Continuous Flow Photocatalytic Hydrogen Production from Water Synergistically Activated by TiO2, Gold Nanoparticles, and Carbon Nanotubes.

Titanium dioxide nanoparticles were combined with carbon nanotubes and gold to develop improved photocatalysts for the production of hydrogen from water. The entangled nature of the nanotubes allowed for the integration of the photoactive hybrid catalyst, as a packed-bed, in a microfluidic photoreactor, and the chips were studied in the photocatalyzed continuous flow production of hydrogen. The combination of titanium dioxide with carbon nanotubes and gold significantly improved hydrogen production due to a synergistic effect between the multi-component system and the stabilization of the active catalytic species. The titanium dioxide/carbon nanotubes/gold system permitted a 2.5-fold increase in hydrogen production, compared to that of titanium dioxide/carbon nanotubes, and a 20-fold increase, compared to that of titanium dioxide.

Proof of concept of a two-stage GMR sensor-based lab-on-a-chip for early diagnostic tests.

The development of rapid, sensitive, portable and inexpensive early diagnostic techniques is a real challenge in the fields of health, defense and in the environment. The current global pandemic has also shown the need for such tests. The World Health Organization has defined ASSURED criteria (affordable, sensitive, specific, user-friendly, rapid and robust, equipment-free and deliverable to end-users) that field diagnostic tests must fulfill, which proves the real need in terms of public health. Giant magnetoresistance (GMR) sensors, which have flourished in a wide variety of spintronic applications (automobile industry, Information Technology, etc.), also have real potential in the field of health, particularly for the development of early diagnostic point-of-care devices. This work presents a new type of innovative biochip, consisting of GMR sensors arranged on both sides of a microfluidic channel which allow on the one hand to count magnetic objects one by one but also to better distinguish false positives (aggregates of beads, etc.) from labelled biological targets of interest by determining their magnetic moment. We present the operating principle of this new tool and its great potential as a versatile diagnostic test.

Formation and stabilization of multiple w/o/w emulsions encapsulating catechin, by mechanical and microfluidic methods using a single pH-sensitive copolymer: Effect of copolymer/drug interaction.

Multiple w/o/w emulsions (MEs) are promising systems for protecting fragile hydrophilic drugs and controlling their release. We explore the capacity of a single pH-sensitive copolymer, PDMS60-b-PDMAEMA50, and salts, to form and stabilize MEs loaded with sucrose or catechin by a one-step mechanical process or a microfluidic method. ME cytotoxicity was evaluated in various conditions of pH. Using the mechanical process, the most stable emulsions were obtained with Miglyol®812 N and isopropyl myristate in a final pH range of 8-12 and [0.3 M-1 M] NaCl concentrations. Conversely, with the microfluidic method, isopropyl myristate at pH 3 without salt was more efficient. Catechin strongly affected the formation of droplets by the mechanical process but did not modify the conditions of stability of MEs obtained by the microfluidic method. The antioxidant power of catechin was preserved in the inner droplets, even in emulsions prepared by the mechanical method at pH 8. An incomplete release of sucrose and catechin from the emulsions was observed and attributed to the interaction of molecules with the copolymer through hydrogen bonding. This study highlights some of the barriers to break to formulate multiple emulsions stabilized by a PDMS-b-PDMAEMA copolymer or other polymers which can form hydrogen bonds interaction with encapsulated drugs.

Direct integration of gold-carbon nanotube hybrids in continuous-flow microfluidic chips: A versatile approach for nanocatalysis.

A carbon nanotube-based packed-bed microreactor was developed for the on-chip oxidation of silanes. The process is catalyzed by a heterogeneous gold-carbon nanotube hybrid that was embedded in the device using a micrometric restriction zone. Integration of the nanohybrid permitted efficient flow aerobic oxidation of the substrates into the corresponding silanols with high selectivity and under sustainable conditions.

Microfluidic platform for monitoring Saccharomyces cerevisiae mutation accumulation.

Mutations in DNA have large-ranging consequences, from evolution to disease. Many mechanisms contribute to mutational processes such as dysfunctions in DNA repair pathways and exogenous or endogenous mutagen exposures. Model organisms and mutation accumulation (MA) experiments are indispensable to study mutagenesis. Classical MA is, however, time consuming and laborious. To fill the need for more efficient approaches to characterize mutational profiles, we have developed an innovative microfluidic-based system that automatizes MA culturing over many generations in budding yeast. This unique experimental tool, coupled with high-throughput sequencing, reduces by one order of magnitude the time required for genome-wide measurements of mutational profiles, while also parallelizing and simplifying the cell culture. To validate our approach, we performed microfluidic MA experiments on two different genetic backgrounds, a wild-type strain and a base-excision DNA repair ung1 mutant characterized by a well-defined mutational profile. We show that the microfluidic device allows for mutation accumulation comparable to the traditional method on plate. Our approach thus paves the way to massively-parallel MA experiments with minimal human intervention that can be used to investigate mutational processes at the origin of human diseases and to identify mutagenic compounds relevant for medical and environmental research.

OSTE+ for in situ SAXS analysis with droplet microfluidic devices.

In recent years, microfluidic-based sample preparation techniques have emerged as a powerful tool for measurements at large scale X-ray facilities. Most often the microfluidic device was a form of hybrid system, i.e. an assembly of different materials, because a simple, versatile and inexpensive microfabrication method, on the one hand, and X-ray compatibility, on the other hand, cannot generally be achieved by the same material. The arrival of a new polymer family based on off-stoichiometric thiol-ene-epoxy (OSTE+) has recently redistributed the cards. In this context, we studied the relevance and the compatibility of OSTE+ for small-angle X-ray scattering (SAXS) studies. The material was characterized regarding its X-ray properties (transmission coefficient, attenuation coefficient, scattering pattern and polymer aging under X-ray light) and their comparison with those of the usual polymers used in microfluidics and/or for synchrotron radiation experiments. We show that OSTE+ has a better SAXS signal than polyimide, the polymer of reference in the SAXS community. Then a detailed protocol to manufacture a suitably thin full OSTE+ chip (total thickness <500 µm) is described and the potency of full OSTE+ devices for in situ SAXS studies is highlighted in two case-studies: the characterization of gold nanoparticles and the precipitation of cerium oxalate particles, both in moving droplets. Additionally, a method to analyze the scattering signals from droplet and carrier phase in a segmented flow is proposed.

Replication of a Printed Volatile Mold: a novel microfabrication method for advanced microfluidic systems.

A novel and simple method to fabricate microchannels is reported based on an inkjet printing of a volatile solid mold. A liquid ink -1,6 hexanediol- ejected from a piezoelectric nozzle is instantaneously frozen when touching a cooled substrate. The created mold is then poured with PDMS. Once the PDMS is crosslinked, the ink is sublimated and the device is ready. With this approach it is possible to make microchannels on different nature surfaces such as glass, paper, uncross-linked PDMS layer or non planar substrates. The versatility of this method is illustrated by printing channels directly on commercial electrodes and measuring the channel capacitance. Moreover, millimetric height microfluidic systems are easily produced (aspect ratio [Formula: see text] 25) as well as 3D structures such as bridges. To demonstrate, we have fabricated a combinatorial microfluidic system which makes 6 mixtures from 4 initial solutions without any stacking and tedious alignment procedure.

DMF-MALDI: droplet based microfluidic combined to MALDI-TOF for focused peptide detection.

We present an automated droplet microfluidic system (DMF) to generate monitored nanoliter aqueous droplets in oil and their deposition on a commercial stainless steel plate for MALDI-TOF analysis of peptides or protein digests. We demonstrate that DMF-MALDI combination focuses the analyte on the MALDI plate, increasing considerably the homogeneity of the dried material. This results in a 30times enhanced MALDI-TOF MS signal for a model peptide, allowing a significant improvement of the detection sensitivity limit (down to few tens of attomoles). Moreover, positive detection can be achieved from sub-nanomolar peptides solutions and better overall protein sequence coverages are obtained from few tens attomoles of protein digest. These results make DMF-MALDI a promising approach for the treatment of peptides samples as well as a key component for an integrated approach in the proteomic field.

Electrolytes at interfaces: accessing the first nanometers using X-ray standing waves.

Ion-surface interactions are of high practical importance in a wide range of technological, environmental and biological problems. In particular, they ultimately control the electric double layer structure, hence the interaction between particles in aqueous solutions. Despite numerous achievements, progress in their understanding is still limited by the lack of experimental determination of the surface composition with appropriate resolution. Tackling this challenge, we have developed a method based on X-ray standing waves coupled to nano-confinement which allows the determination of ion concentrations at a solid-solution interface with a sub-nm resolution. We have investigated mixtures of KCl/CsCl and KCl/KI in 0.1 mM to 10 mM concentrations on silica surfaces and obtained quantitative information on the partition of ions between bulk and Stern layer as well as their distribution in the Stern layer. Regarding partition of potassium ions, our results are in agreement with a recent AFM study. We show that in a mixture of KCl and KI, chloride ions exhibit a higher surface propensity than iodide ions, having a higher concentration within the Stern layer and being on average closer to the surface by ≈1-2 Å, in contrast to the solution water interface. Confronting such data with molecular simulations will lead to a precise understanding of ionic distributions at aqueous interfaces.

Designing Colloidal Molecules with Microfluidics.

The creation of new colloidal materials involves the design of functional building blocks. Here, a microfluidic method for designing building blocks one by one, at high throughput, with a broad range of shapes is introduced. The method exploits a coupling between hydrodynamic interactions and depletion forces that controls the configurational dynamics of droplet clusters traveling in microfluidic channels. Droplet clusters can be solidified in situ with UV. By varying the flow parameters, clusters are prescribed a given size, geometry, chemical and/or magnetic heterogeneities enabling local bonding. Compact structures (chains, triangles, diamonds, tetrahedrons,...) and noncompact structures, such as crosses and T, difficult to obtain with current techniques are produced. Size dispersions are small (2%) and throughputs are high (30 000 h-1). The work opens a new pathway, based on microfluidics, for designing colloidal building blocks with a potential to enable the creation of new materials.

Biocompatible Stimuli-Responsive W/O/W Multiple Emulsions Prepared by One-Step Mixing with a Single Diblock Copolymer Emulsifier.

Multiple water-in-oil-in-water (W/O/W) emulsions are promising materials in designing carriers of hydrophilic molecules or drug delivery systems, provided stability issues are solved and biocompatible chemicals can be used. In this work, we designed a biocompatible amphiphilic copolymer, poly(dimethylsiloxane)-b-poly(2-(dimethylamino)ethyl methacrylate) (PDMS-b-PDMAEMA), that can stabilize emulsions made with various biocompatible oils. The hydrophilic/hydrophobic properties of the copolymer can be adjusted using both pH and ionic strength stimuli. Consequently, the making of O/W (oil in water), W/O (water in oil), and W/O/W emulsions can be achieved by sweeping the pH and ionic strength. Of importance, W/O/W emulsions are formulated over a large pH and ionic strength domain in a one-step emulsification process via transitional phase inversion and are stable for several months. Cryo-TEM and interfacial tension studies show that the formation of these W/O/W emulsions is likely to be correlated to the interfacial film curvature and microemulsion morphology.

Investigation of PDMS based bi-layer elasticity via interpretation of apparent Young's modulus.

As the need of new methods for the investigation of thin films on various kinds of substrates becomes greater, a novel approach based on AFM nanoindentation is explored. Substrates of polydimethylsiloxane (PDMS) coated by a layer of hard material are probed with an AFM tip in order to obtain the force profile as a function of the indentation. The equivalent elasticity of those composite systems is interpreted using a new numerical approach, the Coated Half-Space Indentation Model of Elastic Response (CHIMER), in order to extract the thicknesses of the upper layer. Two kinds of coating are investigated. First, chitosan films of known thicknesses between 30 and 200 nm were probed in order to test the model. A second type of samples is produced by oxygen plasma oxidation of the PDMS substrate, which results in the growth of a relatively homogeneous oxide layer. The local nature of this protocol enables measurements at long oxidation time, where the apparition of cracks prevents other kinds of measurements.

Aging mechanism in model Pickering emulsion.

We study the stability of a model Pickering emulsion system using fluorinated oil and functionalized silica nanoparticles. A special counter-flow microfluidic set-up was used to prepare monodisperse oil droplets in water. The wettability of the monodisperse silica nanoparticles (NPs) could be tuned by surface grafting and the surface coverage of the droplets was controlled using the microfluidic setup. For surface coverage as low as 23%, we observed a regime of Pickering emulsion stability where the surface coverage of emulsion droplets of constant size increases with time, coexisting with an excess of oil phase. Our results demonstrate that the previously observed limited coalescence regime where surface coverage tends to control the average size of the final droplets must be put in a broader perspective.

Vapour processed self-rolled poly(dimethylsiloxane) microcapillaries form microfluidic devices with engineered inner surface.

We propose a microfluidics device whose main functional part consists of a microcapillary produced by the self-rolling of a thin poly(dimethylsiloxane) film. Rolling is caused by inhomogeneous swelling of the film, pre-treated by oxygen plasma, in the vapour of chloroform. The capillaries are integrated with external electrical circuits by co-rolling electrodes and micro-resistors. The local control of temperature in the tubes by Joule heating is illustrated via the rate of an intra-tubular chemiluminescent reaction. The novel tubes with engineered inner structure can find numerous advanced applications such as functional elements of integrated microfluidics circuits.

A Review of Heating and Temperature Control in Microfluidic Systems: Techniques and Applications.

This review presents an overview of the different techniques developed over the last decade to regulate the temperature within microfluidic systems. A variety of different approaches has been adopted, from external heating sources to Joule heating, microwaves or the use of lasers to cite just a few examples. The scope of the technical solutions developed to date is impressive and encompasses for instance temperature ramp rates ranging from 0.1 to 2,000 °C/s leading to homogeneous temperatures from -3 °C to 120 °C, and constant gradients from 6 to 40 °C/mm with a fair degree of accuracy. We also examine some recent strategies developed for applications such as digital microfluidics, where integration of a heating source to generate a temperature gradient offers control of a key parameter, without necessarily requiring great accuracy. Conversely, Temperature Gradient Focusing requires high accuracy in order to control both the concentration and separation of charged species. In addition, the Polymerase Chain Reaction requires both accuracy (homogeneous temperature) and integration to carry out demanding heating cycles. The spectrum of applications requiring temperature regulation is growing rapidly with increasingly important implications for the physical, chemical and biotechnological sectors, depending on the relevant heating technique.

Microfluidic trap-and-release system for lab-on-a-chip-based studies on giant vesicles.

We present a microfluidic array that allows lab-on-a-chip-based studies on hundreds of giant vesicles through immobilization, engineering and release of the vesicles. Real-time observations of the vesicular response are reported. This trap-and-release system is also used to efficiently narrow the size distribution of the vesicle population. In addition, it can be applied to a wide range of deformable objects.

Microchip integrating magnetic nanoparticles for allergy diagnosis.

We report on the development of a simple and easy to use microchip dedicated to allergy diagnosis. This microchip combines both the advantages of homogeneous immunoassays i.e. species diffusion and heterogeneous immunoassays i.e. easy separation and preconcentration steps. In vitro allergy diagnosis is based on specific Immunoglobulin E (IgE) quantitation, in that way we have developed and integrated magnetic core-shell nanoparticles (MCSNPs) as an IgE capture nanoplatform in a microdevice taking benefit from both their magnetic and colloidal properties. Integrating such immunosupport allows to perform the target analyte (IgE) capture in the colloidal phase thus increasing the analyte capture kinetics since both immunological partners are diffusing during the immune reaction. This colloidal approach improves 1000 times the analyte capture kinetics compared to conventional methods. Moreover, based on the MCSNPs' magnetic properties and on the magnetic chamber we have previously developed the MCSNPs and therefore the target can be confined and preconcentrated within the microdevice prior to the detection step. The MCSNPs preconcentration factor achieved was about 35,000 and allows to reach high sensitivity thus avoiding catalytic amplification during the detection step. The developed microchip offers many advantages: the analytical procedure was fully integrated on-chip, analyses were performed in short assay time (20 min), the sample and reagents consumption was reduced to few microlitres (5 µL) while a low limit of detection can be achieved (about 1 ng mL(-1)).

Magnetic core shell nanoparticles trapping in a microdevice generating high magnetic gradient.

Magnetic core shell nanoparticles (MCSNPs) 30 nm diameter with a magnetic weight of 10% are usually much too small to be trapped in microfluidic systems using classical external magnets. Here, a simple microchip for efficient MCSNPs trapping and release is presented. It comprises a bed of micrometric iron beads (6-8 µm diameter) packed in a microchannel against a physical restriction and presenting a low dead volume of 0.8 nL. These beads of high magnetic permeability are used to focus magnetic field lines from an external permanent magnet and generate local high magnetic gradients. The nanoparticles magnetic trap has been characterised both by numerical simulations and fluorescent MCSNPs imaging. Numerical simulations have been performed to map both the magnetic flux density and the magnetic force, and showed that MCSNPs are preferentially trapped at the iron bead magnetic poles where the magnetic force is increased by 3 orders of magnitude. The trapping efficiency was experimentally determined using fluorescent MCSNPs for different flow rates, different iron beads and permanent magnet positions. At a flow rate of 100 µL h(-1), the nanoparticles trapping/release can be achieved within 20 s with a preconcentration factor of 4000.

Monodisperse colloids synthesized with nanofluidic technology.

Limitations in the methods employed to generate micrometric colloidal droplets hinder the emergence of key applications in the fields of material science and drug delivery. Through the use of dedicated nanofluidic devices and by taking advantage of an original physical effect called capillary focusing, we could circumvent some of these limitations. The nanofluidic (i.e., submicrometric) devices introduced herein are made of soft materials, and their fabrication relies upon rapid technologies. The objects that we have generated are simple droplets, multiple droplets, particles, and Janus particles whose sizes lie between 900 nm and 3 microm (i.e., within the colloidal range). Colloidal droplets have been assembled on-chip into clusters and crystals, yielding discrete diffraction patterns. We illustrate potential applications in the field of drug delivery by demonstrating the ability of multiple droplets to be phagocytosed by murine macrophage-type cells.

Nonlocal rheological properties of granular flows near a jamming limit.

We study the rheology of sheared granular flows close to a jamming transition. We use the approach of partially fluidized theory (PFT) with a full set of equations extending the thin layer approximation derived previously for the description of the granular avalanches phenomenology. This theory provides a picture compatible with a local rheology at large shear rates [G. D. R. Midi, Eur. Phys. J. E 14, 341 (2004)] and it works in the vicinity of the jamming transition, where a description in terms of a simple local rheology comes short. We investigate two situations displaying important deviations from local rheology. The first one is based on a set of numerical simulations of sheared soft two-dimensional circular grains. The next case describes previous experimental results obtained on avalanches of sandy material flowing down an incline. Both cases display, close to jamming, significant deviations from the now standard Pouliquen's flow rule [O. Pouliquen, Phys. Fluids 11, 542 (1999); 11, 1956 (1999)]. This discrepancy is the hallmark of a strongly nonlocal rheology and in both cases, we relate the empirical results and the outcomes of PFT. The numerical simulations show a characteristic constitutive structure for the fluid part of the stress involving the confining pressure and the material stiffness that appear in the form of an additional dimensionless parameter. This constitutive relation is then used to describe the case of sandy flows. We show a quantitative agreement as far as the effective flow rules are concerned. A fundamental feature is identified in PFT as the existence of a jammed layer developing in the vicinity of the flow arrest that corroborates the experimental findings. Finally, we study the case of solitary erosive granular avalanches and relate the outcome with the PFT analysis.