Fate of Magnetic Nanoparticles during Stimulated Healing of Thermoplastic Elastomers.

We have investigated the heating mechanism in industrially relevant, multi-block copolymers filled with Fe nanoparticles and subjected to an oscillatory magnetic field that enables polymer healing in a contactless manner. While this procedure aims to extend the lifetime of a wide range of thermoplastic polymers, repeated or prolonged stimulus healing is likely to modify their structure, mechanics, and ability to heat, which must therefore be characterized in depth. In particular, our work sheds light on the physical origin of the secondary heating mechanism detected in soft systems subjected to magnetic hyperthermia and triggered by copolymer chain dissociation. In spite of earlier observations, the origin of this additional heating remained unclear. By using both static and dynamic X-ray scattering methods (small-angle X-ray scattering and X-ray photon correlation spectroscopy, respectively), we demonstrate that beyond magnetic hysteresis losses, the enormous drop of viscosity at the polymer melting temperature enables motion of nanoparticles that generates additional heat through friction. Additionally, we show that applying induction heating for a few minutes is found to magnetize the nanoparticles, which causes them to align in dipolar chains and leads to nonmonotonic translational dynamics. By extrapolating these observations to rotational dynamics and the corresponding amount of heat generated through friction, we not only clarify the origin of the secondary heating mechanism but also rationalize the presence of a possible temperature maximum observed during induction heating.

Enhanced microscopic dynamics in mucus gels under a mechanical load in the linear viscoelastic regime.

Mucus is a biological gel covering the surface of several tissues and ensuring key biological functions, including as a protective barrier against dehydration, pathogen penetration, or gastric acids. Mucus biological functioning requires a finely tuned balance between solid-like and fluid-like mechanical response, ensured by reversible bonds between mucins, the glycoproteins that form the gel. In living organisms, mucus is subject to various kinds of mechanical stresses, e.g., due to osmosis, bacterial penetration, coughing, and gastric peristalsis. However, our knowledge of the effects of stress on mucus is still rudimentary and mostly limited to macroscopic rheological measurements, with no insight into the relevant microscopic mechanisms. Here, we run mechanical tests simultaneously to measurements of the microscopic dynamics of pig gastric mucus. Strikingly, we find that a modest shear stress, within the macroscopic rheological linear regime, dramatically enhances mucus reorganization at the microscopic level, as signaled by a transient acceleration of the microscopic dynamics, by up to 2 orders of magnitude. We rationalize these findings by proposing a simple, yet general, model for the dynamics of physical gels under strain and validate its assumptions through numerical simulations of spring networks. These results shed light on the rearrangement dynamics of mucus at the microscopic scale, with potential implications in phenomena ranging from mucus clearance to bacterial and drug penetration.

Role of Normal Stress in the Creep Dynamics and Failure of a Biopolymer Gel.

We investigate the delayed rupture of biopolymer gels under a constant shear load by simultaneous dynamic light scattering and rheology measurements. We unveil the crucial role of normal stresses built up during gelation: All samples that eventually fracture self-weaken during the gelation process, as revealed by a partial relaxation of the normal stress concomitant to a burst of microscopic plastic rearrangements. Upon applying a shear stress, weakened gels exhibit in the creep regime distinctive signatures in their microscopic dynamics, which anticipate macroscopic fracture by up to thousands of seconds. The dynamics in fracturing gels are faster than those of nonfracturing gels and exhibit large spatiotemporal fluctuations. A spatially localized region with significant plasticity eventually nucleates, expands progressively, and finally invades the whole sample, triggering macroscopic failure.

High-frequency linear rheology of hydrogels probed by ultrasound-driven microbubble dynamics.

Ultrasound-driven microbubble dynamics are central to biomedical applications, from diagnostic imaging to drug delivery and therapy. In therapeutic applications, the bubbles are typically embedded in tissue, and their dynamics are strongly affected by the viscoelastic properties of the soft solid medium. While the behaviour of bubbles in Newtonian fluids is well characterised, a fundamental understanding of the effect on ultrasound-driven bubble dynamics of a soft viscoelastic medium is still being developed. We characterised the resonant behaviour in ultrasound of isolated microbubbles embedded in agarose gels, commonly used as tissue-mimicking phantoms. Gels with different viscoelastic properties were obtained by tuning agarose concentration, and were characterised by standard rheological tests. Isolated bubbles (100-200 µm) were excited by ultrasound (10-50 kHz) at small pressure amplitudes (<1 kPa), to ensure that the deformation of the material and the bubble dynamics remained in the linear regime. The radial dynamics of the bubbles were recorded by high-speed video microscopy. Resonance curves were measured experimentally and fitted to a model combining the Rayleigh-Plesset equation governing bubble dynamics, with the Kelvin-Voigt model for the viscoelastic medium. The resonance frequency of the bubbles was found to increase with increasing shear modulus of the medium, with implications for optimisation of imaging and therapeutic ultrasound protocols. In addition, the viscoelastic properties inferred from ultrasound-driven bubble dynamics differ significantly from those measured at low frequency with the rheometer. Hence, rheological characterisation of biomaterials for medical ultrasound applications requires particular attention to the strain rate applied.

Surface waves on a soft viscoelastic layer produced by an oscillating microbubble.

Ultrasound-driven bubbles can cause significant deformation of soft viscoelastic layers, for instance in surface cleaning and biomedical applications. The effect of the viscoelastic properties of a boundary on the bubble-boundary interaction has been explored only qualitatively, and remains poorly understood. We investigate the dynamic deformation of a viscoelastic layer induced by the volumetric oscillations of an ultrasound-driven microbubble. High-speed video microscopy is used to observe the deformation produced by a bubble oscillating at 17-20 kHz in contact with the surface of a hydrogel. The localised oscillating pressure applied by the bubble generates surface elastic (Rayleigh) waves on the gel, characterised by elliptical particle trajectories. The tilt angle of the elliptical trajectories varies with increasing distance from the bubble. Unexpectedly, the direction of rotation of the surface elements on the elliptical trajectories shifts from prograde to retrograde at a distance from the bubble that depends on the viscoelastic properties of the gel. To explain these behaviours, we develop a simple three-dimensional model for the deformation of a viscoelastic solid by a localised oscillating force. By using as input for the model the values of the shear modulus obtained from the propagation velocity of the Rayleigh waves, we find good qualitative agreement with the experimental observations.

Selective flow-induced vesicle rupture to sort by membrane mechanical properties.

Vesicle and cell rupture caused by large viscous stresses in ultrasonication is central to biomedical and bioprocessing applications. The flow-induced opening of lipid membranes can be exploited to deliver drugs into cells, or to recover products from cells, provided that it can be obtained in a controlled fashion. Here we demonstrate that differences in lipid membrane and vesicle properties can enable selective flow-induced vesicle break-up. We obtained vesicle populations with different membrane properties by using different lipids (SOPC, DOPC, or POPC) and lipid:cholesterol mixtures (SOPC:chol and DOPC:chol). We subjected vesicles to large deformations in the acoustic microstreaming flow generated by ultrasound-driven microbubbles. By simultaneously deforming vesicles with different properties in the same flow, we determined the conditions in which rupture is selective with respect to the membrane stretching elasticity. We also investigated the effect of vesicle radius and excess area on the threshold for rupture, and identified conditions for robust selectivity based solely on the mechanical properties of the membrane. Our work should enable new sorting mechanisms based on the difference in membrane composition and mechanical properties between different vesicles, capsules, or cells.

Using optical tweezers for the characterization of polyelectrolyte solutions with very low viscoelasticity.

Recently, optical tweezing has been used to provide a method for microrheology addressed to measure the rheological properties of small volumes of samples. In this work, we corroborate this emerging field of microrheology by using these optical methods for the characterization of polyelectrolyte solutions with very low viscoelasticity. The influence of polyelectrolyte (i.e., polyacrylamide, PAM) concentration, specifically its aging, of the salt concentration is shown. The close agreement of the technique with classical bulk rheological measurements is demonstrated, illustrating the advantages of the technique.

Shear-induced deformation of surfactant multilamellar vesicles.

Surfactant multilamellar vesicles (SMLVs) play a key role in the formulation of many industrial products, such as detergents, foodstuff, and cosmetics. In this Letter, we present the first quantitative investigation of the flow behavior of single SMLVs in a shearing parallel plate apparatus. We found that SMLVs are deformed and oriented by the action of shear flow while keeping constant volume and exhibit complex dynamic modes (i.e., tumbling, breathing, and tank treading). This behavior can be explained in terms of an excess area (as compared to a sphere of the same volume) and of microstructural defects, which were observed by 3D shape reconstruction through confocal microscopy. Furthermore, the deformation and orientation of SMLVs scale with radius R in analogy with emulsion droplets and elastic capsules (instead of R(3), such as in unilamellar vesicles). A possible application of the physical insight provided by this Letter is in the rationale design of processing methods of surfactant-based systems.