Electrophoretic mobility of oil droplets in electrolyte and surfactant solutions

Electrophoretic mobility of oil droplets of micron sizes in PBS and ionic surfactant solutions was measured in this paper. The experimental results show that, in addition to the applied electric field, the speed and the direction of electrophoretic motion of oil droplets depend on the surfactant concentration and on if the droplet is in negatively charged SDS solutions or in positively charged hexadecyltrimethylammonium bromide (CTAB) solutions. The absolute value of the electrophoretic mobility increases with increased surfactant concentration before the surfactant concentration reaches to the CMC. It was also found that there are two vortices around the oil droplet under the applied electric field. The size of the vortices changes with the surfactant and with the electric field. The vortices around the droplet directly affect the drag of the flow field to the droplet motion and should be considered in the studies of electrophoretic mobility of oil droplets. The existence of the vortices will also influence the determination and the interpretation of the zeta potential of the oil droplets based on the measured mobility data.     

Droplet evaporation study applied to DNA chip manufacturing

DNA chips are potentially powerful technologies for genotyping and gene expression profiling that rely on comparative analyses of up to thousands of "spots of analysis" on a glass support. The spot quality throughout the support influences spot-to-spot variations within an array and the repeatability of data across experiments. For glass slide DNA microarrays, droplets of DNA solution are deposited on functionalized glass slides and left to react through complete evaporation of the droplet. On hydrophobic flat surfaces, different modes of droplet evaporation can be attained. Under atmospheric pressure, water droplets tend to evaporate under two main regimes. Initially, the droplet flattens with a constant contact area, and then the droplet shrinks at a constant contact angle. As a result, the diameter and morphology of thousands of spots on microarrays are not uniform. This leads to poor and unreliable data processing results. In this work, we report the evaporation of an aqueous solution under a constant contact area mode. Evaporation under reduced pressure and the effect of reagent additives to the solution have been investigated. Video microscopy and digital image analysis techniques were applied to monitor the evaporation of the droplets. A mixture of surfactants was developed to maintain a constant area regime during evaporation and to form homogeneous spots. The control of some physicochemical properties (wetting, evaporation rate) of the droplet allows the formation of well-controlled spots compatible with DNA grafting. The influence of surfactant molecules on the mechanisms of evaporation is also discussed.     

pH-Sensitive self-propelled motion of oil droplets in the presence of cationic surfactants containing hydrolyzable ester linkages

Self-propelled oil droplets in a nonequilibrium system have drawn much attention as both a primitive type of inanimate chemical machinery and a dynamic model of the origin of life. Here, to create the pH-sensitive self-propelled motion of oil droplets, we synthesized cationic surfactants containing hydrolyzable ester linkages. We found that n-heptyloxybenzaldehyde oil droplets were self-propelled in the presence of ester-containing cationic surfactant. In basic solution prepared with sodium hydroxide, oil droplets moved as molecular aggregates formed on their surface. Moreover, the self-propelled motion in the presence of the hydrolyzable cationic surfactant lasted longer than that in the presence of nonhydrolyzable cationic surfactant. This is probably due to the production of a fatty acid by the hydrolysis of the ester-containing cationic surfactant and the subsequent neutralization of the fatty acid with sodium hydroxide. A complex surfactant was formed in the aqueous solution because of the cation and anion combination. Because such complex formation can induce both a decrease in the interfacial tension of the oil droplet and self-assembly with n-heptyloxybenzaldehyde and lauric acid in the aqueous dispersion, the prolonged movement of the oil droplet may be explained by the increase in heterogeneity of the interfacial tension of the oil droplet triggered by the hydrolysis of the ester-containing surfactant.     

Mechanistic studies of droplet electrophoresis: A review

Electrophoresis (EP) of droplets is an intriguing phenomenon that has applications in biological systems, separation strategies, and reactor engineering. Droplet EP is significantly different from the classic particle EP because of droplet characteristics such as a mobile surface charge and the nonrigidity of the interface. Also, the liquid–liquid system, where there is an interplay between the hydrodynamic and electrokinetic forces in both phases, adds to the complexity of electrophoretic motion. Due to the vast amount of potential applications of droplet EP, a mechanistic understanding of the droplet motion in the presence of an external electric field is crucial. This review provides a background on the mechanism of droplet EP and summarizes the intrinsic interplay between the different relevant forces in these systems. The review also describes the key differences between droplet EP and particle EP, and the impact of these differences on droplet mobility. Additionally, we schematically summarize the effects of key parameters on droplet EP mobility, such as electric double layer polarization, the development of internal flow inside a droplet and boundary effects.     

Rounded multi-level microchannels with orifices made in one exposure enable aqueous two-phase system droplet microfluidics

Exposure of a negative photoresist-coated glass slide with diffused light from the backside through a mask with disconnected features provides multi-level rounded channels with narrow orifices in one exposure. Using these structures, we construct microfluidic systems capable of creating aqueous two-phase system droplets where one aqueous phase forms droplets and the other aqueous phase forms the surrounding matrix. Unlike water-in-oil droplet systems, aqueous two-phase systems can have very low interfacial tensions that prevent spontaneous droplet formation. The multi-level channels fabricated by backside lithography satisfy two conflicting needs: (i) the requirement to have narrowed channels for efficient valve closure by channel deformation and (ii) the need to have wide channels to reduce the flow velocity, thus reducing the capillary number and enhancing droplet formation.     

A single-molecule enzymatic assay in a directly accessible femtoliter droplet array

The enzyme assay in a femtoliter chamber array is a simple and efficient method for concentrating the reaction product; it greatly improves the detection sensitivity down to the single-molecule level. However, in previous methods, controlling the initiation and termination of the reaction in each chamber is difficult once enclosed. Furthermore, the recovery of the enzyme and product is also difficult. To overcome these drawbacks, we developed a femtoliter droplet array in which the individual droplets are fixed on the substrate and are directly accessible from outside. A hydrophilic-in-hydrophobic micropatterned surface was used for the preparation of the droplets. When the aqueous solution on the surface is exchanged with oil, the hydrophilic surface retains the aqueous solution, and more than 10(6) dome-shaped droplets that are usable for further assay can be prepared simultaneously. The curvature radius of the droplet obeys the Young-Laplace equation, and the volume can be precisely controlled by the micropipette, which applies pressure into the droplet. Changing the pressure makes the addition, collection, and exchange of the aqueous content for individual droplets possible. Using these advantages, we successfully measured the kinetic parameters of the single-molecule enzyme β-galactosidase and rotary motor protein F(1)-ATPase enclosed in a droplet.     

Atomic force microscopy of emulsion droplets: probing droplet-droplet interactions

A method has been developed for attaching oil (tetradecane) droplets to the end of an atomic force microscopy (AFM) cantilever and for immobilizing droplets on a glass substrate. This approach has permitted the monitoring of droplet-droplet interactions in aqueous solution as a function of interdroplet separation. Coating the droplet surfaces with added proteins or surfactants has allowed the production of model emulsions. We demonstrate that AFM measurements of droplet deformability are sensitive to interfacial rheology by modifying the interfacial film on a pair of droplets in situ. For droplets coated with the anionic surfactant sodium dodecyl sulfate, screening of the double layer has been found to facilitate coalescence. Direct imaging of the droplets has revealed the presence of regularly spaced concentric rings on the droplet surfaces. Careful experimental studies suggest that these structures may be imaging artifacts and are not perturbations of the droplet surface determined by the composition of the interface.     

Microfluidic chip-based liquid-liquid extraction and preconcentration using a subnanoliter-droplet trapping technique

A robust and simple approach for microfluidic liquid-liquid (L-L) extraction at the subnanoliter-scale was developed for on-chip sample pretreatment. Organic solvent droplets of a few hundred pL were trapped within micro recesses fabricated in the channel walls of a microfabricated glass chip. L-L extraction was performed by delivering aqueous samples through the channel, with the sample stream continuously flowing adjacent to the droplets. The analytes in aqueous streams were enriched within the droplet with high preconcentration factors owing to both phase transfer and dissolution of organic solvent into the bypassing aqueous sample. An aqueous solution of butyl rhodamine B (BRB) and 1-hexanol were used, respectively, as sample and extractant to demonstrate the performance of the system. The fluorescence intensity of the dye extracted into the droplet was monitored in situ by LIF. The system proved to be an efficient means for achieving high enrichment factors of over 1000, with sample consumption of a few microL. Quantitative measurement of the extracted analyte was achieved with a linear response in the range 1 x 10(-9)-8 x 10(-7) M BRB. The precision of the measured fluorescence values for a 10(-7) M BRB standard with a 12.5 min preconcentration period was 6.6% RSD (n = 5).     

Fatty acid chemistry at the oil-water interface: self-propelled oil droplets

Fatty acids have been investigated as boundary structures to construct artificial cells due to their dynamic properties and phase transitions. Here we have explored the possibility that fatty acid systems also demonstrate movement. An oil phase was loaded with a fatty acid anhydride precursor and introduced to an aqueous fatty acid micelle solution. The oil droplets showed autonomous, sustained movement through the aqueous media. Internal convection created a positive feedback loop, and the movement of the oil droplet was sustained as convection drove fresh precursor to the surface to become hydrolyzed. As the system progressed, more surfactant was produced and some of the oil droplets transformed into supramolecular aggregates resembling multilamellar vesicles. The oil droplets also moved directionally within chemical gradients and exhibited a type of chemotaxis.     

液滴数字聚合酶链式反应芯片及其在致病菌检测中的应用

设计与制作了一种基于聚二甲基硅氧烷-玻璃(PDMS-Glass)的多功能集成式液滴数字聚合酶链式反应(ddPCR)芯片,该芯片由产生液滴的PDMS模块和收集液滴的玻璃腔体模块组成。PDMS模块采用双通道的T形结构设计,液滴产生速度快且通量高,在30 min内可生成2×10~6个直径约为20μm的微液滴。玻璃腔体模块中存储的液滴在整个实验过程中无需转移,可直接在原位PCR仪上进行扩增,每个液滴均是一个微反应器,经过多次热循环后,液滴仍能保持良好的稳定性。选用副溶血性弧菌(VP)作为食源性致病菌的研究模型,考察了ddPCR芯片对其基因组DNA的绝对定量能力,结果表明,该ddPCR芯片对VP基因组DNA绝对定量的线性范围宽,可跨越5个数量级(10~1~10~6 copies/μL),定量结果与DNA理论参考浓度间有很好的相关性。     

Modeling oil droplets in plateau borders

It is widely known that oil droplets can decrease the stability of aqueous films and foams. While less widely recognized, it has also been observed that oil droplets can, under certain circumstances, increase the stability of foams, especially if they are caught in the Plateau borders. In this paper, how the oil droplet deforms and is, in turn, deformed by the Plateau border is modeled using Surface Evolver. The two dimensionless parameters that affect these shapes are the size of the oil droplet relative to the Plateau border and the ratio of the oil-water interfacial tension to the air-water interfacial tension. The calculated pressures in all the phases were used to obtain the pressure exerted on the oil-water-air pseudoemulsion film, which allows the factors that influence the stability of these droplets in the Plateau border to be investigated. The final section of the paper demonstrates that the presence of an oil droplet in a Plateau border can have a major influence on the drainage of the aqueous phase along the Plateau border. This retardation of the flow would result in the oil droplets in the Plateau borders increasing the stability of foams in which they are found.     

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.     

Optimizing stirred cell membrane emulsification process for making a food-grade multiple emulsion

The stirred cell membrane emulsification process that was used to produce a food-grade multiple emulsion was optimized. The produced water-in-oil-in-water emulsion contained garlic ethanol extract water solution-in-pumpkin seed and sunflower oil mixture (1:1 w/w)-in-glucose water solution. A sintered glass filter-disk membrane was employed in the stirred cell device. The transmembrane pressure and the impeller rotational speed values were varied in a range from 0.2 to 1 10⁵ Pa, and in a range from 140 to 1400 rpm, respectively. For the investigated ranges of the process parameters, the primary emulsion flux through the membrane was in a range from 26 to 366 Lm^?2 h^?1, and the obtained values of the Sauter mean diameter of oil droplets and the span of droplet size distribution was in a range from 45 to 112 μm, and in a range from 0.46 to 1.62, respectively. Optimization procedure was applied to obtain the smallest oil droplets with the narrowest droplet size distribution at the highest flux of the dispersed phase through the membrane.     

Effect of the type of the oil phase on stability of highly concentrated water-in-oil emulsions

The water-in-oil high internal phase emulsions were the subject of the study. The emulsions consisted of a super-cooled aqueous solution of inorganic salt as a dispersed phase and industrial grade oil as a continuous phase. The influence of the industrial grade oil type on a water-in-oil high internal phase emulsion stability was investigated. The stability of emulsions was considered in terms of the crystallization of the dispersed phase droplets (that are super-cooled aqueous salt solution) during ageing. The oils were divided into groups: one that highlighted the effect of oil/aqueous phase interfacial tension and another that investigated the effect of oil viscosity on the emulsion rheological properties and shelf-life. For a given set of experimental conditions the influence of oil viscosity for the emulsion stability as well as the oil/aqueous interfacial tension plays an important role. Within the frames of our experiment it was found that there are oil types characterized by optimal parameters: oil/aqueous phase interfacial tension being in the region of 19–24 mN/m and viscosity close to 3 mPa s; such oils produced the most stable high internal phase emulsions. It was assumed that the oil with optimal parameters kept the critical micelle concentration and surfactant diffusion rate at optimal levels allowing the formation of a strong emulsifier layer at the interface and at the same time creating enough emulsifier micelles in the inter-droplet layer to prevent the droplet crystallization.     

Detachment of liquid droplets from fibres--experimental and theoretical evaluation of detachment force due to interfacial tension effects

The detachment of barrel-shaped oil droplets from metal, glass and polymer fibres was examined using an atomic force microscope (AFM). The AFM was used to detach the droplets from the fibres while measuring the force-distance relationship. A novel fibre-droplet interfacial tension model was applied to predict the force required to draw the droplet away from its preferential axisymmetric position on the fibre, and also to predict the maximal force required to detach the droplet. The model assumes that the droplet retains a spherical shape during detachment, i.e., that droplet distortion is negligible. This assumption was found to be reasonably accurate for small radius oil droplets (<10 microm), however less accurate for larger droplets (>25 microm). However, it was found that the model produced a good agreement with the maximal detachment force measured experimentally--regardless of droplet size and degree of deformation--even though the model could not predict droplet extension beyond a length of one droplet radius.     

Electrical actuation of dielectric droplets by negative liquid dielectrophoresis

This paper presents an electrical actuation scheme of dielectric droplet by negative liquid dielectrophoresis. A general model of lumped parameter electromechanics for evaluating the electromechanical force acting on the droplets is established. The model reveals the influence of actuation voltage, device geometry, and dielectric parameter on the actuation force for both conductive and dielectric medium. Using this model, we compare the actuation forces for four liquid combinations in the parallel-plate geometry and predict the low voltage actuation of dielectric droplets by negative dielectrophoresis. Parallel experimental results demonstrate such electric actuation of dielectric droplets, including droplet transport, splitting, merging, and dispending. All these dielectric droplet manipulations are achieved at voltages < 100 V_rms. The frequency dependence of droplet actuation velocity in aqueous solution is discussed and the existence of surfactant molecules is believed to play an important role by realigning with the AC electric field. Finally, we present coplanar manipulation of oil and water droplets and formation of oil-in-water emulsion droplet by applying the same low voltage.     

A review of: “Nineteenth Century Attitudes: Men of Science (Chemists and Chemistry Series,Vol. 13)”. Sydney Ross. Kluwer Academic Publishers; Dordrecht, 1991. pp. xi+235. $69.00.

Abstract

The potential of polytetrafluoroethylene (PTFE) membranes as water‐in‐oil (W/O) emulsification devices was investigated to obtain uniformly sized droplets and to convert them into microcapsules and polymer particles via subsequent treatments. Uniform W/O emulsion droplets have not been achieved using glass membranes unless the membrane was rendered hydrophobic by treatment with silanes. If a PTFE membrane is capable of providing uniform droplets for a W/O emulsion, a coordinated membrane emulsification system can be established since glass membranes have been so successful for O/W (oil‐in‐water) emulsification. In order to examine the feasibility of PTFE membrane emulsification, O/W and W/O emulsion characteristics prepared using PTFE membranes were compared with those prepared by the conventional SPG (Shirasu porous glass) membrane emulsification method. A 3 wt.% sodium chloride solution was dispersed in kerosene using a low HLB surfactant. Effects of the membrane pore size, permeation pressure, and the type of emulsifiers and concentration on the droplet size and on the size distribution (CV, coefficient of variation) were investigated. The CV of the droplets was fairly low, and the average droplet size was correlated with the critical permeation pressure of the dispersed phase, revealing that the PTFE membrane could be used as a one‐pass membrane emulsification device. Low CV values were maintained with a Span 85 (HLB = 1.8) concentration, 0.2–5.0 wt.% and a range of HLB from 1.8–5.0. For a brief demonstration of practical applications, nylon‐6,10 microcapsules prepared by interfacial polycondensation and poly(acrylamide) hydrogels from inverse suspension polymerization are illustrated.     

Sensitive Detection of Trypsin using Liquid‐Crystal Droplet Patterns Modulated by Interactions between Poly‐L‐Lysine and a Phospholipid Monolayer

Liquid‐crystal (LC) droplet patterns are formed on a glass slide by evaporating a solution of nematic LC dissolved in heptane. In the presence of an anionic phospholipid, 1,2‐dioleoyl‐sn‐glycero‐3‐phospho‐rac‐(1‐glycerol) (DOPG), the LCs display a dark cross pattern, indicating a homeotropic orientation. When LC patterns are incubated with an aqueous mixture of DOPG and poly‐L ‐lysine (PLL), there is a transition in the LC pattern from a dark cross to a bright fan shape due to the electrostatic interaction between DOPG and PLL. Known to catalyze the hydrolysis of PLL into oligopeptide fragments, trypsin is preincubated with PLL, significantly decreasing the interactions between PLL and DOPG. LCs adopt a perpendicular orientation at the water–LC droplet interface, which gives rise to a dark cross pattern. This optical response of LC droplets is the basis for a quick and sensitive biosensor for trypsin.     

Background theory and applications of microemulsion electrokinetic chromatography

Microemulsion electrokinetic chromatography (MEEKC) is an electrodriven separation technique. Separations are achieved using microemulsions which are nanometre-sized oil droplets suspended in aqueous buffer. The surface tension between the oil and water components is reduced by covered the oil droplet with an anionic surfactant such as sodium dodecyl sulphate and a co-surfactant such as a short-chain alcohol. This review summarises the various microemulsion types and compositions that have been used in MEEKC. The effects of key operating variables such as pH and temperature are also described. The application areas of MEEKC are also described in some detail. MEEKC has been applied to a wide range of water-soluble and insoluble both charged and neutral compounds. Examples are described which include analysis of derivatised sugars, proteins, pesticides and a wide range of pharmaceuticals. At present there are only a limited number of publications describing the use of MEEKC but it is anticipated that this number will increase rapidly in the near future as more awareness of the separation possibilities that MEEKC presents increases.     

Droplet surface properties and rheology of concentrated oil in water emulsions stabilized by heat-modified beta-lactoglobulin B

Effects of substituting native beta-lactoglobulin B (beta-lactoglobulin) with heat-treated beta-lactoglobulin as emulsifier in oil in water emulsions were investigated. The emulsions were prepared with a dispersed phase volume fraction of Phi=0.6, and accordingly, oil droplets rather closely packed. Native beta-lactoglobulin and beta-lactoglobulin heated at 69 degrees C for 30 and 45 min, respectively, in aqueous solution at pH 7.0 were compared. Molar mass determination of the species formed upon heating as well as measurements of surface hydrophobicity and adsorption to a planar air/water interface were made. The microstructure of the emulsions was characterized using confocal laser scanning microscopy, light scattering measurements of oil droplet sizes, and assessment of the amount of protein adsorbed to surfaces of oil droplets. Furthermore, oil droplet interactions in the emulsions were quantified rheologically by steady shear and small and large amplitude oscillatory shear measurements. Adsorption of heated and native beta-lactoglobulin to oil droplet surfaces was found to be rather similar while the rheological properties of the emulsions stabilized by heated beta-lactoglobulin and the emulsions stabilized by native beta-lactoglobulin were remarkably different. A 200-fold increase in the zero-shear viscosity and elastic modulus and a 10-fold increase in yield stress were observed when emulsions were stabilized by heat-modified beta-lactoglobulin instead of native beta-lactoglobulin. Aggregates with a radius of gyration in the range from 25 to 40 nm, formed by heating of beta-lactoglobulin, seem to increase oil droplet interactions. Small quantities of emulsifier substituted with aggregates have a major impact on the rheology of oil in water emulsions that consist of rather closely packed oil droplets.