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At least 55 records · Page 3

Microfluidic In-Situ Spectrophotometric Approaches to Tackle Actinides Analysis in Multiple Oxidation States

The study and development of present and future processes for the treatment/recycling of spent nuclear fuels require many steps, from design in the laboratory to setting up on an industrial scale. In all of these steps, analysis and instrumentation are key points. For scientific reasons (small-scale studies, control of phenomena, etc.) but also with regard to minimizing costs, risks, and waste, such developments are increasingly carried out on milli- or microfluidic devices. The logic is the same for the chemical analyses associated with their follow-up and interpretation. Due to this, over the last few years, opto–microfluidic analysis devices adapted to the monitoring of different processes (dissolution, liquid–liquid extraction, precipitation, etc.) have been increasingly designed and developed. In this work, we prove that photonic lab-on-a-chip (PhLoC) technology is fully suitable for all actinides concentration monitoring along the plutonium uranium refining extraction (plutonium, uranium, reduction, extraction, or Purex) process. Several PhLoC microfluidic platforms were specifically designed and used in different nuclear research and development (R&D) laboratories, to tackle actinides analysis in multiple oxidation states even in mixtures. The detection limits reached (tens of µmol·L −1 ) are fully compliant with on-line process monitoring, whereas a range of analyzable concentrations of three orders of magnitude can be covered with less than 150 µL of analyte. Finally, this work confirms the possibility and the potential of coupling Raman and ultraviolet–visible (UV–Vis) spectroscopies at the microfluidic scale, opening the perspective of measuring very complex mixtures.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A sui generis whipping-instability-based self-sequencing multi-monodisperse 2D spray from an anisotropic microfluidic liquid jet device

Well-defined aerosols pave the way for versatile basic and applied research. Here, we demonstrate a unique whipping instability that generates from a high-aspect-ratio microfluidic device resulting in a unique steady-state gas-focused whipping jet (WJ) without any need for electrification. This WJ device emanates a multi-monodisperse whipping spray jet with a two-dimensional (2D) profile. We demonstrate this phenomenon based on various fluidic parameters theoretically and experimentally. The 2D WJ’s unique behavior is derived using analytical fluid dynamics to explain jet diameter, whipping regime, and spreading angle. The phenomenon is further characterized experimentally by measuring the angle with respect to the flow rate, the distances between droplets, the droplet shapes, and the reproducibility of these parameters. We also explain the precise fabrication of such inexpensive devices. Lastly, we highlight these devices’ potential use as sample environments in versatile applications ranging from cryoelectron microscopy over mass spectrometry to drug formulation and structural studies at X-ray free-electron lasers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Detection of Amino Acids from Bacterial Biofilms and Plant Root Exudates by Liquid Microjunction Surface-Sampling Probe Mass Spectrometry

The plant rhizosphere is a complex and dynamic chemical environment where the exchange of molecular signals between plants, microbes, and fungi drives the development of the entire biological system. Exogenous compounds in the rhizosphere are known to affect plant-microbe organization, interactions between organisms, and ultimately, growth and survivability. The function of exogenous compounds in the rhizosphere is still under much investigation, specifically with respect to their roles in plant growth and development, the assembly of the associated microbial community, and the spatiotemporal distribution of molecular components. A major challenge for spatiotemporal measurements is developing a nondisruptive and nondestructive technique capable of analyzing the exogenous compounds contained within the environment. A methodology using liquid microjunction-surface sampling probe-mass spectrometry (LMJ-SSP-MS) and microfluidic devices with attached microporous membranes was developed for in situ, spatiotemporal measurement of amino acids (AAs) from bacterial biofilms and plant roots. Exuded arginine was measured from a living Pantoea YR 343 biofilm, which resulted in a chemical image indicative of biofilm growth within the device. Spot sampling along the roots of Populus trichocarpa with the LMJ-SSP-MS resulted in the detection of 15 AAs. Of note, variation in AA concentrations across the root system was observed, indicating that exudation is not homogeneous and may be linked to local rhizosphere architecture and different biological processes along the root.

59 BASIC BIOLOGICAL SCIENCES↗

Picoliter droplet sample processing and deposition for mass spectrometry

Disclosed herein include systems, devices, and methods for droplet deposition for mass spectrometry. In some embodiments, a microfluidic device comprising wells is reversibly sealed to a mass spectrometry surface and used to deposit contents of droplets (e.g., enzymes and substrates), or products thereof, onto the mass spectrometry surface. The contents of droplets can be analyzed by laser desorption/ionization to, for example, identify a substrate of an enzyme or an enzyme capable of catalyzing a substrate to a product.

Ha, Noel↗

Scalable fabrication of an array-type fixed-target device for automated room temperature X-ray protein crystallography

X-ray crystallography is one of the leading tools to analyze the 3-D structure, and therefore, function of proteins and other biological macromolecules. Traditional methods of mounting individual crystals for X-ray diffraction analysis can be tedious and result in damage to fragile protein crystals. Furthermore, the advent of multi-crystal and serial crystallography methods explicitly require the mounting of larger numbers of crystals. To address this need, we have developed a device that facilitates the straightforward mounting of protein crystals for diffraction analysis, and that can be easily manufactured at scale. Inspired by grid-style devices that have been reported in the literature, we have developed an X-ray compatible microfluidic device that can be used to trap protein crystals in an array configuration, while also providing excellent optical transparency, a low X-ray background, and compatibility with the robotic sample handling and environmental controls used at synchrotron macromolecular crystallography beamlines. At the Stanford Synchrotron Radiation Lightsource (SSRL), these capabilities allow for fully remote-access data collection at controlled humidity conditions. Furthermore, we have demonstrated continuous manufacturing of these devices via roll-to-roll fabrication to enable cost-effective and efficient large-scale production.

chemical engineering↗

Electrochemical pH regulation in droplet microfluidics

Here we report a method for electrochemical pH regulation in microdroplets generated in a microfluidic device. The key finding is that controlled quantities of reagents can be generated electrochemically in moving microdroplets confined within a microfluidic channel. Additionally, products generated at the anode and cathode can be isolated within descendant microdroplets. Specifically, ~5 nL water-in-oil microdroplets are produced at a T-junction and then later split into two descendant droplets. During splitting, floor-patterned microelectrodes drive water electrolysis within the aqueous microdroplets to produce H + and OH - . This results in a change in the pHs of the descendant droplets. The droplet pH can be regulated over a range of 5.9 to 7.7 by injecting controlled amounts of charge into the droplets. When the injected charge is between -6.3 and 54.5 nC nL -1 , the measured pH of the resulting droplets is within ±0.1 pH units of that predicted based on the magnitude of the injected charge. This technique can likely be adapted to electrogeneration of other reagents within microdroplets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CRADA Number NFE-19-07845 with American Nanotechnologies, Inc. (CRADA Final Report)

Cooperative Research and Development Agreement (CRADA) NFE-19-07845 between Oak Ridge National Laboratory (ORNL) and American Nanotechnologies, Inc. (ANI) focused on studying the use of dielectrophoresis as a mechanism to purify nanoparticles, particularly semiconducting carbon nanotubes (CNTs). The successful development of low-cost purification processes is a significant bottleneck in the adoption of semiconducting CNTs in commercial semiconducting devices. ANI is a startup company developing scalable systems for performing nanoparticle dielectrophoresis, which has previously been used only in microfluidic devices. The work done under this CRADA is exploring the use of ANI’s patent resonant dielectrophoresis (rDEP) technology and its ability to purify semiconducting CNTs at large scale. While continued work is on-going, r-DEP has proven to be a viable way to control nanoparticles in bulk dispersions. Optimization of the process is now underway to reach minimum viable product and begin material sales. Additionally, ANI and ORNL continue to collaborate on leveraging this technology to reach down the value chain and create new commercial devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Kinetics and Mechanism of Tetravalent Cerium Extraction by Di-2-Ethylhexyl Isobutyramide (DEHiBA)

DEHiBA is a fully-incinerable, CHON extractant with a high selectivity for hexavalent actinides. However, as a recently-developed ligand, much remains unknown about its physical and chemical properties, including its extraction and phase disengagement rates. Here, we present data on the phase transfer kinetics of Ce(IV) extraction and stripping by both DEHiBA and TBP collected using microfluidic devices. Ce(IV) was selected as a surrogate for Pu(IV) and Np(IV) in the initial tests of the microfluidics system prior to testing with the actinides. Pseudo first-order reaction rate constants are determined for both systems, and the corresponding Damköhler numbers (Da) are calculated to establish whether the extraction and stripping processes are kinetically or diffusion controlled. The stoichiometry of the extracted Ce(IV)-DEHiBA complex is determined, and the phase disengagement properties under extraction conditions are assessed using the dimensionless dispersion number. A possible explanation for the favorable extraction of Ce(IV) by DEHiBA, which is known to poorly extract many tetravalent cations, is presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dean vortex-enhanced blood plasma separation in self-driven spiral microchannel flow with cross-flow microfilters

Point-of-care (POC) diagnostic devices have been developing rapidly in recent years, but they are mainly using saliva instead of blood as a test sample. A highly efficient self-separation during the self-driven flow without power systems is desired for expanding the point-of-care diagnostic devices. Microfiltration stands out as a promising technique for blood plasma separation but faces limitations due to blood cell clogging, resulting in reduced separation speed and efficiency. These limitations are mainly caused by the high viscosity and hematocrit in the blood flow. A small increment in the hematocrit of the blood significantly increases the pressure needed for the blood plasma separation in the micro-filters and decreases the separation speed and efficiency. Addressing this challenge, this study explores the feasibility of diluting whole blood within a microfluidic device without external power systems. This study implemented a spiral microchannel utilizing the inertial focusing and Dean vortex effects to focus the red blood cells and extract the blood with lower hematocrit. The inertial migration of the particles during the capillary flow was first investigated experimentally; a maximum of 88% of the particles migrated to the bottom and top equilibrium positions in the optimized 350 × 60 μm (cross-sectional area, 5.8 aspect ratio) microchannel. With the optimized dimension of the microchannel, the whole blood samples within the physiological hematocrit range were tested in the experiments, and more than 10% of the hematocrit reduction was compared between the outer branch outlet and inner branch outlet in the 350 × 60 μm microchannel.

Biochemistry & Molecular Biology↗

Wetting transition and fluid trapping in a microfluidic fracture

Immiscible fluid–fluid displacement in confined geometries is a fundamental process occurring in many natural phenomena and technological applications, from geological CO 2 sequestration to microfluidics. Due to the interactions between the fluids and the solid walls, fluid invasion undergoes a wetting transition from complete displacement at low displacement rates to leaving a film of the defending fluid on the confining surfaces at high displacement rates. While most real surfaces are rough, fundamental questions remain about the type of fluid–fluid displacement that can emerge in a confined, rough geometry. Here, we study immiscible displacement in a microfluidic device with a precisely controlled structured surface as an analogue for a rough fracture. We analyze the influence of the degree of surface roughness on the wetting transition and the formation of thin films of the defending liquid. We show experimentally, and rationalize theoretically, that roughness affects both the stability and dewetting dynamics of thin films, leading to distinct late-time morphologies of the undisplaced (trapped) fluid. Finally, we discuss the implications of our observations for geologic and technological applications.

42 ENGINEERING↗

Enriching Cations Using Electric Field Gradients Generated by Bipolar Electrodes in the Absence of Buffer

We discuss that ionic current gradients and corresponding electric field gradients formed at bipolar electrodes are useful for enriching cations up to ~350-fold at specific locations in microfluidic devices. The enrichment mechanism is determined by collecting current data, measuring solution conductivity, and by performing pH indicator experiments. These data reveal the dynamic nature of the enrichment mechanism. Specifically, they show the complex relationship between the ionic current gradients formed at the bipolar electrode and the extent of cation enrichment. Finally, we demonstrate cation enrichment is possible in buffer-free solutions containing up to 50.0 mM KCl. This finding is significant because it broadens the range of solutions in which membrane-free, electrochemical separations using bipolar electrodes can be performed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coupling between DNA replication, segregation, and the onset of constriction in Escherichia coli

Escherichia coli cell cycle features two critical cell-cycle checkpoints: initiation of replication and the onset of constriction. While the initiation of DNA replication has been extensively studied, it is less clear what triggers the onset of constriction and when exactly it occurs during the cell cycle. Here, using high-throughput fluorescence microscopy in microfluidic devices, we determine the timing for the onset of constriction relative to the replication cycle in different growth rates. Our single-cell data and modeling indicate that the initiation of constriction is coupled to replication-related processes in slow growth conditions. Furthermore, our data suggest that this coupling involves the mid-cell chromosome blocking the onset of constriction via some form of nucleoid occlusion occurring independently of SlmA and the Ter linkage proteins. This work highlights the coupling between replication and division cycles and brings up a new nucleoid mediated control mechanism in E. coli.

59 BASIC BIOLOGICAL SCIENCES↗

Cation-Specific Electrokinetic Separations Using Prussian Blue Intercalation Reactions

In this work, we report a new approach for forming ion depletion zones (IDZs) using intercalation reactions at an electrochemically controlled Prussian blue (PB) film. The experiments described here were performed using a microfluidic device, wherein a charged fluorophore in solution was used as a proxy to monitor IDZ formation. In the presence of K + , intercalation reactions proceed readily to form an IDZ, and thus enrich the fluorophore up to 37-fold. In the presence of the larger hydrated Li + or tetrabutylammonium (TBA + ) ions, however, ion intercalation proceeded less quickly than with K + . Slower ion intercalation resulted in a weaker IDZ and correspondingly lower enrichment factors of eight- and six-fold, respectively. These results are significant because they show that PB intercalation reactions selectively form an IDZ. Accordingly, we anticipate that these findings will lead to a better understanding and further interesting applications of intercalation materials like PB for efficient and selective enrichment and separations.

99 GENERAL AND MISCELLANEOUS↗

A microfluidic study of transient flow states in permeable media using fluorescent particle image velocimetry

Velocity fields in flow in permeable media are of great importance to many subsurface processes such as geologic storage of CO 2 , oil and gas extraction, and geothermal systems. Steady-state flow is characterized by velocity fields that do not change significantly over time. The flow field transitions to a new steady state once it experiences a disturbance such as a change in flow rate or in pressure gradient. This transition is often assumed to be instantaneous, which justifies the expression of constitutive relations as functions of instantaneous phase saturations. This work examines the evolution of velocity fields in a surrogate quasi-2D permeable medium using a microfluidic device, a microscopy system, and a high-speed camera. Tracer particles are injected into the medium along with DI water. The evolution of the velocity field is examined by tracing these particles in the captured images using the standard high-density particle image velocimetry algorithm founded on cross-correlation. The results suggest that the transition between steady states for an incompressible fluid takes a finite and non-negligible amount of time that is independent of the magnitude of the change in pressure gradient. The existence of transient states and the nature of the response during these states are readily interpreted by the principle of least action where flow gradually establishes an optimal configuration such that energy dissipation is 2 minimized. The findings provide evidence against the applicability of the assumption that flowing phases relax instantaneously to their steady states and, hence, against the accuracy of the classical multiphase extension of Darcy's law.

42 ENGINEERING↗

Controlling matric potential in microfluidics to examine microbial dynamics in unsaturated porous media

The use of microfluidics for the study of soil microbial ecology is an emerging field. Most microfluidic studies of biological systems, however, have been performed under fully saturated conditions that are not representative of natural soil. Therefore, while microfluidics offer many unique capabilities that other methodologies cannot, they are not currently suited to address the effects of matric potential, an important variable defining the microbial moisture niche. Here, a methodology is presented that allows the user to control the aqueous conditions within microfluidic networks by manipulating matric potential using a hanging water column. The method relies on hydrophilic surface treatment of the microfluidic device using polyvinyl alcohol (PVA) and incorporating a bed of small pores at the network boundaries, which serve as a porous ceramic plate analogue (PPA). The method was validated on a simple capillary bundle and then on a more complex pore network. A water retention curve, exhibiting hysteresis, was generated for the pore network over a narrow matric potential range of 0 to – 5 kPa. Both the drainage and wetting curves were reproducible, as were the spatial configuration and the number of fragmented moisture niches in the pore network, particularly on the drainage curve. In contrast, the wetting curve exhibited greater variability in spatial configuration due to the “ink bottle effect,” where capillarity was interrupted by wider pore bodies. Ultimately, the methodology provides realistic pore-scale moisture conditions that can be easily manipulated and maintained, enabling new opportunities to explore soil biophysics and microbial biogeography in unsaturated porous media. As a brief example, images showing the localization of fluorescently tagged Pantoea sp. YR343 at −4.3 kPa are presented, highlighting bacterial distributions in water films and air-water interfaces.

59 BASIC BIOLOGICAL SCIENCES↗

Transport and Assembly of Magnetic Surface Rotors**

This minireview focuses on recent advances with surface magnetic rotors, namely field-responsive spherical or anisotropic microparticles that translate close to, or are embedded in a confining surface. The application of external magnetic modulations allows these microscopic wheels to be remotely spun and steered while also tuning their interactions and inducing assembly from a collection of disordered, moving units. With optical microscopy one can observe and characterize the complex collective phenomena that emerge in dissipative colloidal systems driven far from equilibrium by external fields. From a technological point of view, magnetic surface rotors envisage implementation into microfluidic devices, and can be used for drug delivery, mixing as well as a model system for biological active matter.

36 MATERIALS SCIENCE↗

Temporal Sampling of Enzymes from Live Cells by Localized Electroporation and Quantification of Activity by SAMDI Mass Spectrometry

Abstract Measuring changes in enzymatic activity over time from small numbers of cells remains a significant technical challenge. In this work, a method for sampling the cytoplasm of cells is introduced to extract enzymes and measure their activity at multiple time points. A microfluidic device, termed the live cell analysis device (LCAD), is designed, where cells are cultured in microwell arrays fabricated on polymer membranes containing nanochannels. Localized electroporation of the cells opens transient pores in the cell membrane at the interface with the nanochannels, enabling extraction of enzymes into nanoliter‐volume chambers. In the extraction chambers, the enzymes modify immobilized substrates, and their activity is quantified by self‐assembled monolayers for matrix‐assisted laser desorption/ionization (SAMDI) mass spectrometry. By employing the LCAD‐SAMDI platform, protein delivery into cells is demonstrated. Next, it is shown that enzymes can be extracted, and their activity measured without a loss in viability. Lastly, cells are sampled at multiple time points to study changes in phosphatase activity in response to oxidation by hydrogen peroxide. With this unique sampling device and label‐free assay format, the LCAD with SAMDI enables a powerful new method for monitoring the dynamics of cellular activity from small populations of cells.

Mukherjee, Prithvijit↗

Breakdown of electroneutrality in nanopores

Ion transport in extremely narrow nanochannels has gained increasing interest in recent years due to unique physical properties at the nanoscale and the technological advances that allow us to study them. It is tempting to approach this confined regime with the theoretical tools and knowledge developed for membranes and microfluidic devices, and naively apply continuum models, such as the Poisson-Nernst-Planck and Navier-Stokes equations. However, it turns out that some of the most basic principles we take for granted in larger systems, such as the complete screening of surface charge by counter-ions, can break down under extreme confinement. Additionally, we show that in a truly one-dimensional system of ions interacting with three-dimensional electrostatic interactions, the screening length is exponentially large, and can easily exceed the macroscopic length of a nanotube. Without screening, electroneutrality breaks down within the nanotube, with fundamental consequences for ion transport and electrokinetic phenomena. In this work, we build a general theoretical framework for electroneutrality breakdown in nanopores, focusing on the most interesting case of a one-dimensional nanotube, and show how it provides an elegant interpretation for the peculiar scaling observed in experimental measurements of ionic conductance in carbon nanotubes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗