Creaming Stability of Flocculated Monodisperse Oil-in-Water Emulsions

The influence of droplet flocculation on the creaming stability of monodisperse n-hexadecane oil-in-water emulsions was studied. The creaming velocity of emulsions with different droplet radii (0.43 and 0.86 μm), droplet concentrations (1-67 vol%), and sodium dodecyl sulfate (SDS) concentrations (7-80 mM) were measured. Depletion flocculation was observed in the emulsions when the aqueous phase SDS concentration exceeded a particular level ( approximately 40 mM for 0.43-μm droplets and approximately 15 mM for 0.86-μm droplets). Creaming was monitored by measuring the back-scattered light from an emulsion as a function of its height. The creaming velocity increased with increasing flocculation and decreased with increasing droplet concentration. These results have important implications for the formulation of emulsion-based materials. Copyright 2000 Academic Press.     

Droplet size based separation by deterministic lateral displacement-separating droplets by cell--induced shrinking

We present a novel method for passive separation of microfluidic droplets by size at high throughput using deterministic lateral displacement (DLD). We also show that droplets containing Saccharomyces cerevisiae shrink significantly during incubation while droplets containing only yeast media retain or slightly increase their size. We demonstrate the DLD device by sorting out shrunken yeast-cell containing droplets from 31% larger diameter droplets which were generated at the same time containing only media, present at a >40-fold excess. This demonstrates the resolving power of droplet separation by DLD and establishes that droplets can be separated for a biological property of the droplet contents discriminated by a change of the physical properties of the droplet. Thus suggesting that this technique may be used for e.g. clonal selection. The same device also separates 11 μm from 30 μm droplets at a rate of 12,000 droplets per second, more than twofold faster than previously demonstrated passive hydrodynamic separation devices.     

A method for investigating size distributions of aqueous droplets in the range 0.5–10 μm produced by pneumatic nebulizers

A novel method is described for the measurement of the droplet size distributions produced by nebulizers commonly employed in analytical atomic spectroscopy. It is shown theoretically that, at sufficiently high concentrations of dissolved sodium chloride, the evaporation of water from droplets as small as 0.5 μm in diameter may be reduced to a negligible level. When evaporation is reduced by the presence of a dissolved salt, a conventional cascade impactor may be used to elucidate the droplet size distribution. Empirical observations confirm that, at a sodium concentration of 10,000 μg ml^?1, evaporation is negligible: the method may be used to study particle size distributions over the size range 0.5–10 μm.     

Deformation and breakup of micro- and nanoparticle stabilized droplets in microfluidic extensional flows

Using a microfluidic flow-focusing device, monodisperse water droplets in oil were generated and their interface populated by either 1 μm or 500 nm amine modified silica particles suspended in the water phase. The deformation and breakup of these Pickering droplets were studied in both pure extensional flow and combined extensional and shear flow at various capillary numbers using a microfluidic hyperbolic contraction. The shear resulted from droplet confinement and increased with droplet size and position along the hyperbolic contraction. Droplet deformation was found to increase with increasing confinement and capillary number. At low confinements and low capillary numbers, the droplet deformation followed the predictions of theory. For fully confined droplets, where the interface was populated by 1 μm silica particles, the droplet deformation increased precipitously and two tails were observed to form at the rear of the droplet. These tails were similar to those seen for surfactant covered droplets. At a critical capillary number, daughter droplets were observed to stream from these tails. Due to the elasticity of the particle-laden interface, these drops did not return to a spherical shape, but were observed to buckle. Although increases in droplet deformation were observed, no tail streaming occurred for the 500 nm silica particle covered droplets over the range of capillary numbers studied.     

Homogeneous ice nucleation from aqueous inorganic/organic particles representative of biomass burning: water activity, freezing temperatures, nucleation rates

Homogeneous ice nucleation plays an important role in the formation of cirrus clouds with subsequent effects on the global radiative budget. Here we report on homogeneous ice nucleation temperatures and corresponding nucleation rate coefficients of aqueous droplets serving as surrogates of biomass burning aerosol. Micrometer-sized (NH(4))(2)SO(4)/levoglucosan droplets with mass ratios of 10:1, 1:1, 1:5, and 1:10 and aqueous multicomponent organic droplets with and without (NH(4))(2)SO(4) under typical tropospheric temperatures and relative humidities are investigated experimentally using a droplet conditioning and ice nucleation apparatus coupled to an optical microscope with image analysis. Homogeneous freezing was determined as a function of temperature and water activity, a(w), which was set at droplet preparation conditions. The ice nucleation data indicate that minor addition of (NH(4))(2)SO(4) to the aqueous organic droplets renders the temperature dependency of water activity negligible in contrast to the case of aqueous organic solution droplets. The mean homogeneous ice nucleation rate coefficient derived from 8 different aqueous droplet compositions with average diameters of ～60 μm for temperatures as low as 195 K and a(w) of 0.82-1 is 2.18 × 10(6) cm(-3) s(-1). The experimentally derived freezing temperatures and homogeneous ice nucleation rate coefficients are in agreement with predictions of the water activity-based homogeneous ice nucleation theory when taking predictive uncertainties into account. However, the presented ice nucleation data indicate that the water activity-based homogeneous ice nucleation theory overpredicts the freezing temperatures by up to 3 K and corresponding ice nucleation rate coefficients by up to ～2 orders of magnitude. A shift of 0.01 in a(w), which is well within the uncertainty of typical field and laboratory relative humidity measurements, brings experimental and predicted freezing temperatures and homogeneous ice nucleation rate coefficients into agreement. The experimentally derived ice nucleation data are applied to constrain the water activity-based homogeneous ice nucleation theory to smaller than ±1 order of magnitude compared to the predictive uncertainty of larger than ±6 orders of magnitude. The atmospheric implications of these findings are discussed.     

Emulsion Templating of Poly(lactic acid) Particles: Droplet Formation Behavior

Monodisperse poly(dl-lactic acid) (PLA) particles of diameters between 11 and 121 μm were fabricated in flow focusing glass microcapillary devices by evaporation of dichloromethane (DCM) from emulsion droplets at room temperature. The dispersed phase was 5% (w/w) PLA in DCM containing 0.1-2 mM Nile Red and the continuous phase was 5% (w/w) poly(vinyl alcohol) in reverse osmosis water. Particle diameter was 2.7 times smaller than the diameter of the emulsion droplet template, indicating very low particle porosity. Monodisperse droplets have only been produced under dripping regime using a wide range of dispersed phase flow rates (0.002-7.2 cm(3)·h(-1)), continuous phase flow rates (0.3-30 cm(3)·h(-1)), and orifice diameters (50-237 μm). In the dripping regime, the ratio of droplet diameter to orifice diameter was inversely proportional to the 0.39 power of the ratio of the continuous phase flow rate to dispersed phase flow rate. Highly uniform droplets with a coefficient of variation (CV) below 2% and a ratio of the droplet diameter to orifice diameter of 0.5-1 were obtained at flow rate ratios of 4-25. Under jetting regime, polydisperse droplets (CV > 6%) were formed by detachment from relatively long jets (between 4 and 10 times longer than droplet diameter) and a ratio of the droplet size to orifice size of 2-5.     

A surface topography assisted droplet manipulation platform for biomarker detection and pathogen identification

This paper reports a droplet microfluidic, sample-to-answer platform for the detection of disease biomarkers and infectious pathogens using crude biosamples. The platform exploited the dual functionality of silica superparamagnetic particles (SSP) for solid phase extraction of DNA and magnetic actuation. This enabled the integration of sample preparation and genetic analysis within discrete droplets, including the steps of cell lysis, DNA binding, washing, elution, amplification and detection. The microfluidic device was self contained, with all reagents stored in droplets, thereby eliminating the need for fluidic coupling to external reagent reservoirs. The device incorporated unique surface topographic features to assist droplet manipulation. Pairs of micro-elevations were created to form slits that facilitated efficient splitting of SSP from droplets. In addition, a compact sample handling stage, which integrated the magnet manipulator, the droplet microfluidic device and a Peltier thermal cycler, was built for convenient droplet manipulation and real-time detection. The feasibility of the platform was demonstrated by analysing ovarian cancer biomarker Rsf-1 and detecting Escherichia coli with real time polymerase chain reaction and real time helicase dependent amplification.     

Emulsion of aqueous-based nonspherical droplets in aqueous solutions by single-chain surfactants: templated assembly by nonamphiphilic lyotropic liquid crystals in water

Single-chain surfactants usually emulsify and stabilize oily substances into droplets in an aqueous solution. Here, we report a coassembly system, in which single types of anionic or non-ionic surfactants emulsify a class of water-soluble nonamphiphilic organic salts with fused aromatic rings in aqueous solutions. The nonamphiphilic organic salts are in turn promoted to form droplets of water-based liquid crystals (chromonic liquid crystals) encapsulated by single-chain surfactants. The droplets, stabilized against coalescence by encapsulated in a layer (or layers) of single chain surfactants, are of both nonspherical tactoid (elongated ellipsoid with pointy ends) and spherical shapes. The tactoids have an average long axis of ～9 μm and a short axis of ～3.5 μm with the liquid crystal aligning parallel to the droplet surface. The spherical droplets are 5-10 μm in diameter and have the liquid crystal aligning perpendicular to the droplet surface and a point defect in the center. Cationic and zwitterionic surfactants studied in this work did not promote the organic salt to form droplets. These results illustrate the complex interplay of self-association and thermodynamic incompatibility of molecules in water, which can cause new assembly behavior, including potential formation of vesicles or other assemblies, from surfactants that usually form only micelles. These unprecedented tactoidal shaped droplets also provide potential for the fabrication of new soft organic microcapsules.     

New Pickering emulsions stabilized by bacterial cellulose nanocrystals

We studied oil in water Pickering emulsions stabilized by cellulose nanocrystals obtained by hydrochloric acid hydrolysis of bacterial cellulose. The resulting solid particles, called bacterial cellulose nanocrystals (BCNs), present an elongated shape and low surface charge density, forming a colloidal suspension in water. The BCNs produced proved to stabilize the hexadecane/water interface, promoting monodispersed oil in water droplets around 4 μm in diameter stable for several months. We characterized the emulsion and visualized the particles at the surface of the droplets by scanning electron microscopy (SEM) and calculated the droplet coverage by varying the BCN concentration in the aqueous phase. A 60% coverage limit has been defined, above which very stable, deformable droplets are obtained. The high stability of the more covered droplets was attributed to the particle irreversible adsorption associated with the formation of a 2D network. Due to the sustainability and low environmental impact of cellulose, the BCN based emulsions open opportunities for the development of environmentally friendly new materials.     

Ultrasensitive absorption spectroscopy of optically-trapped aerosol droplets

High-sensitivity optical absorption measurements on individual sub-picoliter aqueous droplets are reported using aerosol optical tweezers to simultaneously manipulate and characterize a sample droplet and a control droplet for comparison. It is demonstrated that the detection sensitivity to trace analytes is set by the weak absorption by the solvent, water, and that absorbances less than 5 x 10(-7) can be measured over pathlengths of less than 10 microm. The potential applications of this approach to analyze aerosol particle composition and to perform trace analysis are discussed.     

High-speed, clinical-scale microfluidic generation of stable phase-change droplets for gas embolotherapy

In this study we report on a microfluidic device and droplet formation regime capable of generating clinical-scale quantities of droplet emulsions suitable in size and functionality for in vivo therapeutics. By increasing the capillary number-based on the flow rate of the continuous outer phase-in our flow-focusing device, we examine three modes of droplet breakup: geometry-controlled, dripping, and jetting. Operation of our device in the dripping regime results in the generation of highly monodisperse liquid perfluoropentane droplets in the appropriate 3-6 μm range at rates exceeding 10(5) droplets per second. Based on experimental results relating droplet diameter and the ratio of the continuous and dispersed phase flow rates, we derive a power series equation, valid in the dripping regime, to predict droplet size, D(d) approximately equal 27(Q(C)/Q(D))(-5/12). The volatile droplets in this study are stable for weeks at room temperature yet undergo rapid liquid-to-gas phase transition, and volume expansion, above a uniform thermal activation threshold. The opportunity exists to potentiate locoregional cancer therapies such as thermal ablation and percutaneous ethanol injection using thermal or acoustic vaporization of these monodisperse phase-change droplets to intentionally occlude the vessels of a cancer.     

Encapsulated droplets with metered and removable oil shells by electrowetting and dielectrophoresis

A water-core and oil-shell encapsulated droplet exhibits several advantages including enhanced fluidic manipulation, reduced biofouling, decreased evaporation, and simplified device packaging. However, obtaining the encapsulated droplet with an adjustable water-to-oil volume ratio and a further removable oil shell is not possible by reported techniques using manual pipetting or droplet splitting. We report a parallel-plate device capable of generation, encapsulation, rinsing, and emersion of water and/or oil droplets to achieve three major aims. The first aim of our experiments was to form encapsulated droplets by merging electrowetting-driven water droplets and dielectrophoresis-actuated oil droplets whose volumes were precisely controlled. 25 nL water droplets and 2.5 nL non-volatile silicone oil droplets with various viscosities (10, 100, and 1000 cSt) were individually created from their reservoirs to form encapsulated droplets holding different water-to-oil volume ratios of 10:1 and 2:1. Secondly, the driving voltages, evaporation rates, and biofouling of the precise encapsulated droplets were measured. Compared with the bare and immersed droplets, we found the encapsulated droplets (oil shells with lower viscosities and larger volumes) were driven at a smaller voltage or for a wider velocity range. In the dynamic evaporation tests, at a temperature of 20 ± 1 °C and relative humidity of 45 ± 3%, 10 cSt 10:1 and 2:1 encapsulated droplets were moved at the velocity of 0.25 mm s(-1) for 22 and 35 min until losing 16.6 and 17.5% water, respectively, while bare droplets followed the driving signal for only 6 min when 11.4% water was lost. Evaporation was further diminished at the rate of 0.04% min(-1) for a carefully positioned stationary encapsulated droplet. Biofouling of 5 μg ml(-1) FITC-BSA solution was found to be eliminated by the encapsulated droplet from the fluorescent images. The third aim of our research was to remove the oil shell by dissolving it in an on-chip rinsing reservoir containing hexane. After emersion from the rinsing reservoir, the bare droplet was restored as hexane rapidly evaporated. Removal of the oil shell would not only increase the evaporation of the core droplet when necessary, but also enhance the signal-to-noise ratio in the following detection steps.     

Droplet-based microextraction in the aqueous two-phase system

This report is about microfluidic extraction systems based on droplets of aqueous two-phase system. Mass transfer between continuous phase and dispersed droplet is demonstrated by microextraction of ruthenium red in a microfluidic device. Droplets are generated with electrohydrodynamic method in the same device. By comparing brightness in the digital image of a solution with known concentrations of ruthenium red and those of a droplet in the microextraction, ruthenium red concentration was measured along the microextraction channel, resulting in good agreement with a simple diffusion model. The maximum partition coefficient was 9.58 in the experiment with the 70-mm-long-channel microextractor. The method is usable for terminating microextraction by electrohydrodynamic manipulation of droplet movement direction. Droplets of different ruthenium red concentration, 0.12 and 0.24% (w/w) in this experiment, can be moved to desired place of microfluidic system for further reaction through respectively branched outlets. In this study droplet-based microextraction is demonstrated and the mass transport is numerically analyzed by solving the diffusion–dissolution model.     

Modulation of emulsion rheology through electrostatic heteroaggregation of oppositely charged lipid droplets: influence of particle size and emulsifier content

The influence of electrostatically-induced heteroaggregation of oppositely charged lipid droplets on the rheology and stability of emulsions has been studied. 20 wt.% oil-in-water emulsions (pH 6) containing oppositely charged droplets were fabricated by mixing cationic lactoferrin-coated lipid droplets with anionic β-lactoglobulin-coated lipid droplets. Emulsions containing mixtures of droplets with different charges (positive or negative) and sizes (large or small) were prepared, and then their overall particle characteristics (ζ-potential and size) and rheology were measured. Emulsions formed by mixing positive droplets and negative droplets that were both relatively small (d(43) ≈ 0.3 μm) exhibited extensive flocculation and had paste-like properties at intermediate positive-to-negative particle ratios. On the other hand, emulsions formed by mixing positive droplets and negative droplets that were both relatively large (d(43) ≈ 3 μm) exhibited little aggregation and had relatively low viscosities at all particle ratios. Emulsions with small negative droplets and large positive droplets (or vice versa), exhibited some aggregation and viscosity enhancement at intermediate particle ratios. The presence of relatively high levels of protein in the aqueous phase of mixed emulsions reduced the level of droplet aggregation and viscosity enhancement observed, which was attributed to the ability of protein molecules to bind to droplet surfaces and neutralize their charges. Electrostatically-induced heteroaggregation of lipid droplets may be a useful means of controlling the physicochemical properties of emulsion-based products in the food, personal care, pharmaceutical and cosmetic industries.     

Characterization of a novel particle into liquid sampler for analysis of single fluorescent aerosol particles through capillary electrophoresis

An approach to sample and analyze single aerosolized droplets (<10 nL) of solutions containing fluorescein isothiocyanate (FITC) labeled glycine (GLY) and glutamic acid (GLU) is demonstrated. The sampling approach is based on inertial impaction in which the sample particle is accelerated through a nozzle and directly into a small drop of buffered solution (20 mM borate, pH = 10) suspended at the end of a coaxial tube of stainless steel and a fused silica capillary. A spherical light scattering cell and laser (λ = 532 nm) is used to detect the arrival of particles at the buffered droplet. Upon dissolution and/or mixing, a portion of the sample is injected onto the fused silica capillary for subsequent chemical analysis by capillary electrophoresis (CE) and detection by laser-induced fluorescence (LIF). It was found that the inertial impaction approach sampled particles >1 μm diameter with an efficiency of 80% or greater. At 15 kV applied potential, the FITC conjugates of GLY and GLU could be resolved in less than 120 s allowing qualitative analysis of the contents of single dispersed particles. However, the extent to which the sample is diluted into the buffer droplet varied significantly on a per-particle basis that caused >80% R.S.D. in fluorescence peak heights. This aspect of the method would necessitate the use of internal standards for quantitative analysis of materials present within the particles. It is envisaged that further improvements to the device described may ultimately lead to analysis of the contents of single particles dispersed in earth's atmosphere.     

Controlled generation of droplets using an electric field in a flow-focusing paper-based device

Droplet-based microfluidics is a modular platform in high-throughput single-cell and small sample analyses. However, this droplet microfluidic system was widely fabricated using soft lithography or glass capillaries, which is expensive and technically demanding for various applications, limiting use in resource-poor settings. Besides, the variation in droplet size is also restricted due to the limitations on the operating forces that the paper-based platform is able to withstand. Herein, we develop a fully integrated paper-based droplet microfluidic platform for conducting droplet generation and cell encapsulation in independent aqueous droplets dispersed in a carrier oil by incorporating electric fields. Through imposing an electric field, the droplet size would decrease with increasing the electric field and smaller droplets can be produced at high applied voltage. The droplet diameter can be adjusted by the ratio of inner and outer flow velocities as well as the applied electric field. We also demonstrated the proof of concept encapsulation application of our paper device by encapsulating yeast cells under an electric field. Using a simple wax printing method, carbon electrodes can be integrated on the paper. The integrated paper-based microfluidic platform can be fabricated easily and conducted outside of centralized laboratories. This microfluidic system shows great potential in drug and cell investigations by encapsulating cells in resource-limited environments.     

基于超声振动的微液滴生成装置设计与实验研究

设计了一种基于V型直线超声电机驱动的微液滴生成装置用于制备具有微米级尺寸的微液滴.此装置由基于V型直线超声电机驱动的微液滴生成部件、基于V型直线超声电机的三维位移控制平台和基于压电振子的微液滴分离部件组成.其中,生成部件包含超声电机、医用注射器、硅胶软管和自制的玻璃基微喷嘴.利用控制器驱动直线超声电机高精度地移动,由滑台推动注射器,在玻璃基喷嘴尖端产生附着的微小液滴;再利用压电振子激发杆状喷嘴的固有振型,使得附着的液滴克服粘性力从微喷嘴尖端分离,落在一定的范围内, 并计算生成的球形微液滴的半径.以蒸馏水作为初始液体,探究此装置生成的微液滴的特性.研究结果表明,蒸馏水在直线电机的精密驱动下,在微喷嘴尖端形成附着的球冠状液滴.通过分离部件的振动,附着的液滴克服自身的粘性力从喷嘴尖端分离, 形成球形液滴,通过测量得出此装置生成的球形液滴的半径小于40 μm.     

Hydrogel droplet microarrays with trapped antibody-functionalized beads for multiplexed protein analysis

Antibody microarrays are a powerful tool for rapid, multiplexed profiling of proteins. 3D microarray substrates have been developed to improve binding capacity, assay sensitivity, and mass transport, however, they often rely on photopolymers which are difficult to manufacture and have a small pore size that limits mass transport and demands long incubation time. Here, we present a novel 3D antibody microarray format based on the entrapment of antibody-coated microbeads within alginate droplets that were spotted onto a glass slide using an inkjet. Owing to the low concentration of alginate used, the gels were highly porous to proteins, and together with the 3D architecture helped enhance mass transport during the assays. The spotting parameters were optimized for the attachment of the alginate to the substrate. Beads with 0.2 μm, 0.5 μm and 1 μm diameter were tested and 1 μm beads were selected based on their superior retention within the hydrogel. The beads were found to be distributed within the entire volume of the gel droplet using confocal microscopy. The assay time and the concentration of beads in the gels were investigated for maximal binding signal using one-step immunoassays. As a proof of concept, six proteins including cytokines (TNFα, IL-8 and MIP/CCL4), breast cancer biomarkers (CEA and HER2) and one cancer-related protein (ENG) were profiled in multiplex using sandwich assays down to pg mL(-1) concentrations with 1 h incubation without agitation in both buffer solutions and 10% serum. These results illustrate the potential of beads-in-gel microarrays for highly sensitive and multiplexed protein analysis.     

Electro-optic effect,propagation loss,and switching speed in polymers containing nano-sized droplets of liquid crystal

Polymers containing droplets of liquid crystal smaller than 100 nm, which have good transparency and easily form films, were prepared under various conditions to evaluate their potential as electro-optic materials for waveguide-type devices. By varying the liquid crystal concentration and the strength of the UV irradiation causing photo-induced phase separation of the droplets, we were able to control the droplet size and density. We have clarified how the birefringence generated in an applied electric field, switching speed, and optical loss of light propagating in the film depend on droplet size and density. Polymer materials having a large electro-optic effect (δn = 0.001 at 8 V μm^-1), low propagation loss (~2.5 dB cm^-1), and fast response time (~10 μs) have been developed.     

Coalescence-assisted generation of single nanoliter droplets with predefined composition

We demonstrate the generation of highly accurate nanoliter droplets with a predefined composition. This composition control over a single droplet is achieved by merging two droplets with known concentrations and defined volumes. A forced coalescence is accomplished by synchronizing two piezoelectric-based active droplet generators. A microscope-mounted CCD camera is used to record, quantify and monitor the process to assure its high fidelity. The device is disposable, surfactant free, simple to operate and does not require microelectrode fabrication. It delivers a single on-demand droplet with adjustable high resolution mixing ratios up to 9 at a volume range of 1-10 nanoliters. The presented platform offers, for the first time, a means to perform droplet-based high-throughput screening in the nanoliter range.