Elucidating the role of water in collagen self-assembly by isotopically modulating collagen hydration.

Water is known to play an important role in collagen self-assembly, but it is still largely unclear how water-collagen interactions influence the assembly process and determine the fibril network properties. Here, we use the H[Formula: see text]O/D[Formula: see text]O isotope effect on the hydrogen-bond strength in water to investigate the role of hydration in collagen self-assembly. We dissolve collagen in H[Formula: see text]O and D[Formula: see text]O and compare the growth kinetics and the structure of the collagen assemblies formed in these water isotopomers. Surprisingly, collagen assembly occurs ten times faster in D[Formula: see text]O than in H[Formula: see text]O, and collagen in D[Formula: see text]O self-assembles into much thinner fibrils, that form a more inhomogeneous and softer network, with a fourfold reduction in elastic modulus when compared to H[Formula: see text]O. Combining spectroscopic measurements with atomistic simulations, we show that collagen in D[Formula: see text]O is less hydrated than in H[Formula: see text]O. This partial dehydration lowers the enthalpic penalty for water removal and reorganization at the collagen-water interface, increasing the self-assembly rate and the number of nucleation centers, leading to thinner fibrils and a softer network. Coarse-grained simulations show that the acceleration in the initial nucleation rate can be reproduced by the enhancement of electrostatic interactions. These results show that water acts as a mediator between collagen monomers, by modulating their interactions so as to optimize the assembly process and, thus, the final network properties. We believe that isotopically modulating the hydration of proteins can be a valuable method to investigate the role of water in protein structural dynamics and protein self-assembly.

Capillary Forces Lead to Pendant Crystals at the Liquid-Air Interface of Evaporating Salt Solutions.

We investigated the nucleation and growth processes of individual NaCl crystals from an evaporating salt solution that is supersaturated. We find that crystals nucleate at the liquid/vapor interface, resulting in distinct "pendant" crystals, which reach millimeter dimensions. The substantial size of the crystals induces deformation of the interface. This process and the evaporation rate, in turn, determine the final crystal shape, which features a deep central cavity. Our findings reveal that a delicate balance exists between gravity, buoyancy, and the surface tension of the liquid/vapor interface that allows the crystal to remain pendant. When the contact angle of the crystal with the meniscus reaches 90°, the crystal disconnects from the interface and falls into the solution. We quantitatively predict the critical mass at which this occurs.

Worm blobs as entangled living polymers: from topological active matter to flexible soft robot collectives.

Recently, the study of long, slender living worms has gained attention due to their unique ability to form highly entangled physical structures, exhibiting emergent behaviors. These organisms can assemble into an active three-dimensional soft entity referred to as the "blob", which exhibits both solid-like and liquid-like properties. This blob can respond to external stimuli such as light, to move or change shape. In this perspective article, we acknowledge the extensive and rich history of polymer physics, while illustrating how these living worms provide a fascinating experimental platform for investigating the physics of active, polymer-like entities. The combination of activity, long aspect ratio, and entanglement in these worms gives rise to a diverse range of emergent behaviors. By understanding the intricate dynamics of the worm blob, we could potentially stimulate further research into the behavior of entangled active polymers, and guide the advancement of synthetic topological active matter and bioinspired tangling soft robot collectives.

Surface-Mediated Molecular Transport of a Lipophilic Fluorescent Probe in Polydisperse Oil-in-Water Emulsions.

Emulsions often act as carriers for water-insoluble solutes that are delivered to a specific target. The molecular transport of solutes in emulsions can be facilitated by surfactants and is often limited by diffusion through the continuous phase. We here investigate this transport on a molecular scale by using a lipophilic molecular rotor as a proxy for solutes. Using fluorescence lifetime microscopy we track the transport of these molecules from the continuous phase toward the dispersed phase in polydisperse oil-in-water emulsions. We show that this transport comprises two time scales, which vary significantly with droplet size and surfactant concentration, and, depending on the type of surfactant used, can be limited either by transport across the oil-water interface or by diffusion through the continuous phase. By studying the time-resolved fluorescence of the fluorophore, accompanied by molecular dynamics simulations, we demonstrate how the rate of transport observed on a macroscopic scale can be explained in terms of the local environment that the probe molecules are exposed to.

Infrared Diffusion-Ordered Spectroscopy Reveals Molecular Size and Structure.

Inspired by ideas from NMR, we have developed Infrared Diffusion-Ordered Spectroscopy (IR-DOSY), which simultaneously characterizes molecular structure and size. We rely on the fact that the diffusion coefficient of a molecule is determined by its size through the Stokes-Einstein relation, and achieve sensitivity to the diffusion coefficient by creating a concentration gradient and tracking its equilibration in an IR-frequency resolved manner. Analogous to NMR-DOSY, a two-dimensional IR-DOSY spectrum has IR frequency along one axis and diffusion coefficient (or equivalently, size) along the other, so the chemical structure and the size of a compound are characterized simultaneously. In an IR-DOSY spectrum of a mixture, molecules with different sizes are nicely separated into distinct sets of IR peaks. Extending this idea to higher dimensions, we also perform 3D-IR-DOSY, in which we combine the conformation sensitivity of femtosecond multi-dimensional IR spectroscopy with size sensitivity.

Understanding the Behaviour of Real Metaborates in Solution.

Alkali metal borohydrides are promising candidates for large-scale hydrogen storage. They react spontaneously with water, generating dihydrogen and metaborate salts. While sodium borohydride is the most studied, potassium has the best chance of commercial application. Here we examine the physical and chemical properties of such self-hydrolysis solutions. We do this by following the hydrogen evolution, the pH changes, and monitoring the reaction intermediates using NMR. Most studies on such systems are done using dilute solutions, but real-life applications require high concentrations. We show that increasing the borohydride concentration radically changes the system's microstructure and rheology. The changes are seen already at concentrations as low as 5 w/w%, and are critical above 10 w/w%. While dilute solutions are Newtonian, concentrated reaction solutions display non-Newtonian behaviour, that we attribute to the formation and (dis)entanglement of metaborate oligomers. The implications of these findings towards using borohydride salts for hydrogen storage are discussed.

Chromatographic separation of active polymer-like worm mixtures by contour length and activity.

The convective transport rate of polymers through confined geometries depends on their size, allowing for size-based separation of polymer mixtures (chromatography). Here, we investigate whether mixtures of active polymers can be separated in a similar manner based on their activity. We use thin, living Tubifex tubifex worms as a model system for active polymers and study the transport of these worms by an imposed flow through a channel filled with a hexagonal pillar array. The transport rate through the channel depends strongly on the degree of activity, an effect that we assign to the different distribution of conformations sampled by the worms depending on their activity. Our results demonstrate a unique way to sort mixtures of active polymers based on their activity and provide a versatile and convenient experimental system to investigate the hydrodynamics of active polymers.

Predicting thickness perception of liquid food products from their non-Newtonian rheology.

The "mouthfeel" of food products is a key factor in our perception of food quality and in our appreciation of food products. Extensive research has been performed on what determines mouthfeel, and how it can be linked to laboratory measurements and eventually predicted. This was mainly done on the basis of simple models that do not accurately take the rheology of the food products into account. Here, we show that the subjectively perceived "thickness" of liquid foods, or the force needed to make the sample flow or deform in the mouth, can be directly related to their non-Newtonian rheology. Measuring the shear-thinning rheology and modeling the squeeze flow between the tongue and the palate in the oral cavity allows to predict how a panel perceives soup "thickness". This is done for various liquid bouillons with viscosities ranging from that of water to low-viscous soups and for high-viscous xanthan gum solutions. Our findings show that our tongues, just like our eyes and ears, are logarithmic measuring instruments in agreement with the Weber-Fechner law that predicts a logarithmic relation between stimulus amplitude and perceived strength. Our results pave the way for more accurate prediction of mouthfeel characteristics of liquid food products.

Light-switchable deposits from evaporating drops containing motile microalgae.

Deposits from evaporating drops have been shown to take a variety of shapes, depending on the physicochemical properties of both solute and solvent. Classically, the evaporation of drops of colloidal suspensions leads to the so-called coffee ring effect, caused by radially outward flows. Here we investigate deposits from evaporating drops containing living motile microalgae (Chlamydomonas reinhardtii), which are capable of resisting these flows. We show that utilizing their light-sensitivity allows control of the final pattern: adjusting the wavelength and incident angle of the light source enables forcing the formation, completely suppressing and even directing the spatial structure of algal coffee rings.

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.

The Dynamic Surface Tension of Water.

The surface tension of water is an important parameter for many biological or industrial processes, and roughly a factor of 3 higher than that of nonpolar liquids such as oils, which is usually attributed to hydrogen bonding and dipolar interactions. Here we show by studying the formation of water drops that the surface tension of a freshly created water surface is even higher (∼90 mN m-1) than under equilibrium conditions (∼72 mN m-1) with a relaxation process occurring on a long time scale (∼1 ms). Dynamic adsorption effects of protons or hydroxides may be at the origin of this dynamic surface tension. However, changing the pH does not significantly change the dynamic surface tension. It also seems unlikely that hydrogen bonding or dipole orientation effects play any role at the relatively long time scale probed in the experiments.