the system. Because bacterial cellulose is chemically very pure, it can be used to study the interaction of attractive and highly shape-anisotropic, semiflexible fiberlike colloidal particles.