Periodic emission of droplets from an oscillating electrified meniscus of a low-viscosity, highly conductive liquid

The generation of identical droplets of controllable size in the micrometer range is a problem of much interest owing to the numerous technological applications of such droplets. This work reports an investigation of the regime of periodic emission of droplets from an electrified oscillating meniscus of a liquid of low viscosity and high electrical conductivity attached to the end of a capillary tube, which may be used to produce droplets more than ten times smaller than the diameter of the tube. To attain this periodic microdripping regime, termed axial spray mode II by Juraschek and Röllgen [R. Juraschek and F. W. Röllgen, Int. J. Mass Spectrom. 177, 1 (1998)], liquid is continuously supplied through the tube at a given constant flow rate, while a dc voltage is applied between the tube and a nearby counter electrode. The resulting electric field induces a stress at the surface of the liquid that stretches the meniscus until, in certain ranges of voltage and flow rate, it develops a ligament that eventually detaches, forming a single droplet, in a process that repeats itself periodically. While it is being stretched, the ligament develops a conical tip that emits ultrafine droplets, but the total mass emitted is practically contained in the main droplet. In the parametrical domain studied, we find that the process depends on two main dimensionless parameters, the flow rate nondimensionalized with the diameter of the tube and the capillary time, q, and the electric Bond number BE, which is a nondimensional measure of the square of the applied voltage. The meniscus oscillation frequency made nondimensional with the capillary time, f, is of order unity for very small flow rates and tends to decrease as the inverse of the square root of q for larger values of this parameter. The product of the meniscus mean volume times the oscillation frequency is nearly constant. The characteristic length and width of the liquid ligament immediately before its detachment approximately scale as powers of the flow rate and depend only weakly on the applied voltage. The diameter of the main droplets nondimensionalized with the diameter of the tube satisfies dd≈(6/π)1/3(q/f)1/3, from mass conservation, while the electric charge of these droplets is about 1/4 of the Rayleigh charge. At the minimum flow rate compatible with the periodic regimen, the dimensionless diameter of the droplets is smaller than one-tenth, which presents a way to use electrohydrodynamic atomization to generate droplets of highly conducting liquids in the micron-size range, in marked contrast with the cone-jet electrospray whose typical droplet size is in the nanometric regime for these liquids. In contrast with other microdripping regimes where the mass is emitted upon the periodic formation of a narrow capillary jet, the present regime gives one single droplet per oscillation, except for the almost massless fine aerosol emitted in the form of an electrospray.

Regimes of spray vaporization and combustion in counterflow configurations

This article addresses the problem of spray vaporization and combustion in axisymmetric opposed-jet configurations involving a stream of hot air counterflowing against a stream of nitrogen carrying a spray of fuel droplets. The Reynolds numbers of the jets are assumed to be large, so that mixing of the two streams is restricted to a thin mixing layer that separates the counterflowing streams. The evolution of the droplets in their feed stream from the injection location is seen to depend fundamentally on the value of the droplet Stokes number, St, defined as the ratio of the droplet acceleration time to the mixing layer strain time close to the stagnation point. Two different regimes of spray vaporization and combustion can be identified depending on the value of St. For values of St below a critical value, equal to 1/4 for dilute sprays with small values of the spray liquid mass loading ratio, the droplets decelerate to approach the gas stagnation plane with a vanishing axial velocity. In this case, the droplets located initially near the axis reach the mixing layer, where they can vaporize due to the heat received from the hot air, producing fuel vapor that can burn with the oxygen in a diffusion flame located on the air side of the mixing layer. The character of the spray combustion is different for values of St of order unity, because the droplets cross the stagnation plane and move into the opposing air stream, reaching distances that are much larger than the mixing layer thickness before they turn around. The vaporization of these crossing droplets, and also the combustion of the fuel vapor generated by them, occur in the hot air stream, without significant effects of molecular diffusion, generating a vaporization-assisted nonpremixed flame that stands on the air side outside the mixing layer. Separate formulations will be given below for these two regimes of combustion, with attention restricted to the near-stagnation-point region, where the solution is self-similar and all variables are only dependent on the distance to the stagnation plane. The resulting formulations display a reduced number of controlling parameters that effectively embody dependences of the structure of the spray flame on spray dilution, droplet inertia, and fuel preferential diffusion. Sample solutions are given for the limiting cases of pure vaporization and of infinitely fast chemistry, with the latter limit formulated in terms of chemistry-free coupling functions that allow for general nonunity Lewis numbers of the fuel vapor.

O papel da lisofosfatidilcolina na ativação do inflamassoma NLRP3 e sua relação com a formação de células gordurosas

Dissertação (mestrado)—Universidade de Brasília, Instituto de Ciências Biológicas, Programa de Pós-Graduação em Biologia Molecular, 2016.

Formulation and stability of topical water in oil emulsion containing corn silk extract

Purpose: To formulate the water in oil (W/O) emulsion of corn silk (CS) extract and to evaluate its stability at various storage conditions. Methods: Ethanol CS extract was prepared using maceration (cold) technique. A 4 % CS emulsion was prepared using varying concentrations of liquid paraffin, ABIL EM90 and water. The formulations were kept at 40 oC for 28 days and to screen out the less stable formulations. The remaining formulations were further stressed at 50 oC to choose the most stable formulation. The optimized formulation was evaluated for physical characteristics including phase separation, rheology and mean droplet size. The physical stability of the formulation was evaluated by monitoring these parameters over a period of 12 weeks at 8, 25, 40 and 40 oC, and 75 % RH. Results: The chosen formulation showed good resistance to phase separation on centrifugation under all storage conditions. Rheological behavior followed non-Newtonian pseudoplastic pattern at various storage conditions. Mean droplet size of freshly prepared formulation was 2.98 ± 1.32 µm and did not show significant (p < 0.05) changes at normal storage conditions (8 and 25 oC). Conclusion: The findings indicate that the developed CS extract W/O emulsion is stable and therefore may be suitable for topical use on skin as an antioxidant preparation.

Chemical Reaction Dynamics of the Liquid/Vapor Interface Studied by Mass Spectrometry

This thesis presents investigations of chemical reactions occurring at the liquid/vapor interface studied using novel sampling methodologies coupled with detection by mass spectrometry. Chapters 2 and 3 utilize the recently developed technique of field-induced droplet ionization mass spectrometry (FIDI-MS), in which the application of a strong electric field to a pendant microliter droplet results in the ejection of highly charged progeny droplets from the liquid surface. In Chapter 2, this method is employed to study the base-catalyzed dissociation of a surfactant molecule at the liquid/vapor interface upon uptake of ammonia from the gas phase. This process is observed to occur without significant modulation of the bulk solution pH, suggesting a transient increase in surface pH following the uptake of gaseous ammonia. Chapter 3 presents real-time studies of the oxidation of the model tropospheric organic compound glycolaldehyde by photodissociation of iron (III) oxalate complexes. The oxidation products of glycolaldehyde formed in this process are identified, and experiments in a deoxygenated environment identify the role of oxygen in the oxidation pathway and in the regeneration of iron (III) following photo-initiated reduction. Chapter 4 explores alternative methods for the study of heterogeneous reaction processes by mass spectrometric sampling from liquid surfaces. Bursting bubble ionization (BBI) and interfacial sampling with an acoustic transducer (ISAT) generate nanoliter droplets from a liquid surface that can be sampled via the atmospheric pressure interface of a mass spectrometer. Experiments on the oxidation of oleic acid by ozone using ISAT are also presented. Chapters 5 and 6 detail mechanistic studies and applications of free-radical-initiated peptide sequencing (FRIPS), a technique employing gas-phase free radical chemistry to the sequencing of peptides and proteins by mass spectrometry. Chapter 5 presents experimental and theoretical studies on the anomalous mechanism of dissociation observed in the presence of serine and threonine residues in peptides. Chapter 6 demonstrates the combination of FRIPS with ion mobility-mass spectrometry (IM-MS) for the separation of isomeric peptides.

The effect of polypropylene-graft-maleic anhydride on the morphology and dynamic mechanical properties of polypropylene/polystyrene blends

Polypropylene (PP) and polystyrene (PS) blends were prepared by melt processing in a haake at 180 °C. PP/PS blends are immiscible and the blend morphologies were characterized by scanning electron microscopy. The viscoelastic properties were characterized using dynamic mechanical analysis (DMA) with reference to blend ratio. The blend morphologies such as matrix droplet and phase inverted morphologies were observed. The storage modulus of the blends increased with increase in PS content and the value was maximum for neat PS. DMA showed changes in the polystyrene glass transition temperatures (Tg) over the entire composition range. There was a sharp increase in the Tg of PS with increasing PP content in the blend and a 12 °C elevation in Tg was observed. The increase in Tg was explained by proposing a new model based on the physical interaction between the blend components. It is assumed that the different effects by the PP phase resulted in the formation of constrained PS chains leading to high Tg values. The addition of PP-g-MAH has a positive effect on the morphology, increases the storage modulus, and decreases the Tg till 80/20 blends. However, for PP/PS blends with higher concentrations of PS, the PP-g-MAH has little effect or adverse effect on the morphology, and storage modulus, but decreases the Tg.

Directional water transport fabrics with durable ultra-high one-way transport capacity

Fabrics with automatic one-way water transport ability are highly desirable for applications in daily life, industry, health, and defense. However, most of the studies on one-way water transport fabrics only report the qualitative water transport results. The lack of quantitative measure makes it hard to assess the directional transport quality. Here, it is proved that a hydrophilic fabric after being electrosprayed with a thin layer of hydrophobic coating on one side shows one-way water transport ability. By using moisture management tester, the water transport property is qualitatively characterized and the effect of hydrophobic fabric layer thickness on one-way water transport feature is examined. The hydrophobic fabric layer thickness is found to play a key role in deciding the one-way transport ability. When a plain woven fabric with an overall thickness of 420 μm and average pore size of 33 μm is used as fabric substrate, a hydrophobic fabric layer thickness between 22 and 62 μm allows the treated fabric to show a one-way droplet transport feature. A one-way transport index as high as 861 can be attained. The one-way water transport is durable enough to withstand repeated washing. This novel fabric may be useful for development of “smart” textiles for various applications.

Reducing electrowetting-on-dielectric actuation voltage using a novel electrode shape and a multi-layer dielectric coating

This paper presents design and fabrication of an electrowetting-on-dielectric (EWOD) device using a novel electrode shape and a multi-layer dielectric coating that reduce the actuation voltage of the device to less than 12.6 V. The fabrication of the EWOD electrodes is carried out in several steps including laser exposure, wet developing, etching, and stripping. A high-dielectric-constant multi-layer dielectric coating containing a 770 nm thick Polyvinylidene difluoride (PVDF) layer and a 1 µm thick Cyanoethyl pullulan (CEP) layer, is deposited on the EWOD electrodes for insulation. This multi-layer dielectric structure exhibits a high capacitance per unit area, and the novel electrode shape changes the actuation force at the droplet contact line reducing the voltage required to operate the device. In addition, an overlaying Teflon layer of 50 nm is placed on top of the dielectric structure to provide a hydrophobic surface for droplet manipulation. It is observed from the experiments that the electrode shape and the dielectric structure have contributed to the reduction of the actuation voltage of the EWOD device.

Kinetic resolution of the interactions between agrochemical products and adjuvant systems upon mixing

The addition of an adjuvant to a pesticide usually occurs in a mix-tank, before spray application to the crop. Their interaction is potentially crucial to overall efficacy but has received little attention from a physical-chemical perspective. Study was undertaken by laser diffraction, Raman spectroscopy, and small-angle X-ray scattering to resolve these physical processes. It was shown that migration of the pesticide into the adjuvant droplet occurred in all cases studied. The level of transfer was dependent upon adjuvant level, adjuvant solubility, and surfactant level. For suspension pesticides, dissolution of crystallites within the droplet occurred to a degree limited by solubility. The results directly demonstrate the transfer of the pesticide into the adjuvant carrier. This indicates that for emulsion-based pesticides, application to the target is likely as a homogeneously mixed droplet, whereas for suspension pesticides, solubility may limit transfer and dissolution, leading to heterogeneity in the applied particles.

Microchannel emulsification study on formulation and stability characterization of monodisperse oil-in-water emulsions encapsulating quercetin

The study used microchannel emulsification (MCE) to encapsulate quercetin in food grade oil-in-water (O/W) emulsions. A silicon microchannel plate (Model WMS 1-2) comprised of 10,300 discrete 10 × 104 μm microslots was connected to a circular microhole with an inner diameter of 10 μm. 1% (w/w) Tween 20 was used as optimized emulsifier in Milli-Q water, while 0.4 mg ml-1 quercetin in different oils served as a dispersed phase. The MCE was carried by injecting the dispersed phase at 2 ml h-1. Successful emulsification was conducted below the critical dispersed phase flux, with a Sauter mean diameter of 29 μm and relative span factor below 0.25. The O/W emulsions remained stable in terms of droplet coalescence at 4 and 25 °C for 30 days. The encapsulation efficiency of quercetin in the O/W emulsions was 80% at 4 °C and 70% at 25 °C during the evaluated storage period.

Formulation characteristics of triacylglycerol oil-in-water emulsions loaded with ergocalciferol using microchannel emulsification

Ergocalciferol is one important form of vitamin D that is needed for proper functioning of the human metabolic system. The study formulates monodisperse food grade ergocalciferol loaded oil-in-water (O/W) emulsions by microchannel emulsification (MCE). The primary characterization was performed with grooved MCE, while the storage stability and encapsulating efficiency (EE) were investigated with straight-through MCE. The grooved microchannel (MC) array plate has 5 × 18 μm MCs, while the asymmetric straight-through MC array plate consists of numerous 10 × 80 μm microslots each connected to a 10 μm diameter circular MC. Ergocalciferol at a concentration of 0.2-1.0% (w/w) was added to various oils and served as the dispersed phase, while the continuous phase constituted either of 1% (w/w) Tween 20, decaglycerol monolaurate (Sunsoft A-12) or β-lactoglobulin. The primary characterization indicated successful emulsification in the presence of 1% (w/w) Tween 20 or Sunsoft A-12. The average droplet diameter increased slowly with the increasing concentration of ergocalciferol and ranged from 28.3 to 30.0 μm with a coefficient of variation below 6.0%. Straight-through MCE was conducted with 0.5% (w/w) ergocalciferol in soybean oil together with 1% (w/w) Tween 20 in Milli-Q water as the optimum dispersed and continuous phases. Monodisperse O/W emulsions with a Sauter mean diameter (d3,2) of 34 μm with a relative span factor of less than 0.2 were successfully obtained from straight-through MCE. The resultant oil droplets were physically stable for 15 days (d) at 4 °C without any significant increase in d3,2. The monodisperse O/W emulsions exhibited an ergocalciferol EE of more than 75% during the storage period.

Formulation of monodisperse water-in-oil emulsions encapsulating calcium ascorbate and ascorbic acid 2-glucoside by microchannel emulsification

The aim of this study was to investigate the effects of the emulsifying conditions and emulsifier type on production of water-in-oil (W/O) emulsions encapsulating ascorbic acid derivatives by microchannel (MC) emulsification. The ascorbic acid derivatives added in a dispersed aqueous phase are calcium ascorbate (AA-Ca) and ascorbic acid 2-glucoside (AA-2G). The continuous phase used was decane, soybean oil or their mixture, containing 5% (w/w) tetraglycerin monolaurate condensed ricinoleic acid ester or sorbitan trioleate. A hydrophobized silicon MC array plate (model: MS407) with a channel depth of 7μm was used for MC emulsification. The use of MC emulsification enabled successful encapsulation of AA-Ca and AA-2G in monodisperse W/O emulsion droplets with coefficients of variation (CV) less than 7%. Their average droplet diameter (dav) increased with increasing the continuous-phase viscosity that is similar or higher than the dispersed-phase viscosity. The dav and CV of the resultant monodisperse W/O emulsions were unaffected by the dispersed-phase flow rate below critical values of 1.2-1.6mLh-1 when using decane as the continuous-phase medium.

Monodisperse W/O/W emulsions encapsulating L-ascorbic acid: Insights on their formulation using microchannel emulsification and stability studies

Stabilizing l-ascorbic acid is a challenge for food industries. The present study aimed to formulate monodisperse food-grade water-in-oil-in-water (W/O/W) emulsions containing a high concentration of l-ascorbic acid in an inner aqueous phase using homogenization and subsequent microchannel emulsification (MCE). The microchannel (MC) array plate used here was a silicon asymmetric straight-through MC array that consists of numerous 10. μm. ×. 100. μm microslots with a 30. μm depth, each connected to a 10. μm-diameter circular MC with a 70. μm depth. Water-in-oil (W/O) emulsions contained a soybean oil solution with 4-8% (w/w) tetraglycerin condensed ricinoleic acid ester as a continuous phase and an aqueous solution with 10-30% (w/v) l-ascorbic acid, 1% (w/w) magnesium sulfate, and 1% (w/v) gelatin as an inner aqueous phase. The W/O emulsion droplets formulated using a rotor-starter homogenizer had average droplet diameters of 2.6-2.9. μm and coefficients of variation (CVs) of 13-17%. MCE was performed using a dispersed W/O emulsion phase and a 5. mM phosphate buffer containing 1% (w/w) decaglycerol monolaurate and 10-30% (w/v) D(+)-glucose as an outer aqueous phase. Monodisperse W/O/W emulsions containing W/O droplets with average diameters of 26.0-31.5. μm and CVs below 10% were successfully formulated via an asymmetric straight-through MC array at a low hydrophobic emulsifier concentration, regardless of l-ascorbic acid concentration. The W/O droplets dispersed in these monodisperse W/O/W emulsions were physically stable in variation of average diameter and CV for more than 10d of storage at 4. °C. The monodisperse W/O/W emulsions also exhibited l-ascorbic acid retention exceeding 80% during storage.

Industrial lab-on-a-chip: design, applications and scale-up for drug discovery and delivery

Microfluidics is an emerging and promising interdisciplinary technology which offers powerful platforms for precise production of novel functional materials (e.g., emulsion droplets, microcapsules, and nanoparticles as drug delivery vehicles- and drug molecules) as well as high-throughput analyses (e.g., bioassays, detection, and diagnostics). In particular, multiphase microfluidics is a rapidly growing technology and has beneficial applications in various fields including biomedicals, chemicals, and foods. In this review, we first describe the fundamentals and latest developments in multiphase microfluidics for producing biocompatible materials that are precisely controlled in size, shape, internal morphology and composition. We next describe some microfluidic applications that synthesize drug molecules, handle biological substances and biological units, and imitate biological organs. We also highlight and discuss design, applications and scale up of droplet- and flow-based microfluidic devices used for drug discovery and delivery.

Preparation and characterization of water-in-oil-in-water emulsions containing a high concentration of L-ascorbic acid

This study sought to encapsulate a high concentration of L-ascorbic acid, up to 30% (w/v), in the inner aqueous phase of water-in-oil-water (W/O/W) emulsions with soybean oil as the oil phase. Two-step homogenization was conducted to prepare W/O/W emulsions stabilized by a hydrophobic emulsifier and 30% (v/v) of W/O droplets stabilized by a hydrophilic emulsifier. First-step homogenization prepared W/O emulsions with an average aqueous droplet diameter of 2.0 to 3.0 μm. Second-step homogenization prepared W/O/W emulsions with an average W/O droplet diameter of 14 to 18 μm and coefficients of variation (CVs) of 18% to 25%. The results indicated that stable W/O/W emulsions containing a high concentration of L-ascorbic acid were obtained by adding gelatin and magnesium sulfate in the inner aqueous phase and glucose in both aqueous phases. L-Ascorbic acid retention in the W/O/W emulsions was 40% on day 30 and followed first-order kinetics.