2.5D printing of a yield-stress fluid.

We report on direct ink writing of a model yield-stress fluid and focus on the printability of the first layer, the one in contact with the supporting substrate. We observe a diversity of deposition morphologies that depends on a limited set of operational parameters, mainly ink flow rate, substrate speed and writing density, and also on material properties (e.g., yield-stress). Among these morphologies, one of them does not depend on fluid properties (as long as the fluid displays some yield-stress) and consists of flat films whose thickness is controllable in a significant range, about [Formula: see text] mm, and tunable in real time during printing. We thus demonstrate the ability to print films with thickness gradients and prove that the printing fidelity is mainly due to a competition between yield-stress and capillarity.

Silver Nanoshells with Optimized Infrared Optical Response: Synthesis for Thin-Shell Formation, and Optical/Thermal Properties after Embedding in Polymeric Films.

We describe a new approach to making ultrathin Ag nanoshells with a higher level of extinction in the infrared than in the visible. The combination of near-infrared active ultrathin nanoshells with their isotropic optical properties is of interest for energy-saving applications. For such applications, the morphology must be precisely controlled, since the optical response is sensitive to nanometer-scale variations. To achieve this precision, we use a multi-step, reproducible, colloidal chemical synthesis. It includes the reduction of Tollens' reactant onto Sn2+-sensitized silica particles, followed by silver-nitrate reduction by formaldehyde and ammonia. The smooth shells are about 10 nm thick, on average, and have different morphologies: continuous, percolated, and patchy, depending on the quantity of the silver nitrate used. The shell-formation mechanism, studied by optical spectroscopy and high-resolution microscopy, seems to consist of two steps: the formation of very thin and flat patches, followed by their guided regrowth around the silica particle, which is favored by a high reaction rate. The optical and thermal properties of the core-shell particles, embedded in a transparent poly(vinylpyrrolidone) film on a glass substrate, were also investigated. We found that the Ag-nanoshell films can convert 30% of the power of incident near-infrared light into heat, making them very suitable in window glazing for radiative screening from solar light.

Multiphase Microreactors Based on Liquid-Liquid and Gas-Liquid Dispersions Stabilized by Colloidal Catalytic Particles.

Pickering emulsions, foams, bubbles, and marbles are dispersions of two immiscible liquids or of a liquid and a gas stabilized by surface-active colloidal particles. These systems can be used for engineering liquid-liquid-solid and gas-liquid-solid microreactors for multiphase reactions. They constitute original platforms for reengineering multiphase reactors towards a higher degree of sustainability. This Review provides a systematic overview on the recent progress of liquid-liquid and gas-liquid dispersions stabilized by solid particles as microreactors for engineering eco-efficient reactions, with emphasis on biobased reagents. Physicochemical driving parameters, challenges, and strategies to (de)stabilize dispersions for product recovery/catalyst recycling are discussed. Advanced concepts such as cascade and continuous flow reactions, compartmentalization of incompatible reagents, and multiscale computational methods for accelerating particle discovery are also addressed.

Microfluidic Evaporation, Pervaporation, and Osmosis: From Passive Pumping to Solute Concentration.

Evaporation, pervaporation, and forward osmosis are processes leading to a mass transfer of solvent across an interface: gas/liquid for evaporation and solid/liquid (membrane) for pervaporation and osmosis. This Review provides comprehensive insight into the use of these processes at the microfluidic scales for applications ranging from passive pumping to the screening of phase diagrams and micromaterials engineering. Indeed, for a fixed interface relative to the microfluidic chip, these processes passively induce flows driven only by gradients of chemical potential. As a consequence, these passive-transport phenomena lead to an accumulation of solutes that cannot cross the interface and thus concentrate solutions in the microfluidic chip up to high concentration regimes, possibly up to solidification. The purpose of this Review is to provide a unified description of these processes and associated microfluidic applications to highlight the differences and similarities between these three passive-transport phenomena.

Sensory neurons from dorsal root ganglia regulate endothelial cell function in extracellular matrix remodelling.

BACKGROUND: Recent physiological and experimental data highlight the role of the sensory nervous system in bone repair, but its precise role on angiogenesis in a bone regeneration context is still unknown. Our previous work demonstrated that sensory neurons (SNs) induce the osteoblastic differentiation of mesenchymal stem cells, but the influence of SNs on endothelial cells (ECs) was not studied. METHODS: Here, in order to study in vitro the interplay between SNs and ECs, we used microfluidic devices as an indirect co-culture model. Gene expression analysis of angiogenic markers, as well as measurements of metalloproteinases protein levels and enzymatic activity, were performed. RESULTS: We were able to demonstrate that two sensory neuropeptides, calcitonin gene-related peptide (CGRP) and substance P (SP), were involved in the transcriptional upregulation of angiogenic markers (vascular endothelial growth factor, angiopoietin 1, type 4 collagen, matrix metalloproteinase 2) in ECs. Co-cultures of ECs with SNs also increased the protein level and enzymatic activity of matrix metalloproteinases 2 and 9 (MMP2/MMP9) in ECs. CONCLUSIONS: Our results suggest a role of sensory neurons, and more specifically of CGRP and SP, in the remodelling of endothelial cells extracellular matrix, thus supporting and enhancing the angiogenesis process. Video abstract.

Diffusion-limited dissolution of calcium carbonate in a hydrogel.

In the process of fabricating porous polymers, we use dispersed calcite as a sacrificial solid that generates porosity after dissolution. To do this, we trap calcite particles in a hydrogel, dissolve the particles and dry the hydrogel; here, we describe in detail the dissolution kinetics. We prepare PEGDA [poly(ethylene glycol)-diacrylate] water solutions loaded with micron-sized calcite particles (containing mostly calcium carbonate) up to about 30% volume fraction; these dispersions are photo-polymerized into hydrogels as flat and shallow monoliths with a typical thickness of ≈100 µm and a lateral extent on the order of 1 cm. These soft hydrogels are then soaked into an acidic solution (HCl) which induces the dissolution of the carbonates. The dissolution fronts remain sharp throughout the dissolution and progress inward in a diffusive manner. Such a kinetics is well described numerically using a mean-field diffusion-reaction model where the diffusion of the acid strongly limits the process.

Fluidic Patterning of Transparent Polymer Heaters.

Semi-conducting polymers are promising materials for current and next generations of electronic devices, sensors and actuators, especially regarding their ability to conform to flexibles architectures. In particular, aqueous-based dispersions of semi-conducting complexes such as PEDOT:PSS can be printed using a variety of coating techniques and the conductivity of the final deposit may reach high values upon a proper treatment. The micro-structuration of these polymeric deposits remains challenging and of prime importance for further integration. We show here that a microfluidic post-treatment of PEDOT:PSS films of permits us to boost locally only their conductivity by several orders of magnitude, with a micron scale resolution. This is a fast process (~second), straightforward to upscale, that yields conductive patterns within the pristine film. Taking advantage of the localized Joule's effect, we evidence using quantitative thermography a very efficient heating behaviour of the conductive tracks, which makes these polymeric structures promising candidates for low cost, clean-room free electrodes for lab-on-chip applications.

Calibration Procedure for Attenuation Coefficient Measurements in Highly Opaque Media Using Infrared Focal Plane Array (IRFPA) Spectroscopy.

The purpose of this article is to present a new calibration procedure for spectroscopic measurements using an infrared focal plane array (IRFPA) spectrometer on highly opaque middle-wave infrared (MWIR) media. The procedure is based on the properties of the IRFPA camera and especially the integration time (IT), which is the main parameter that can be adjusted to control the sensitivity of the measurements. The goal of the paper is to experimentally validate this dependence with the direct reference intensity light coming out of the IR monochromator in order to predict the spectrum shape and intensity level in a range out of the camera saturation. This method allows determining spectrum used as background for transmittance calculation. It has been applied in the case of measurement of water transmittance, which is a highly opaque medium and whose measurement requires high ITs. The main result is the ability to take an IR spectroscopic imaging measurement through 300 µm of water and the determination of its transmittance with sufficient sensitivity due to the proposed calibration procedure. This procedure allows the possibility of transitory studies in heterogeneous aqueous media.

Dorsal root ganglion neurons regulate the transcriptional and translational programs of osteoblast differentiation in a microfluidic platform.

Innervation by the sensory nervous system plays a key role in skeletal development and in orchestration of bone remodeling and regeneration. However, it is unclear how and in which bone cells can sensory nerves act to control these processes. Here, we show a microfluidic coculture system comprising dorsal root ganglion (DRG) neurons and mesenchymal stem cells (MSCs) that more faithfully represents the in vivo scenario of bone sensory innervation. We report that DRG neurons promote the osteogenic differentiation capacity of MSCs, by mediating the increase of alkaline phosphatase activity and the upregulation of osteoblast-specific genes. Furthermore, we show that DRG neurons have a positive impact on Cx43 levels in MSCs during osteoblastogenesis, especially at an early stage of this process. Conversely, we described a negative impact of DRG neurons on MSCs N-cadherin expression at a later stage. Finally, we demonstrate a cytoplasmic accumulation of ß-catenin translocation into the nucleus, and subsequently Lymphoid Enhancer Binding Factor 1-responsive transcriptional activation of downstream genes in cocultured MSCs. Together, our study provides a robust body of evidence that the direct interaction of DRG neurons with MSCs in a bone-like microenvironment leads to an enhancement of osteoblast differentiation potential of MSCs. The osteogenic effect of DRG neurons on MSCs is mediated through the regulation of Cx43 and N-cadherin expression and activation of the canonical/ß-catenin Wnt signaling pathway.

A Soft 3D Acoustic Metafluid with Dual-Band Negative Refractive Index.

Spherical silica xerogels are efficient acoustic Mie resonators. When these sub-wavelength inclusions are dispersed in a matrix, the final metafluid may display a negative acoustic refractive index upon a set of precise constraints concerning material properties, concentration, size, and dispersity of the inclusions. Because xerogels may sustain both pressure and shear waves, several bands with negative index can be tailored.

Drying with no concentration gradient in large microfluidic droplets.

In most situations, drying is accompanied by the development of strong concentration gradients. Here, we evidence theoretically and experimentally that there exist microfluidic geometries for which confined drying becomes homogeneous, i.e., with no concentration gradient regardless of the type of solute involved in the process; ions, molecules, and colloids do concentrate in the same way providing a limited set of assumptions concerning the microfluidic geometry. It thus makes possible the establishment of phase diagrams of multi-component mixtures at the nanoliter scale.

Soft 3D acoustic metamaterial with negative index.

Many efforts have been devoted to the design and achievement of negative-refractive-index metamaterials since the 2000s. One of the challenges at present is to extend that field beyond electromagnetism by realizing three-dimensional (3D) media with negative acoustic indices. We report a new class of locally resonant ultrasonic metafluids consisting of a concentrated suspension of macroporous microbeads engineered using soft-matter techniques. The propagation of Gaussian pulses within these random distributions of 'ultra-slow' Mie resonators is investigated through in situ ultrasonic experiments. The real part of the acoustic index is shown to be negative (up to almost - 1) over broad frequency bandwidths, depending on the volume fraction of the microbeads as predicted by multiple-scattering calculations. These soft 3D acoustic metamaterials open the way for key applications such as sub-wavelength imaging and transformation acoustics, which require the production of acoustic devices with negative or zero-valued indices.

Design of a fluorinated magneto-responsive material with tuneable ultrasound scattering properties.

In this work, we describe the preparation of emulsions of fluorinated ferrofluid droplets suspended in a yield-stress hydrogel (Bingham fluid) with potential applications for ultrasound (US) spectroscopy and imaging. Fluorinated ferrofluids were obtained using an original multi-step process leading to an appropriate suspension of magnetic nanoparticles (MNPs) coated by a layer of fluoroalkylsilane in fluorinated oil. The efficiency of the sol-gel coating reaction was assessed by several methods including infrared and X-ray photoelectron spectroscopy, small angle neutron scattering and magnetometry. The resulting suspension of silanized-MNPs behaves as a true fluorinated ferrofluid, remaining stable (i.e. a monophasic suspension of well dispersed MNPs) in magnetic inductions as high as 7 T. These ferrofluids were employed to prepare monodisperse emulsions in a Bingham gel using a robotic injection device. Using ultrasound spectroscopy, we show that the emulsion droplets behave as Mie-type acoustic wave resonators due to the high sound-speed contrast between the droplets and the matrix. When subjected to a magnetic field, the ferrofluid droplets elongate in the field direction, which in return modifies the acoustic response of the material. The resonance frequency peaks scale as the inverse of the emulsion droplet size encountered by the wave propagation vector. These results might open a new road towards the realisation of ultrasound contrast agents guided by magnetic fields and with a tuneable attenuation spectrum.

Microfluidic-induced growth and shape-up of three-dimensional extended arrays of densely packed nanoparticles.

We use evaporation within a microfluidic device to extract the solvent of a (possibly very dilute) dispersion of nanoparticles and concentrate the dispersion until a solid made of densely packed nanoparticles grows and totally invades the microfluidic geometry. The growth process can be rationalized as an interplay between evaporation-induced flow and kinetic and thermodynamic coefficients which are system-dependent; this yields limitations to the growth process illustrated here on two main cases: evaporation- and transport-limited growth. Importantly, we also quantify how colloidal stability may hinder the growth and show that care must be taken as to the composition of the initial dispersion, especially regarding traces of ionic species that can destabilize the suspension upon concentration. We define a stability chart, which, when fulfilled, permits us to grow and shape-up solids, including superlattices and extended and thick arrays of nanoparticles made of unary and binary dispersions, composites, and heterojunctions between distinct types of nanoparticles. In all cases, the geometry of the final solid is imparted by that of the microfluidic device.

Impact of polydispersity on multipolar resonant scattering in emulsions.

The influence of size polydispersity on the resonant acoustic properties of dilute emulsions, made of fluorinated-oil droplets, is quantitatively investigated. Ultrasound attenuation and dispersion measurements on various samples with controlled size polydispersities, ranging from 1% to 13%, are found to be in excellent agreement with predictions based on the independent scattering approximation. By relating the particle-size distribution of the synthesized emulsions to the quality factor of the predicted multipolar resonances, the number of observable acoustic resonances is shown to be imposed by the sample polydispersity. These results are briefly discussed into the context of metamaterials for which scattering resonances are central to their effective properties.

Steady and out-of-equilibrium phase diagram of a complex fluid at the nanolitre scale: combining microevaporation, confocal Raman imaging and small angle X-ray scattering.

We engineered specific microfluidic devices based on the pervaporation of water through a PDMS membrane, to formulate continuous and steady concentration gradients of a binary aqueous molecular mixture at the nanolitre scale. In the case of a model complex fluid (a triblock copolymer solution), we demonstrate that such a steady gradient crosses the phase diagram from pure water up to a succession of highly viscous mesophases. We then performed in situ spatially resolved measurements (confocal spectroscopy and small-angle X-ray scattering) to quantitatively measure the concentration profile and to determine the microstructure of the different textures. Within a single microfluidic channel, we thus screen quantitatively and continuously the phase diagram of a complex fluid. Beside, as such a gradient corresponds to an out-of-equilibrium regime, we also extract from the concentration measurement a precise estimate of the collective diffusion coefficient of the mixture as a function of the concentration. In the present case of the triblock copolymer, this transport coefficient features discontinuities at some phase boundaries, which have never been observed before.

Elastic instability in stratified core annular flow.

We study experimentally the interfacial instability between a layer of dilute polymer solution and water flowing in a thin capillary. The use of microfluidic devices allows us to observe and quantify in great detail the features of the flow. At low velocities, the flow takes the form of a straight jet, while at high velocities, steady or advected wavy jets are produced. We demonstrate that the transition between these flow regimes is purely elastic--it is caused by the viscoelasticity of the polymer solution only. The linear stability analysis of the flow in the short-wave approximation supplemented with a kinematic criterion captures quantitatively the flow diagram. Surprisingly, unstable flows are observed for strong velocities, whereas convected flows are observed for low velocities. We demonstrate that this instability can be used to measure the rheological properties of dilute polymer solutions that are difficult to assess otherwise.

Three-dimensional structure and growth of myelins.

After contact with water, surfactant lamellar phases (L(α)) can show spectacular interface instabilities: multibilayer tubules, so-called myelins, grow from the L(α)/water interface into the water. We have studied the shape, size, and growth of myelins in aqueous solutions of the nonionic surfactant C(12)E(3) (triethylene glycol monododecyl ether) during dissolution. We used a combination of different imaging techniques: optical microscopy providing 2-D projections of the sample and confocal microscopy offering a complete 3-D reconstruction. These techniques provide quantitative information on the shape and growth of myelins, such as their width, length, and depth profile as a function of time. The growth rate of myelins, characterized by a swelling or diffusion coefficient, was found to increase with surfactant mass fraction and, seemingly, with sample thickness. We demonstrate that myelin creaming due to buoyancy can explain the apparent dependence on sample thickness. Our experiments furthermore suggest that myelin growth is controlled by an interplay between the water mobility in the lamellar phase and the osmotic pressure difference between the lamellar phase and the contacting water.