Carboxymethylcellulose adsorption on molybdenite: the effect of electrolyte composition on adsorption, bubble-surface collisions, and flotation.

The adsorption of carboxymethylcellulose polymers on molybdenite was studied using spectroscopic ellipsometry and atomic force microscopy imaging with two polymers of differing degrees of carboxyl group substitution and at three different electrolyte conditions: 1 × 10(-2) M KCl, 2.76 × 10(-2) M KCl, and simulated flotation process water of multicomponent electrolyte content, with an ionic strength close to 2.76 × 10(-2) M. A higher degree of carboxyl substitution in the adsorbing polymer resulted in adsorbed layers that were thinner and with more patchy coverage; increasing the ionic strength of the electrolyte resulted in increased polymer layer thickness and coverage. The use of simulated process water resulted in the largest layer thickness and coverage for both polymers. The effect of the adsorbed polymer layer on bubble-particle attachment was studied with single bubble-surface collision experiments recorded with high-speed video capture and image processing and also with single mineral molybdenite flotation tests. The carboxymethylcellulose polymer with a lower degree of substitution resulted in almost complete prevention of wetting film rupture at the molybdenite surface under all electrolyte conditions. The polymer with a higher degree of substitution prevented rupture only when adsorbed from simulated process water. Molecular kinetic theory was used to quantify the effect of the polymer on the dewetting dynamics for collisions that resulted in wetting film rupture. Flotation experiments confirmed that adsorbed polymer layer properties, through their effect on the dynamics of bubble-particle attachment, are critical to predicting the effectiveness of polymers used to prevent mineral recovery in flotation.

Discontinuous transition in a laminar fluid flow: a change of flow topology inside a droplet moving in a micron-size channel.

Even at moderate values of Reynolds number [e.g., Re=O(1)] a curved interface between liquids can induce an abrupt transition between topologically different configurations of laminar flow. Here we show for the first time direct evidence of a sharp transition in the speed of flow of a droplet upon a small increase of the value of the capillary number above a threshold and the associated change of topology of flow. The quantitative results on the dependence of the threshold capillary number on the contrast of viscosities and on the direction of transition cannot be explained by any of the existing theories and call for a new description.

Geometrical and electrical properties of indium tin oxide clusters in ink dispersions.

The analysis of the TEM images of indium tin oxide (ITO) clusters in ink solutions deposited from ink dispersions reveals that their geometry arises from a diffusion limited cluster aggregation (DLCA) process. We model films of ITO clusters as built through deposition of DLCA clusters made of primary spherical nanoparticles of 13 nm in diameter. The deposition is then followed by a further compactification process that imitates sintering. We determine the conductivity of the sintered films by mapping the problem to that of the resistor network in which the contact regions between the touching spheres provide the dominant electric resistance. For a given volume fraction, conductivity of the sintered films is shown to be larger than that for the randomly packed spheres. However, the larger a typical radius of gyration of the clusters the smaller the enhancement. We also provide numerical tests for the routines used in the interpretation of the TEM images.

Metabolic reprogramming under hypoxic storage preserves faster oxygen unloading from stored red blood cells.

Stored red blood cells (RBCs) incur biochemical and morphological changes, collectively termed the storage lesion. Functionally, the storage lesion manifests as slower oxygen unloading from RBCs, which may compromise the efficacy of transfusions where the clinical imperative is to rapidly boost oxygen delivery to tissues. Recent analysis of large real-world data linked longer storage with increased recipient mortality. Biochemical rejuvenation with a formulation of adenosine, inosine, and pyruvate can restore gas-handling properties, but its implementation is impractical for most clinical scenarios. We tested whether storage under hypoxia, previously shown to slow biochemical degradation, also preserves gas-handling properties of RBCs. A microfluidic chamber, designed to rapidly switch between oxygenated and anoxic superfusates, was used for single-cell oxygen saturation imaging on samples stored for up to 49 days. Aliquots were also analyzed flow cytometrically for side-scatter (a proposed proxy of O2 unloading kinetics), metabolomics, lipidomics, and redox proteomics. For benchmarking, units were biochemically rejuvenated at 4 weeks of standard storage. Hypoxic storage hastened O2 unloading in units stored to 35 days, an effect that correlated with side-scatter but was not linked to posttranslational modifications of hemoglobin. Although hypoxic storage and rejuvenation produced distinct biochemical changes, a subset of metabolites including pyruvate, sedoheptulose 1-phosphate, and 2/3 phospho-d-glycerate, was a common signature that correlated with changes in O2 unloading. Correlations between gas handling and lipidomic changes were modest. Thus, hypoxic storage of RBCs preserves key metabolic pathways and O2 exchange properties, thereby improving the functional quality of blood products and potentially influencing transfusion outcomes.

Integration of capillary-hydrodynamic logic circuitries for built-in control over multiple droplets in microfluidic networks.

Here, we show the successful implementation of advanced sequential logic in droplet microfluidics, whose principles rely on capillary wells establishing stationary states, where droplets can communicate remotely via pressure impulses, influencing each other and switching the device states. All logic operations perform spontaneously due to the utilization of nothing more than capillary-hydrodynamic interactions, inherent for the confined biphasic flow. Our approach offers integration feasibility allowing to encode unprecedentedly long algorithms, e.g., 1000-droplet counting. This work has the potential for the advancement of liquid computers and thereby could participate in the development of the next generation of portable microfluidic systems with embedded control, enabling applications from single-cell analysis and biochemical assays to materials science.

Direction of epithelial folding defines impact of mechanical forces on epithelial state.

Cell shape dynamics during development is tightly regulated and coordinated with cell fate determination. Triggered by an interplay between biochemical and mechanical signals, epithelia form complex tissues by undergoing coordinated cell shape changes, but how such spatiotemporal coordination is controlled remains an open question. To dissect biochemical signaling from purely mechanical cues, we developed a microfluidic system that experimentally triggers epithelial folding to recapitulate stereotypic deformations observed in vivo. Using this system, we observe that the apical or basal direction of folding results in strikingly different mechanical states at the fold boundary, where the balance between tissue tension and torque (arising from the imposed curvature) controls the spread of folding-induced calcium waves at a short timescale and induces spatial patterns of gene expression at longer timescales. Our work uncovers that folding-associated gradients of cell shape and their resulting mechanical stresses direct spatially distinct biochemical responses within the monolayer.

Accounting for corner flow unifies the understanding of droplet formation in microfluidic channels.

While shear emulsification is a well understood industrial process, geometrical confinement in microfluidic systems introduces fascinating complexity, so far prohibiting complete understanding of droplet formation. The size of confined droplets is controlled by the ratio between shear and capillary forces when both are of the same order, in a regime known as jetting, while being surprisingly insensitive to this ratio when shear is orders of magnitude smaller than capillary forces, in a regime known as squeezing. Here, we reveal that further reduction of-already negligibly small-shear unexpectedly re-introduces the dependence of droplet size on shear/capillary-force ratio. For the first time we formally account for the flow around forming droplets, to predict and discover experimentally an additional regime-leaking. Our model predicts droplet size and characterizes the transitions from leaking into squeezing and from squeezing into jetting, unifying the description for confined droplet generation, and offering a practical guide for applications.

Simultaneous Measurement of Viscosity and Optical Density of Bacterial Growth and Death in a Microdroplet.

Herein, we describe a novel method for the assessment of droplet viscosity moving inside microfluidic channels. The method allows for the monitoring of the rate of the continuous growth of bacterial culture. It is based on the analysis of the hydrodynamic resistance of a droplet that is present in a microfluidic channel, which affects its motion. As a result, we were able to observe and quantify the change in the viscosity of the dispersed phase that is caused by the increasing population of interacting bacteria inside a size-limited system. The technique allows for finding the correlation between the viscosity of the medium with a bacterial culture and its optical density. These features, together with the high precision of the measurement, make our viscometer a promising tool for various experiments in the field of analytical chemistry and microbiology, where the rigorous control of the conditions of the reaction and the monitoring of the size of bacterial culture are vital.

Continuous Recirculation of Microdroplets in a Closed Loop Tailored for Screening of Bacteria Cultures.

Emerging microfluidic technology has introduced new precision controls over reaction conditions. Owing to the small amount of reagents, microfluidics significantly lowers the cost of carrying a single reaction. Moreover, in two-phase systems, each part of a dispersed fluid can be treated as an independent chemical reactor with a volume from femtoliters to microliters, increasing the throughput. In this work, we propose a microfluidic device that provides continuous recirculation of droplets in a closed loop, maintaining low consumption of oil phase, no cross-contamination, stabilized temperature, a constant condition of gas exchange, dynamic feedback control on droplet volume, and a real-time optical characterization of bacterial growth in a droplet. The channels (tubing) and junction cubes are made of Teflon fluorinated ethylene propylene (FEP) to ensure non-wetting conditions and to prevent the formation of biofilm, which is particularly crucial for biological experiments. We show the design and operation of a novel microfluidic loop with the circular motion of microdroplet reactors monitored with optical sensors and precision temperature controls. We have employed the proposed system for long term monitoring of bacterial growth during the antibiotic chloramphenicol treatment. The proposed system can find applications in a broad field of biomedical diagnostics and therapy.

Simple modular systems for generation of droplets on demand.

This report provides practical guidelines for the use of inexpensive electromagnetic valves characterized by large dead volumes (tens to hundreds of µL) for the generation of small (nL) droplets on demand in microfluidic chips. We analyze the role of the ratio of resistances and of the elastic capacitance of the fluidic connectors between the reservoir of the liquid, the valve and the microfluidic chip in the reliable and precise formation of micro droplets on demand. We also demonstrate and examine the use of conventional electromagnetic squeeze valves in the generation of small droplets on demand with a similar set of design rules.

Microfluidic traps for hard-wired operations on droplets.

We present microfluidic modules (traps) that allow us to lock, shift, dose and merge micro-aliquots of liquid precisely. The precision is hard-wired into the geometry of the device: small values of the capillary number guarantee reproducibility of operation over a range of rates of flow that need not be controlled precisely. The modules can be integrated into systems that perform complicated protocols on micro-droplets while not requiring precision in forcing the flow.

Custom tailoring multiple droplets one-by-one.

We report automated generation of arbitrary sequences of multiple microdroplets with online and individual control over the number of cores and volumes of all the constituents (cores and shells) of each of the multiple droplets. We show that a given sequence of volumes of the cores always folds to the same final three-dimensional architecture. The method presents the first proof-of-concept for the ability to design the three-dimensional structure of multiple droplets. We discuss the potential use of the technique in the formulation of predetermined distribution of drug release capsules and for automated generation of functional chemical microdroplet networks.

Block-and-break generation of microdroplets with fixed volume.

We introduce a novel type of droplet generator that produces droplets of a volume set by the geometry of the droplet generator and not by the flow rates of the liquids. The generator consists of a classic T-junction with a bypass channel. This bypass directs the continuous fluid around the forming droplets, so that they can fill the space between the inlet of the dispersed phase and the exit of the bypass without breaking. Once filled, the dispersed phase blocks the exit of the bypass and is squeezed by the continuous fluid and broken off from the junction. We demonstrate the fixed-volume droplet generator for (i) the formation of monodisperse droplets from a source of varying flow rates, (ii) the formation of monodisperse droplets containing a gradation of solute concentration, and (iii) the parallel production of monodisperse droplets.

Effects of unsteadiness of the rates of flow on the dynamics of formation of droplets in microfluidic systems.

Oscillations of the input rates of flow have a significant impact on the dynamics of formation of droplets in microfluidic systems and on the quality of generated emulsions.

Automated high-throughput generation of droplets.

We report a microfluidic technique for high-throughput generation of droplets of nanolitre volume in parallel channels with online control of the volumes, volume fraction and distribution of droplet volumes with the use of two external valves.

Speed of flow of individual droplets in microfluidic channels as a function of the capillary number, volume of droplets and contrast of viscosities.

Droplet microfluidic techniques offer an attractive compromise between the throughput (of i.e. reactions per second) and the number of input/output controls needed to control them. Reduction of the number of controls follows from the confinement to essentially one-dimensional flow of slugs in channels which--in turn--relies heavily on the speed of flow of droplets. This speed is a complicated function of numerous parameters, including the volume of droplets (or length L of slugs), their viscosity µ(d), viscosity µ(c) and rate of flow of the continuous phase, interfacial tension and geometry of the cross-section of the channel. Systematic screens of the impact of these parameters on the speed of droplets remain an open challenge. Here we detail an automated system that screens the speeds of individual droplets at a rate of up to 2000 experiments per hour, with high precision and without human intervention. The results of measurements in channels of square cross-section (of width w = 360 µm) for four different values of the contrast of viscosities λ = µ(d)/µ(c) = 0.3, 1, 3, and 33, wide ranges of values of the capillary number Ca ∈ (10(-4), 10(-1)), and wide ranges of lengths of droplets l = L/w∈ (0.8, 30) show that the speed of droplets depends significantly both on l and on λ. The dependence on Ca is very strong for λ > 1, while it is less important both for λ ≤ 1 and for λ ≫ 1.