Electrostatic Model Applied to ISS Charged Water Droplet Experiment

NASA Technical Reports Server (NTRS)

Stevenson, Daan; Schaub, Hanspeter; Pettit, Donald R.

2015-01-01

The electrostatic force can be used to create novel relative motion between charged bodies if it can be isolated from the stronger gravitational and dissipative forces. Recently, Coulomb orbital motion was demonstrated on the International Space Station by releasing charged water droplets in the vicinity of a charged knitting needle. In this investigation, the Multi-Sphere Method, an electrostatic model developed to study active spacecraft position control by Coulomb charging, is used to simulate the complex orbital motion of the droplets. When atmospheric drag is introduced, the simulated motion closely mimics that seen in the video footage of the experiment. The electrostatic force's inverse dependency on separation distance near the center of the needle lends itself to analytic predictions of the radial motion.

Charge Effects on the Efflorescence in Single Levitated Droplets.

PubMed

Hermann, Gunter; Zhang, Yan; Wassermann, Bernhard; Fischer, Henry; Quennet, Marcel; Rühl, Eckart

2017-09-14

The influence of electrical excess charges on the crystallization from supersaturated aqueous sodium chloride solutions is reported. This is accomplished by efflorescence studies on single levitated microdroplets using optical and electrodynamic levitation. Specifically, a strong increase in efflorescence humidity is observed as a function of the droplet's negative excess charge, ranging up to -2.1 pC, with a distinct threshold behavior, increasing the relative efflorescence humidity, at which spontaneous nucleation occurs, from 44% for the neutral microparticle to 60%. These findings are interpreted by using molecular dynamics simulations for determining plausible structural patterns located near the particle surface that could serve as suitable precursors for the formation of critical clusters overcoming the nucleation barrier. These results, facilitating heterogeneous nucleation in the case of negatively charged microparticles, are compared to recent work on charge-induced nucleation of neat supercooled water, where a distinctly different nucleation behavior as a function of droplet charge has been observed.

Visualization of the evolution of charged droplet formation and jet transition in electrostatic atomization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huo, Yuanping, E-mail: huoyuanping@gmail.com; Wang, Junfeng, E-mail: wangjunfeng@ujs.edu.cn; Zuo, Ziwen

2015-11-15

A detailed experimental study on the evolution of charged droplet formation and jet transition from a capillary is reported. By means of high-speed microscopy, special attention has been paid to the dynamics of the liquid thread and satellite droplets in the dripping mode, and a method for calculating the surface charge on the satellite droplet is proposed. Jet transition behavior based on the electric Bond number has been visualized, droplet sizes and velocities are measured to obtain the ejection characteristic of the spray plume, and the charge and hydrodynamic relaxation are linked to give explanations for ejection dynamics with differentmore » properties. The results show that the relative length is very sensitive to the hydrodynamic relaxation time. The magnitude of the electric field strength dominates the behavior of coalescence and noncoalescence, with the charge relationship between the satellite droplet and the main droplet being clear for every noncoalescence movement. Ejection mode transitions mainly depend on the magnitude of the electric Bond number, and the meniscus dynamics is determined by the ratio of the charge relaxation time to the hydrodynamic relaxation time.« less

Numerical Investigation of Two-Phase Flows With Charged Droplets in Electrostatic Field

NASA Technical Reports Server (NTRS)

Kim, Sang-Wook

1996-01-01

A numerical method to solve two-phase turbulent flows with charged droplets in an electrostatic field is presented. The ensemble-averaged Navier-Stokes equations and the electrostatic potential equation are solved using a finite volume method. The transitional turbulence field is described using multiple-time-scale turbulence equations. The equations of motion of droplets are solved using a Lagrangian particle tracking scheme, and the inter-phase momentum exchange is described by the Particle-In-Cell scheme. The electrostatic force caused by an applied electrical potential is calculated using the electrostatic field obtained by solving a Laplacian equation and the force exerted by charged droplets is calculated using the Coulombic force equation. The method is applied to solve electro-hydrodynamic sprays. The calculated droplet velocity distributions for droplet dispersions occurring in a stagnant surrounding are in good agreement with the measured data. For droplet dispersions occurring in a two-phase flow, the droplet trajectories are influenced by aerodynamic forces, the Coulombic force, and the applied electrostatic potential field.

Microfluidic production of single micrometer-sized hydrogel beads utilizing droplet dissolution in a polar solvent

PubMed Central

Sugaya, Sari; Yamada, Masumi; Hori, Ayaka; Seki, Minoru

2013-01-01

In this study, a microfluidic process is proposed for preparing monodisperse micrometer-sized hydrogel beads. This process utilizes non-equilibrium aqueous droplets formed in a polar organic solvent. The water-in-oil droplets of the hydrogel precursor rapidly shrunk owing to the dissolution of water molecules into the continuous phase. The shrunken and condensed droplets were then gelled, resulting in the formation of hydrogel microbeads with sizes significantly smaller than the initial droplet size. This study employed methyl acetate as the polar organic solvent, which can dissolve water at 8%. Two types of monodisperse hydrogel beads—Ca-alginate and chitosan—with sizes of 6–10 μm (coefficient of variation < 6%) were successfully produced. In addition, we obtained hydrogel beads with non-spherical morphologies by controlling the degree of droplet shrinkage at the time of gelation and by adjusting the concentration of the gelation agent. Furthermore, the encapsulation and concentration of DNA molecules within the hydrogel beads were demonstrated. The process presented in this study has great potential to produce small and highly concentrated hydrogel beads that are difficult to obtain by using conventional microfluidic processes. PMID:24396529

Microfluidic production of single micrometer-sized hydrogel beads utilizing droplet dissolution in a polar solvent.

PubMed

Sugaya, Sari; Yamada, Masumi; Hori, Ayaka; Seki, Minoru

2013-01-01

In this study, a microfluidic process is proposed for preparing monodisperse micrometer-sized hydrogel beads. This process utilizes non-equilibrium aqueous droplets formed in a polar organic solvent. The water-in-oil droplets of the hydrogel precursor rapidly shrunk owing to the dissolution of water molecules into the continuous phase. The shrunken and condensed droplets were then gelled, resulting in the formation of hydrogel microbeads with sizes significantly smaller than the initial droplet size. This study employed methyl acetate as the polar organic solvent, which can dissolve water at 8%. Two types of monodisperse hydrogel beads-Ca-alginate and chitosan-with sizes of 6-10 μm (coefficient of variation < 6%) were successfully produced. In addition, we obtained hydrogel beads with non-spherical morphologies by controlling the degree of droplet shrinkage at the time of gelation and by adjusting the concentration of the gelation agent. Furthermore, the encapsulation and concentration of DNA molecules within the hydrogel beads were demonstrated. The process presented in this study has great potential to produce small and highly concentrated hydrogel beads that are difficult to obtain by using conventional microfluidic processes.

Enhancing physicochemical properties of emulsions by heteroaggregation of oppositely charged lactoferrin coated lutein droplets and whey protein isolate coated DHA droplets.

PubMed

Li, Xin; Wang, Xu; Xu, Duoxia; Cao, Yanping; Wang, Shaojia; Wang, Bei; Sun, Baoguo; Yuan, Fang; Gao, Yanxiang

2018-01-15

The formation and physicochemical stability of mixed functional components (lutein & DHA) emulsions through heteroaggregation were studied. It was formed by controlled heteroaggregation of oppositely charged lutein and DHA droplets coated by cationic lactoferrin (LF) and anionic whey protein isolate (WPI), respectively. Heteroaggregation was induced by mixing the oppositely charged LF-lutein and WPI-DHA emulsions together at pH 6.0. Droplet size, zeta-potential, transmission-physical stability, microrheological behavior and microstructure of the heteroaggregates formed were measured as a function of LF-lutein to WPI-DHA droplet ratio. Lutein degradation and DHA oxidation by measurement of lipid hydroperoxides and thiobarbituric acid reactive substances were determined. Upon mixing the two types of bioactive compounds droplets together, it was found that the largest aggregates and highest physical stability occurred at a droplet ratio of 40% LF-lutein droplets to 60% WPI-DHA droplets. Heteroaggregates formation altered the microrheological properties of the mixed emulsions mainly by the special network structure of the droplets. When LF-coated lutein droplets ratios were more than 30% and less than 60%, the mixed emulsions exhibited distinct decreases in the Mean Square Displacement, which indicated that their limited scope of Brownian motion and stable structure. Mixed emulsions with LF-lutein/WPI-DHA droplets ratio of 4:6 exhibited Macroscopic Viscosity Index with 13 times and Elasticity Index with 3 times of magnitudes higher than the individual emulsions from which they were prepared. Compared with the WPI-DHA emulsion or LF-lutein emulsion, the oxidative stability of the heteroaggregate of LF-lutein/WPI-DHA emulsions was improved. Heteroaggregates formed by oppositely charged bioactive compounds droplets may be useful for creating specific food structures that lead to desirable physicochemical properties, such as microrheological property, physical and chemical

Solvent Dependence of Lateral Charge Transfer in a Porphyrin Monolayer

DOE PAGES

Brennan, Bradley J.; Regan, Kevin P.; Durrell, Alec C.; ...

2016-12-19

Lateral charge transport in a redox)active monolayer can be utilized for solar energy harvesting. We chose the porphyrin system to study the influence of the solvent on lateral hole hopping, which plays a crucial role in the charge)transfer kinetics. We also examined the influence of water, acetonitrile, and propylene carbonate as solvents. Hole)hopping lifetimes varied by nearly three orders of magnitude among solvents, ranging from 3 ns in water to 2800 ns in propylene carbonate, and increased nonlinearly as a function of added acetonitrile in aqueous solvent mixtures. Our results elucidate the important roles of solvation, molecular packing dynamics, andmore » lateral charge)transfer mechanisms that have implications for all dye)sensitized photoelectrochemical device designs.« less

Charged Water Droplets can Melt Metallic Electrodes

NASA Astrophysics Data System (ADS)

Elton, Eric; Rosenberg, Ethan; Ristenpart, William

2016-11-01

A water drop, when immersed in an insulating fluid, acquires charge when it contacts an energized electrode. Provided the electric field is strong enough, the drop will move away to the opposite electrode, acquire the opposite charge, and repeat the process, effectively 'bouncing' back and forth between the electrodes. A key implicit assumption, dating back to Maxwell, has been that the electrode remains unaltered by the charging process. Here we demonstrate that the electrode is physically deformed during each charge transfer event with an individual water droplet or other conducting object. We used optical, electron, and atomic force microscopy to characterize a variety of different metallic electrodes before and after drops were electrically bounced on them. Although the electrodes appear unchanged to the naked eye, the microscopy reveals that each charge transfer event yielded a crater approximately 1 micron wide and 50 nm deep, with the exact dimensions proportional to the applied field strength. We present evidence that the craters are formed by localized melting of the electrodes via Joule heating in the metal and concurrent dielectric breakdown of the surrounding fluid, suggesting that the electrode locally achieves temperatures exceeding 3400°C. Present address: Dept. Materials Sci. Engineering, MIT.

Fluorescence and Nonlinear Optical Properties of Alizarin Red S in Solvents and Droplet.

PubMed

Sangsefedi, Seyed Ahmad; Sharifi, Soheil; Rezaion, Hadi Rastegar Moghaddam; Azarpour, Afshin

2018-05-28

The enhancement of the nonlinear properties of materials is an interesting topic since it has many applications in optical devices and medicines. The Z-scan technique was used to study the values of the two-photon absorption (β), second-order molecular hyperpolarizability (γ R ), third-order susceptibility (χ R ), and nonlinear refractive index (n 2 ) of Alizarin Red S in different media using a continuous-wave diode-pump laser radiation at 532 nm. For Alizarin Red S in a droplet, the β, n 2 , χ R, and γ R were estimated at the order of 10 -7  cm 2 /W and 10 -12  cm/W, 10 -3  m 3  W -1  s -1 and 10 -24  m 6  W -1  s -1 , respectively. The results indicated that the values of β and n 2 reduced, whereas the values of χ R and γ R were enhanced when the solvent was changed from droplet to water, DMF, and dimethyl sulfoxide due to the change in the solvent's dielectric constant (ε). Moreover, the values of β were enhanced by an increase in the concentration of the surfactant in the aqueous solution. The absorption spectra of Alizarin Red S in the aqueous solution was observed at 428 nm, and a few red shifts in the absorption spectra were observed with a reduction in the dielectric constant of the medium. The same effect was observed in the absorption spectra of Alizarin Red S in the droplet when the bulk dielectric constant reduced. The dielectric constant can affect the fluorescence spectra of Alizarin Red S when the solution is changed from water to dimethyl sulfoxide. The dipole moments of Alizarin Red S in the different media were studied using the quantum perturbation theory.

Microfluidic solvent extraction of poly(vinyl alcohol) droplets: effect of polymer structure on particle and capsule formation.

PubMed

Sharratt, W N; Brooker, A; Robles, E S J; Cabral, J T

2018-04-26

We investigate the formation of poly(vinyl alcohol) microparticles by the selective extraction of aqueous polymer solution droplets, templated by microfluidics and subsequently immersed in a non-solvent bath. The role of polymer molecular mass (18-105 kg mol-1), degree of hydrolysis (88-99%) and thus solubility, and initial solution concentration (0.01-10% w/w) are quantified. Monodisperse droplets with radii ranging from 50 to 500 μm were produced at a flow-focusing junction with carrier phase hexadecane and extracted into ethyl acetate. Solvent exchange and extraction result in droplet shrinkage, demixing, coarsening and phase-inversion, yielding polymer microparticles with well-defined dimensions and internal microstructure. Polymer concentration, varied from below the overlap concentration c* to above the concentrated crossover c**, as estimated by viscosity measurements, was found to have the largest impact on the final particle size and extraction timescale, while polymer mass and hydrolysis played a secondary role. These results are consistent with the observation that the average polymer concentration upon solidification greatly exceeds c**, and that the internal microparticle porosity is largely unchanged. However, reducing the initial polymer concentration to well below c* (approximately 100×) and increasing droplet size yields thin-walled (100's of nm) capsules which controllably crumple upon extraction. The symmetry of the process can be readily broken by imposing extraction conditions at an impermeable surface, yielding large, buckled, cavity morphologies. Based on these results, we establish robust design criteria for polymer capsules and particles, demonstrated here for poly(vinyl alcohol), with well-defined shape, dimensions and internal microstructure.

Influence of calcium-induced droplet heteroaggregation on the physicochemical properties of oppositely charged lactoferrin coated lutein droplets and whey protein isolate-coated DHA droplets.

PubMed

Li, Xin; Wang, Xu; Xu, Duoxia; Cao, Yanping; Wang, Shaojia; Wang, Bei; Wang, Chengtao; Sun, Baoguo

2017-08-01

The influence of calcium-induced droplet heteroaggregation on the formation and physicochemical stability of mixed lutein and DHA emulsions was studied. Heteroaggregation was induced by mixing oppositely charged lactoferrin (LF)-coated lutein and whey protein isolate (WPI)-coated DHA emulsions with different CaCl 2 concentrations at pH 6.0. The droplet size, zeta-potential, transmission-physical stability and microstructure behavior (CLSM and Cryo-SEM) of single-protein emulsions and mixed emulsions were measured as a function of different CaCl 2 concentrations. Lutein degradation and DHA oxidation by measurement of lipid hydroperoxides and thiobarbituric acid reactive substances were determined during storage. The physical stability of the mixed emulsions could be modulated by controlling CaCl 2 concentrations. Microstructure behavior indicated that a mixed emulsion with 30 mM CaCl 2 promoted more droplets to form a special three-dimensional network and microcluster structures. The chemical stability of the mixed lutein and DHA emulsions was obviously enhanced by the addition of 30 mM CaCl 2 . The decreased surface areas of the DHA and lutein droplets and the physical barrier of the network of heteroaggregates against transition metals and free radicals could mainly explain the improvement in chemical stability. Calcium-induced droplet aggregation may be useful for creating specific food structures that lead to desirable physicochemical properties of multiple functional components.

Flexible particle flow-focusing in microchannel driven by droplet-directed induced-charge electroosmosis.

PubMed

Ren, Yukun; Liu, Xianyu; Liu, Weiyu; Tao, Ye; Jia, Yankai; Hou, Likai; Li, Wenying; Jiang, Hongyuan

2018-02-01

We report herein a novel microfluidic particle concentrator that utilizes constriction microchannels to enhance the flow-focusing performance of induced-charge electroosmosis (ICEO), where viscous hemi-spherical oil droplets are embedded within the mainchannel to form deformable converging-diverging constriction structures. The constriction region between symmetric oil droplets partially coated on the electrode strips can improve the focusing performance by inducing a granular wake flow area at the diverging channel, which makes almost all of the scattered sample particles trapped within a narrow stream on the floating electrode. Another asymmetric droplet pair arranged near the outlets can further direct the trajectory of focused particle stream to one specified outlet port depending on the symmetry breaking in the shape of opposing phase interfaces. By fully exploiting rectification properties of induced-charge electrokinetic phenomena at immiscible water/oil interfaces of tunable geometry, the expected function of continuous and switchable flow-focusing is demonstrated by preconcentrating both inorganic silica particles and biological yeast cells. Physical mechanisms responsible for particle focusing and locus deflection in the droplet-assisted concentrentor are analyzed in detail, and simulation results are in good accordance with experimental observations. Our work provides new routes to construct flexible electrokinetic framework for preprocessing on-chip biological samples before performing subsequent analysis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

WITHDRAWN: Fragmentation of charged aqueous nanodroplets

NASA Astrophysics Data System (ADS)

Ichiki, Kengo

2005-11-01

The whole evaporating process of charged aqueous nanodroplets is studied by systematic molecular dynamics simulations until most of the solvent molecules are evaporated. % The solvent evaporation makes the droplet smaller and smaller, and at a certain point the repulsive force among ions causes an instability, where typically single ion and 10 to 20 water molecules are disintegrated from the main droplet. % This ion fragmentation occurs around 70 to 80% of the charge predicted by the Rayleigh theory [Lord Rayleigh, Phil. Mag. 14, 184 (1882)]. % The numerical results are summarized in the function R(z) which is the fragmentation radius at the charge z. From the fitting by the power law Rz^β, we find that at lower temperature T=350 and 370 K the result is close to the Rayleigh theory β= 2/3, while at higher temperature T=400 and 450 K it is like β= 1/2. % Another fitting on R(z) by the extended ion evaporation mechanism [M. Gamero-Castaño and J. Fern'andez de la Mora, Anal. Chim. Acta 406, 67 (2000)] works well for both cases. % The final state of the evaporation process is typically a single ion with several water molecules. If we put an alanine dipeptide in zwitterionic form at the beginning, two charges remain in some cases.

Structure and Dynamics of Solvent Landscapes in Charge-Transfer Reactions

NASA Astrophysics Data System (ADS)

Leite, Vitor B. Pereira

The dynamics of solvent polarization plays a major role in the control of charge transfer reactions. The success of Marcus theory describing the solvent influence via a single collective quadratic polarization coordinate has been remarkable. Onuchic and Wolynes have recently proposed (J. Chem Phys 98 (3) 2218, 1993) a simple model demonstrating how a many-dimensional-complex model composed by several dipole moments (representing solvent molecules or polar groups in proteins) can be reduced under the appropriate limits into the Marcus Model. This work presents a dynamical study of the same model, which is characterized by two parameters, an average dipole-dipole interaction as a term associated with the potential energy landscape roughness. It is shown why the effective potential, obtained using a thermodynamic approach, is appropriate for the dynamics of the system. At high temperatures, the system exhibits effective diffusive one-dimensional dynamics, where the Born-Marcus limit is recovered. At low temperatures, a glassy phase appears with a slow non-self-averaging dynamics. At intermediate temperatures, the concept of equivalent diffusion paths and polarization dependence effects are discussed. This approach is extended to treat more realistic solvent models. Real solvents are discussed in terms of simple parameters described above, and an analysis of how different regimes affect the rate of charge transfer is presented. Finally, these ideas are correlated to analogous problems in other areas.

Solvent Additive-Assisted Anisotropic Assembly and Enhanced Charge Transport of π-Conjugated Polymer Thin Films.

PubMed

Jeong, Jae Won; Jo, Gyounglyul; Choi, Solip; Kim, Yoong Ahm; Yoon, Hyeonseok; Ryu, Sang-Wan; Jung, Jaehan; Chang, Mincheol

2018-05-30

Charge transport in π-conjugated polymer films involves π-π interactions within or between polymer chains. Here, we demonstrate a facile solution processing strategy that provides enhanced intra- and interchain π-π interactions of the resultant polymer films using a good solvent additive with low volatility. These increased interactions result in enhanced charge transport properties. The effect of the good solvent additive on the intra- and intermolecular interactions, morphologies, and charge transport properties of poly(3-hexylthiophene) (P3HT) films is systematically investigated. We found that the good solvent additive facilitates the self-assembly of P3HT chains into crystalline fibrillar nanostructures by extending the solvent drying time during thin-film formation. As compared to the prior approach using a nonsolvent additive with low volatility, the solvent blend system containing a good solvent additive results in enhanced charge transport in P3HT organic field-effect transistor (OFET) devices [from ca. 1.7 × 10 -2 to ca. 8.2 × 10 -2 cm 2 V -1 s -1 for dichlorobenzene (DCB) versus 4.4 × 10 -2 cm 2 V -1 s -1 for acetonitrile]. The mobility appears to be maximized over a broad spectrum of additive concentrations (1-7 vol %), indicative of a wide processing window. Detailed analysis results regarding the charge injection and transport characteristics of the OFET devices reveal that a high-boiling-point solvent additive decreases both the contact resistance ( R c ) and channel resistance ( R ch ), contributing to the mobility enhancement of the devices. Finally, the platform presented here is proven to be applicable to alternative good solvent additives with low volatility, such as chlorobenzene (CB) and trichlorobenzene (TCB). Specifically, the mobility enhancement of the resultant P3HT films increases in the order CB (bp 131 °C) < DCB (bp 180 °C) < TCB (bp 214 °C), suggesting that solvent additives with higher boiling points provide resultant

The effect of solvent relaxation time constants on free energy gap law for ultrafast charge recombination following photoinduced charge separation.

PubMed

Mikhailova, Valentina A; Malykhin, Roman E; Ivanov, Anatoly I

2018-05-16

To elucidate the regularities inherent in the kinetics of ultrafast charge recombination following photoinduced charge separation in donor-acceptor dyads in solutions, the simulations of the kinetics have been performed within the stochastic multichannel point-transition model. Increasing the solvent relaxation time scales has been shown to strongly vary the dependence of the charge recombination rate constant on the free energy gap. In slow relaxing solvents the non-equilibrium charge recombination occurring in parallel with solvent relaxation is very effective so that the charge recombination terminates at the non-equilibrium stage. This results in a crucial difference between the free energy gap laws for the ultrafast charge recombination and the thermal charge transfer. For the thermal reactions the well-known Marcus bell-shaped dependence of the rate constant on the free energy gap is realized while for the ultrafast charge recombination only a descending branch is predicted in the whole area of the free energy gap exceeding 0.2 eV. From the available experimental data on the population kinetics of the second and first excited states for a series of Zn-porphyrin-imide dyads in toluene and tetrahydrofuran solutions, an effective rate constant of the charge recombination into the first excited state has been calculated. The obtained rate constant being very high is nearly invariable in the area of the charge recombination free energy gap from 0.2 to 0.6 eV that supports the theoretical prediction.

"Inverted" Solvent Effect on Charge Transfer in the Excited State.

PubMed

Nau; Pischel

1999-10-04

Faster in cyclohexane than in acetonitrile is the fluorescence quenching of the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by amines and sulfides. Although this photoreaction is induced by charge transfer (CT; see picture) and exciplexes are formed, the increase in the dipole moment of the exciplex is not large enough to offset the solvent stabilization of the excited reactants, and an "inverted" solvent effect results.

Probing chemical transformation in picolitre volume aerosol droplets

NASA Astrophysics Data System (ADS)

Miloserdov, Anatolij; Day, Calum P. F.; Rosario, Gabriela L.; Horrocks, Benjamin R.; Carruthers, Antonia E.

2017-08-01

We have demonstrated chemical transformation in single microscopic-sized aerosol droplets localised in optical tweezers. Droplets in situ are measured during chemical transformation processes of solvent exchange and solute transformation through an ion exchange reaction. Solvent exchange between deionised water and heavy water in aerosol droplets is monitored through observation of the OH and OD Raman stretches. A change in solute chemistry of aerosol is achieved through droplet coalescence events between calcium chloride and sodium carbonate to promote ion exchange. The transformation forming meta-stable and stable states of CaCO3 is observed and analysed using Gaussian peak decomposition to reveal polymorphs.

Hidden topological constellations and polyvalent charges in chiral nematic droplets

PubMed Central

Posnjak, Gregor; Čopar, Simon; Muševič, Igor

2017-01-01

Topology has an increasingly important role in the physics of condensed matter, quantum systems, material science, photonics and biology, with spectacular realizations of topological concepts in liquid crystals. Here we report on long-lived hidden topological states in thermally quenched, chiral nematic droplets, formed from string-like, triangular and polyhedral constellations of monovalent and polyvalent singular point defects. These topological defects are regularly packed into a spherical liquid volume and stabilized by the elastic energy barrier due to the helical structure and confinement of the liquid crystal in the micro-sphere. We observe, for the first time, topological three-dimensional point defects of the quantized hedgehog charge q=−2, −3. These higher-charge defects act as ideal polyvalent artificial atoms, binding the defects into polyhedral constellations representing topological molecules. PMID:28220770

Hidden topological constellations and polyvalent charges in chiral nematic droplets

NASA Astrophysics Data System (ADS)

Posnjak, Gregor; Čopar, Simon; Muševič, Igor

2017-02-01

Topology has an increasingly important role in the physics of condensed matter, quantum systems, material science, photonics and biology, with spectacular realizations of topological concepts in liquid crystals. Here we report on long-lived hidden topological states in thermally quenched, chiral nematic droplets, formed from string-like, triangular and polyhedral constellations of monovalent and polyvalent singular point defects. These topological defects are regularly packed into a spherical liquid volume and stabilized by the elastic energy barrier due to the helical structure and confinement of the liquid crystal in the micro-sphere. We observe, for the first time, topological three-dimensional point defects of the quantized hedgehog charge q=-2, -3. These higher-charge defects act as ideal polyvalent artificial atoms, binding the defects into polyhedral constellations representing topological molecules.

Mass spectrometry of acoustically levitated droplets.

PubMed

Westphall, Michael S; Jorabchi, Kaveh; Smith, Lloyd M

2008-08-01

Containerless sample handling techniques such as acoustic levitation offer potential advantages for mass spectrometry, by eliminating surfaces where undesired adsorption/desorption processes can occur. In addition, they provide a unique opportunity to study fundamental aspects of the ionization process as well as phenomena occurring at the air-droplet interface. Realizing these advantages is contingent, however, upon being able to effectively interface levitated droplets with a mass spectrometer, a challenging task that is addressed in this report. We have employed a newly developed charge and matrix-assisted laser desorption/ionization (CALDI) technique to obtain mass spectra from a 5-microL acoustically levitated droplet containing peptides and an ionic matrix. A four-ring electrostatic lens is used in conjunction with a corona needle to produce bursts of corona ions and to direct those ions toward the droplet, resulting in droplet charging. Analyte ions are produced from the droplet by a 337-nm laser pulse and detected by an atmospheric sampling mass spectrometer. The ion generation and extraction cycle is repeated at 20 Hz, the maximum operating frequency of the laser employed. It is shown in delayed ion extraction experiments that both positive and negative ions are produced, behavior similar to that observed for atmospheric pressure matrix-assisted laser absorption/ionization. No ion signal is observed in the absence of droplet charging. It is likely, although not yet proven, that the role of the droplet charging is to increase the strength of the electric field at the surface of the droplet, reducing charge recombination after ion desorption.

Charge-Induced Saffman-Taylor Instabilities in Toroidal Droplets

NASA Astrophysics Data System (ADS)

Fragkopoulos, A. A.; Aizenman, A.; Fernández-Nieves, A.

2017-06-01

We show that charged toroidal droplets can develop fingerlike structures as they expand due to Saffman-Taylor instabilities. While these are commonly observed in quasi-two-dimensional geometries when a fluid displaces another fluid of higher viscosity, we show that the toroidal confinement breaks the symmetry of the problem, effectively making it quasi-two-dimensional and enabling the instability to develop in this three-dimensional situation. We control the expansion speed of the torus with the imposed electric stress and show that fingers are observed provided the characteristic time scale associated with this instability is smaller than the characteristic time scale associated with Rayleigh-Plateau break-up. We confirm our interpretation of the results by showing that the number of fingers is consistent with expectations from linear stability analysis in radial Hele-Shaw cells.

Mass Spectrometry of Acoustically Levitated Droplets

PubMed Central

Westphall, Michael S.; Jorabchi, Kaveh; Smith, Lloyd M.

2008-01-01

Containerless sample handling techniques such as acoustic levitation offer potential advantages for mass spectrometry, by eliminating surfaces where undesired adsorption/desorption processes can occur. In addition, they provide a unique opportunity to study fundamental aspects of the ionization process as well as phenomena occurring at the air–droplet interface. Realizing these advantages is contingent, however, upon being able to effectively interface levitated droplets with a mass spectrometer, a challenging task that is addressed in this report. We have employed a newly developed charge and matrix-assisted laser desorption/ionization (CALDI) technique to obtain mass spectra from a 5-μL acoustically levitated droplet containing peptides and an ionic matrix. A four-ring electrostatic lens is used in conjunction with a corona needle to produce bursts of corona ions and to direct those ions toward the droplet, resulting in droplet charging. Analyte ions are produced from the droplet by a 337-nm laser pulse and detected by an atmospheric sampling mass spectrometer. The ion generation and extraction cycle is repeated at 20 Hz, the maximum operating frequency of the laser employed. It is shown in delayed ion extraction experiments that both positive and negative ions are produced, behavior similar to that observed for atmospheric pressure matrix-assisted laser absorption/ionization. No ion signal is observed in the absence of droplet charging. It is likely, although not yet proven, that the role of the droplet charging is to increase the strength of the electric field at the surface of the droplet, reducing chargere combination after ion desorption. PMID:18582090

Influence of solvent species on the charge-discharge characteristics of a natural graphite electrode

NASA Astrophysics Data System (ADS)

Fujimoto, Masahisa; Shoji, Yoshihiro; Kida, Yoshinori; Ohshita, Ryuji; Nohma, Toshiyuki; Nishio, Koji

The charge-discharge characteristics of a natural graphite electrode are examined in a mixed solvent composed of ethylene carbonate (EC) and propylene carbonate (PC). The characteristics are influenced largely by the solvent species. Natural graphite electrode displays good charge-discharge characteristics in an electrolyte containing EC with a high volume fraction. In an electrolyte containing PC, however, the electrode cannot be charged and the solvent is decomposed. X-ray photoelectron spectroscopy is used to obtain information about the surface of natural graphite. A thin LiF layer, the decomposition product of lithium hexafluorophosphate (LiPF 6), is formed on the surface of the natural graphite charged to 0.5 V (vs. Li/Li +) in an electrolyte containing a high volume fraction of EC. On the other hand, LiF and a carbonate compound are formed in the bulk and on the surface of natural graphite when the volume fraction of PC is high. These results suggest that the thin LiF layer, which is produced at a potential higher than 0.5 V (vs. Li/Li +) on the surface of natural graphite, enables the lithium ions to intercalate into the natural graphite without further decomposition of the electrolyte.

Electric field makes Leidenfrost droplets take a leap.

PubMed

Wildeman, Sander; Sun, Chao

2016-12-06

Leidenfrost droplets, i.e. droplets whose mobility is ensured by a thin vapor film between the droplet and a hot plate, are exposed to an external electric field. We find that in a strong vertical electric field the droplet can start to bounce progressively higher, defying gravitational attraction. From the droplet's trajectory we infer the temporal evolution of the amount of charge on the droplet. This reveals that the charge starts high and then decreases in steps as the droplet slowly evaporates. After each discharge event the charge is in a fixed proportion to the droplet's surface area. We show that this behavior can be accurately modeled by treating the droplet as a conducting sphere that occasionally makes electrical contact with the hot plate, at intervals dictated by an electro-capillary instability in the vapor film. An analysis of the kinetic and potential energies of the bouncing droplet reveals that, while the overall motion is damped, the droplet occasionally experiences a sudden boost, keeping its energy close to the value for which the free fall trajectory and droplet oscillation are in sync. This helps the droplet to escape from the hot surface when finally the electrical surface forces overtake gravity.

Droplet-Based Production of Liposomes

NASA Technical Reports Server (NTRS)

Ackley, Donald E.; Forster, Anita

2009-01-01

A process for making monodisperse liposomes having lipid bilayer membranes involves fewer, simpler process steps than do related prior methods. First, a microfluidic, cross junction droplet generator is used to produce vesicles comprising aqueous solution droplets contained in single layer lipid membranes. The vesicles are collected in a lipid-solvent mix that is at most partially soluble in water and is less dense than is water. A layer of water is dispensed on top of the solvent. By virtue of the difference in densities, the water sinks to the bottom and the solvent floats to the top. The vesicles, which have almost the same density as that of water, become exchanged into the water instead of floating to the top. As there are excess lipids in the solvent solution, in order for the vesicles to remain in the water, the addition of a second lipid layer to each vesicle is energetically favored. The resulting lipid bilayers present the hydrophilic ends of the lipid molecules to both the inner and outer membrane surfaces. If lipids of a second kind are dissolved in the solvent in sufficient excess before use, then asymmetric liposomes may be formed.

Electro-coalescence of particle-coated droplets

NASA Astrophysics Data System (ADS)

Shum, Anderson Ho Cheung

Droplets in air or in an immiscible liquid phase are used widely in applications ranging from personal hygiene products to drug delivery. The stability of the droplets are highly linked to their utility, and thus have been systematically studied. To enhance the stability of the droplets, particles are often added to the droplets. In this talk, I will discuss how the particle layer at droplet interfaces responds to electrical charging of the droplets. The electrical forces can distort the droplet shape, which is opposed by the layer of particles adsorbed. A balance of the electrical and interfacial effects provides a quantitative indicator of the droplet instability. The coalescence of droplets in both air and liquid induced by electrically charging, which we call ``electro-coalescence'', will be introduced, with its potential application in devising a digital millifluidic platform. We thank the Research Grants Council of Hong Kong (No. HKU 719813E, 17304514 and 17306315 and C6004-14G) from the and National Natural Science Foundation of China (No. 21476189/B060201 and 91434202).

Scaling laws for first and second generation electrospray droplets

NASA Astrophysics Data System (ADS)

Basaran, Osman; Sambath, Krishnaraj; Anthony, Christopher; Collins, Robert; Wagoner, Brayden; Harris, Michael

2017-11-01

When uncharged liquid interfaces of pendant and free drops (hereafter referred to as parent drops) or liquid films are subject to a sufficiently strong electric field, they can emit thin fluid jets from conical tip structures that form at their surfaces. The disintegration of such jets into a spray consisting of charged droplets (hereafter referred to as daughter droplets) is common to electrospray ionization mass spectrometry, printing and coating processes, and raindrops in thunderclouds. We use simulation to determine the sizes and charges of these first-generation daughter droplets which are shown to be Coulombically stable and charged below the Rayleigh limit of stability. Once these daughter droplets shrink in size due to evaporation, they in turn reach their respective Rayleigh limits and explode by emitting yet even smaller second-generation daughter droplets from their conical tips. Once again, we use simulation and theory to deduce scaling laws for the sizes and charges of these second-generation droplets. A comparison is also provided for scaling laws pertaining to different generations of daughter droplets.

Buckling in armored droplets.

PubMed

Sicard, François; Striolo, Alberto

2017-06-29

The buckling mechanism in droplets stabilized by solid particles (armored droplets) is tackled at a mesoscopic level using dissipative particle dynamics simulations. We consider one spherical water droplet in a decane solvent coated with nanoparticle monolayers of two different types: Janus (particles whose surface shows two regions with different wetting properties) and homogeneous. The chosen particles yield comparable initial three-phase contact angles, selected to maximize the adsorption energy at the interface. We study the interplay between the evolution of droplet shape, layering of the particles, and their distribution at the interface when the volume of the droplets is reduced. We show that Janus particles affect strongly the shape of the droplet with the formation of a crater-like depression. This evolution is actively controlled by a close-packed particle monolayer at the curved interface. In contrast, homogeneous particles follow passively the volume reduction of the droplet, whose shape does not deviate too much from spherical, even when a nanoparticle monolayer/bilayer transition is detected at the interface. We discuss how these buckled armored droplets might be of relevance in various applications including potential drug delivery systems and biomimetic design of functional surfaces.

Coalescence of repelling colloidal droplets: a route to monodisperse populations.

PubMed

Roger, Kevin; Botet, Robert; Cabane, Bernard

2013-05-14

Populations of droplets or particles dispersed in a liquid may evolve through Brownian collisions, aggregation, and coalescence. We have found a set of conditions under which these populations evolve spontaneously toward a narrow size distribution. The experimental system consists of poly(methyl methacrylate) (PMMA) nanodroplets dispersed in a solvent (acetone) + nonsolvent (water) mixture. These droplets carry electrical charges, located on the ionic end groups of the macromolecules. We used time-resolved small angle X-ray scattering to determine their size distribution. We find that the droplets grow through coalescence events: the average radius (R) increases logarithmically with elapsed time while the relative width σR/(R) of the distribution decreases as the inverse square root of (R). We interpret this evolution as resulting from coalescence events that are hindered by ionic repulsions between droplets. We generalize this evolution through a simulation of the Smoluchowski kinetic equation, with a kernel that takes into account the interactions between droplets. In the case of vanishing or attractive interactions, all droplet encounters lead to coalescence. The corresponding kernel leads to the well-known "self-preserving" particle distribution of the coalescence process, where σR/(R) increases to a plateau value. However, for droplets that interact through long-range ionic repulsions, "large + small" droplet encounters are more successful at coalescence than "large + large" encounters. We show that the corresponding kernel leads to a particular scaling of the droplet-size distribution-known as the "second-scaling law" in the theory of critical phenomena, where σR/(R) decreases as 1/√(R) and becomes independent of the initial distribution. We argue that this scaling explains the narrow size distributions of colloidal dispersions that have been synthesized through aggregation processes.

Crater Formation on Electrodes during Charge Transfer with Aqueous Droplets or Solid Particles

NASA Astrophysics Data System (ADS)

Elton, Eric S.; Rosenberg, Ethan R.; Ristenpart, William D.

2017-11-01

We report that metallic electrodes are physically pitted during charge transfer events with water droplets or other conductive objects moving in strong electric fields (>1 kV/cm). Post situ microscopic inspection of the electrode shows that an individual charge transfer event yields a crater approximately 1 to 3 microns wide, often with features similar to splash coronae. We interpret the crater formation in terms of localized melting of the electrode via resistive heating concurrent with dielectric breakdown through the surrounding insulating fluid. A scaling analysis indicates that the crater diameter scales as the inverse cube root of the melting point temperature Tm of the metal, in accord with measurements on several metals (660°C <=Tm <= 3414°C). The process of crater formation provides a possible explanation for the longstanding difficulty in quantitatively corroborating Maxwell's prediction for the amount of charge acquired by spheres contacting a planar electrode.

Solvent annealing induced phase separation and dewetting in PMMA∕SAN blend film: film thickness and solvent dependence.

PubMed

You, Jichun; Zhang, Shuangshuang; Huang, Gang; Shi, Tongfei; Li, Yongjin

2013-06-28

The competition between "dewetting" and "phase separation" behaviors in polymer blend films attracts significant attention in the last decade. The simultaneous phase separation and dewetting in PMMA∕SAN [poly(methyl methacrylate) and poly(styrene-ran-acrylonitrile)] blend ultrathin films upon solvent annealing have been observed for the first time in our previous work. In this work, film thickness and annealing solvent dependence of phase behaviors in this system has been investigated using atomic force microscopy and grazing incidence small-angle X-ray scattering (GISAXS). On one hand, both vertical phase separation and dewetting take place upon selective solvent vapor annealing, leading to the formation of droplet∕mimic-film structures with various sizes (depending on original film thickness). On the other hand, the whole blend film dewets the substrate and produces dispersed droplets on the silicon oxide upon common solvent annealing. GISAXS results demonstrate the phase separation in the big dewetted droplets resulted from the thicker film (39.8 nm). In contrast, no period structure is detected in small droplets from the thinner film (5.1 nm and 9.7 nm). This investigation indicates that dewetting and phase separation in PMMA∕SAN blend film upon solvent annealing depend crucially on the film thickness and the atmosphere during annealing.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOEpatents

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

2017-01-24

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Electrospray Charging of Minerals: Surface Chemistry and Applications to High-Velocity Microparticle Impacts

NASA Astrophysics Data System (ADS)

Daly, T.; Call, S.; Austin, D. E.

2010-12-01

Electrospray is a soft ionization technique commonly used to charge large biomolecules; it has, however, also been applied to inorganic compounds. We are extending this technique to mineral microparticles. Electrospray-charged mineral microparticles are interesting in the context of surface science because surface chemistry dictates where and how charge carriers can bond to mineral surfaces. In addition, using electrospray to charge mineral particles allows these particles to be electrostatically accelerated as projectiles in high- and hyper-velocity impacts. Since current techniques for producing high- and hyper-velocity microparticle impacts are largely limited to metal or metal-coated projectiles, using minerals as projectiles is a significant innovation. Electrospray involves three steps: creation of charged droplets containing solute/particles, evaporation and bifurcation of droplets, and desolvation of the solute/particles. An acidified solution is slowly pumped through a needle in a strong DC field, which causes the solution to break into tiny, charged droplets laden with protons. Solvent evaporates from the electrosprayed droplets as they move through the electric field toward a grounded plate, causing the charge on the droplet to increase relative to its mass. When the electrosprayed droplet’s charge becomes such that the droplet is no longer stable, it bifurcates, and each of the resulting droplets carries some of the original droplet’s charge. Evaporation and bifurcation continues until the solute particle is completely desolvated. The result is a protonated solute molecule or particle. We built an instrument that electrosprays particles into vacuum and measures them using an image charge detector. Mineral microparticles were prepared by grinding natural mineral samples to ~2 µm diameter. These microparticles are then added to a 4:1 methanol:water solution to create a 0.005% w/v suspension. The suspension is electrosprayed into vacuum, where the

Controlled Gelation of Particle Suspensions Using Controlled Solvent Removal in Picoliter Droplets

NASA Astrophysics Data System (ADS)

Vuong, Sharon; Walker, Lynn; Anna, Shelley

2013-11-01

Droplets in microfluidic devices have proven useful as uniform picoliter reactors for nanoparticle synthesis and as components in tunable emulsions. However, there can be significant transport between the component phases depending on solubility and other factors. In the present talk, we show that water droplets trapped within a microfluidic device for tens of hours slowly dehydrate, concentrating the contents encapsulated within. We use this slow dehydration along with control of the initial droplet composition to monitor gelation of aqueous suspensions of spherical silica particles (Ludox) and disk-shaped clay particles (Laponite). Droplets are generated in a microfluidic device containing small wells that trap the droplets. We monitor the concentration process through size and shape changes of these droplets as a function of time in tens of droplets and use the large number of individual reactors to generate statistics regarding the gelation process. We also examine changes in suspension viscosity through fluorescent particle tracking as a function of dehydration rate, initial suspension concentration and initial droplet volume, and added salt, and compare the results with the Krieger-Dougherty model in which viscosity increases dramatically with particle volume fraction.

A simple model of solvent-induced symmetry-breaking charge transfer in excited quadrupolar molecules

NASA Astrophysics Data System (ADS)

Ivanov, Anatoly I.; Dereka, Bogdan; Vauthey, Eric

2017-04-01

A simple model has been developed to describe the symmetry-breaking of the electronic distribution of AL-D-AR type molecules in the excited state, where D is an electron donor and AL and AR are identical acceptors. The origin of this process is usually associated with the interaction between the molecule and the solvent polarization that stabilizes an asymmetric and dipolar state, with a larger charge transfer on one side than on the other. An additional symmetry-breaking mechanism involving the direct Coulomb interaction of the charges on the acceptors is proposed. At the same time, the electronic coupling between the two degenerate states, which correspond to the transferred charge being localised either on AL or AR, favours a quadrupolar excited state with equal amount of charge-transfer on both sides. Because of these counteracting effects, symmetry breaking is only feasible when the electronic coupling remains below a threshold value, which depends on the solvation energy and the Coulomb repulsion energy between the charges located on AL and AR. This model allows reproducing the solvent polarity dependence of the symmetry-breaking reported recently using time-resolved infrared spectroscopy.

Preventing droplet deformation during dielectrophoretic centering of a compound emulsion droplet

NASA Astrophysics Data System (ADS)

Randall, Greg; Blue, Brent

2012-11-01

Compound droplets, or droplets-within-droplets, are traditionally key components in applications ranging from drug delivery to the food industry. Presently, millimeter-sized compound droplets are precursors for shell targets in inertial fusion energy work. However, a key constraint in target fabrication is a uniform shell wall thickness, which in turn requires a centered core droplet in the compound droplet precursor. Previously, Bei et al. (2009, 2010) have shown that compound droplets could be centered in a static fluid using an electric field of 0.7 kV/cm at 20 MHz. Randall et al. (2012) developed a process to center the core of a moving compound droplet, though the ~kV/cm field induced small (< 5%) but undesirable droplet stretching. This work shows that by using macromolecular emulsifiers to strengthen the droplet's interfaces, (proteins, tunable peptides, or biotinylated streptavidin) droplet stretching can be greatly inhibited. Proof-of-principle experiments are performed in either a stagnant density-matched aquarium or a vertical channel of buoyancy-driven droplets in a ~kV/cm electric field. A scaling analysis is given from a fluid mechanics and interfacial rheology perspective and we discuss the effective interfacial charge from an emulsifier and its impact on centering. Work funded by General Atomics Internal R&D.

Crater Formation on Electrodes during Charge Transfer with Aqueous Droplets or Solid Particles

NASA Astrophysics Data System (ADS)

Elton, E. S.; Rosenberg, E. R.; Ristenpart, W. D.

2017-09-01

We report that metallic electrodes are physically pitted during charge transfer events with water droplets or other conductive objects moving in strong electric fields (>1 kV /cm ). Post situ microscopic inspection of the electrode shows that an individual charge transfer event yields a crater approximately 1-3 μ m wide, often with features similar to a splash corona. We interpret the crater formation in terms of localized melting of the electrode via resistive heating concurrent with dielectric breakdown through the surrounding insulating fluid. A scaling analysis indicates that the crater diameter scales as the inverse cube root of the melting point temperature Tm of the metal, in accord with measurements on several metals (660 °C ≤Tm≤3414 °C ). The process of crater formation provides a possible explanation for the longstanding difficulty in quantitatively corroborating Maxwell's prediction for the amount of charge acquired by spheres contacting a planar electrode.

Solvent jet desorption capillary photoionization-mass spectrometry.

PubMed

Haapala, Markus; Teppo, Jaakko; Ollikainen, Elisa; Kiiski, Iiro; Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

2015-03-17

A new ambient mass spectrometry method, solvent jet desorption capillary photoionization (DCPI), is described. The method uses a solvent jet generated by a coaxial nebulizer operated at ambient conditions with nitrogen as nebulizer gas. The solvent jet is directed onto a sample surface, from which analytes are extracted into the solvent and ejected from the surface in secondary droplets formed in collisions between the jet and the sample surface. The secondary droplets are directed into the heated capillary photoionization (CPI) device, where the droplets are vaporized and the gaseous analytes are ionized by 10 eV photons generated by a vacuum ultraviolet (VUV) krypton discharge lamp. As the CPI device is directly connected to the extended capillary inlet of the MS, high ion transfer efficiency to the vacuum of MS is achieved. The solvent jet DCPI provides several advantages: high sensitivity for nonpolar and polar compounds with limit of detection down to low fmol levels, capability of analyzing small and large molecules, and good spatial resolution (250 μm). Two ionization mechanisms are involved in DCPI: atmospheric pressure photoionization, capable of ionizing polar and nonpolar compounds, and solvent assisted inlet ionization capable of ionizing larger molecules like peptides. The feasibility of DCPI was successfully tested in the analysis of polar and nonpolar compounds in sage leaves and chili pepper.

The Evolution of Electrospray Generated Droplets is Not Affected by Ionization Mode

NASA Astrophysics Data System (ADS)

Liigand, Piia; Heering (Suu), Agnes; Kaupmees, Karl; Leito, Ivo; Girod, Marion; Antoine, Rodolphe; Kruve, Anneli

2017-10-01

Ionization efficiency and mechanism in ESI is strongly affected by the properties of mobile phase. The use of mobile-phase properties to accurately describe droplets in ESI source is convenient but may be inadequate as the composition of the droplets is changing in the plume due to electrochemical reactions occurring in the needle tip as well as continuous drying and fission of droplets. Presently, there is paucity of research on the effect of the polarity of the ESI mode on mobile phase composition in the droplets. In this paper, the change in the organic solvent content, pH, and droplet size are studied in the ESI plume in both ESI+ and ESI- ionization mode. We introduce a rigorous way - the absolute pH (pHabs H 2 O) - to describe pH change in the plume that takes into account organic solvent content in the mobile phase. pHabs H 2 O enables comparing acidities of ESI droplets with different organic solvent contents. The results are surprisingly similar for both ionization modes, indicating that the dynamics of the change of mobile-phase properties is independent from the ESI mode used. This allows us to conclude that the evolution of ESI droplets first of all proceeds via the evaporation of the organic modifier and to a lesser extent via fission of smaller droplets from parent droplets. Secondly, our study shows that qualitative findings related to the ESI process obtained on the ESI+ mode can almost directly be applied also in the ESI- mode. [Figure not available: see fulltext.

Substituent and Solvent Effects on Excited State Charge Transfer Behavior of Highly Fluorescent Dyes Containing Thiophenylimidazole-Based Aldehydes

NASA Technical Reports Server (NTRS)

Santos, Javier; Bu, Xiu R.; Mintz, Eric A.

2001-01-01

The excited state charge transfer for a series of highly fluorescent dyes containing thiophenylimidazole moiety was investigated. These systems follow the Twisted Intramolecular Charge Transfer (TICT) model. Dual fluorescence was observed for each substituted dye. X-ray structures analysis reveals a twisted ground state geometry for the donor substituted aryl on the 4 and 5 position at the imidazole ring. The excited state charge transfer was modeled by a linear solvation energy relationship using Taft's pi and Dimroth's E(sub T)(30) as solvent parameters. There is linear relation between the energy of the fluorescence transition and solvent polarity. The degree of stabilization of the excited state charge transfer was found to be consistent with the intramolecular molecular charge transfer. Excited dipole moment was studied by utilizing the solvatochromic shift method.

Regimes of electrostatic collapse of a highly charged polyelectrolyte in a poor solvent.

PubMed

Tom, Anvy Moly; Vemparala, Satyavani; Rajesh, R; Brilliantov, Nikolai V

2017-03-01

We perform extensive molecular dynamics simulations of a highly charged, collapsed, flexible polyelectrolyte chain in a poor solvent for the case when the electrostatic interactions, characterized by the reduced Bjerrum length l B , are strong. We find the existence of several sub-regimes in the dependence of the gyration radius of the chain R g on l B characterized by R g ∼ l. In contrast to a good solvent, the exponent γ for a poor solvent crucially depends on the size and valency of the counterions. To explain the different sub-regimes, we generalize the existing counterion fluctuation theory by including a more complete account of all possible volume interactions in the free energy of the polyelectrolyte chain. We also show that the presence of condensed counterions modifies the effective attraction among the chain monomers and modulates the sign of the second virial coefficient under poor solvent conditions.

Digitally controlled droplet microfluidic system based on electrophoretic actuation

NASA Astrophysics Data System (ADS)

Im, Do Jin; Yoo, Byeong Sun; Ahn, Myung Mo; Moon, Dustin; Kang, In Seok

2012-11-01

Most researches on direct charging and the subsequent manipulation of a charged droplet were focused on an on-demand sorting in microchannel where carrier fluid transports droplets. Only recently, an individual actuation of a droplet without microchannel and carrier fluid was tried. However, in the previous work, the system size was too large and the actuation voltage was too high (1.5 kV), which limits the applicability of the technology to mobile use. Therefore, in the current research, we have developed a miniaturized digital microfluidic system based on the electrophoresis of a charged droplet (ECD). By using a pin header socket for an array of electrodes, much smaller microfluidic system can be made from simple fabrication process with low cost. A full two dimensional manipulation (0.4 cm/s) of a droplet (300 nL) suspended in silicone oil (6 cSt) and multiple droplet actuation have been performed with reasonable actuation voltage (300 V). By multiple droplet actuation and coalescence, a practical biochemical application also has been demonstrated. We hope the current droplet manipulation method (ECD) can be a good alternative or complimentary technology to the conventional ones and therefore contributes to the development of droplet microfluidics. This work has been supported by BK21 program of the Ministry of Education, Science and Technology (MEST) of Korea.

Liquid crystal Janus emulsion droplets: preparation, tumbling, and swimming.

PubMed

Jeong, Joonwoo; Gross, Adam; Wei, Wei-Shao; Tu, Fuquan; Lee, Daeyeon; Collings, Peter J; Yodh, A G

2015-09-14

This study introduces liquid crystal (LC) Janus droplets. We describe a process for the preparation of these droplets, which consist of nematic LC and polymer compartments. The process employs solvent-induced phase separation in emulsion droplets generated by microfluidics. The droplet morphology was systematically investigated and demonstrated to be sensitive to the surfactant concentration in the background phase, the compartment volume ratio, and the possible coalescence of multiple Janus droplets. Interestingly, the combination of a polymer and an anisotropic LC introduces new functionalities into Janus droplets, and these properties lead to unusual dynamical behaviors. The different densities and solubilities of the two compartments produce gravity-induced alignment, tumbling, and directional self-propelled motion of Janus droplets. LC Janus droplets with remarkable optical properties and dynamical behaviors thus offer new avenues for applications of Janus colloids and active soft matter.

Single photon emission of a charge-tunable GaAs/Al{sub 0.25}Ga{sub 0.75}As droplet quantum dot device

DOE Office of Scientific and Technical Information (OSTI.GOV)

Langer, Fabian, E-mail: fabian.langer@physik.uni-wuerzburg.de; Plischke, David; Kamp, Martin

2014-08-25

In this work, we report the fabrication of a charge-tunable GaAs/Al{sub 0.25}Ga{sub 0.75}As quantum dot (QD) device containing QDs deposited by modified droplet epitaxy producing almost strain and composition gradient free QDs. We obtained a QD density in the low 10{sup 9 }cm{sup −2} range that enables us to perform spectroscopy on single droplet QDs showing linewidths as narrow as 40 μeV. The integration of the QDs into a Schottky diode allows us to controllably charge a single QD with up to four electrons, while non-classical photoluminescence is proven by photon auto-correlation measurements showing photon-antibunching (g{sup (2)}(0) = 0.05).

Emulsion droplet interactions: a front-tracking treatment

NASA Astrophysics Data System (ADS)

Mason, Lachlan; Juric, Damir; Chergui, Jalel; Shin, Seungwon; Craster, Richard V.; Matar, Omar K.

2017-11-01

Emulsion coalescence influences a multitude of industrial applications including solvent extraction, oil recovery and the manufacture of fast-moving consumer goods. Droplet interaction models are vital for the design and scale-up of processing systems, however predictive modelling at the droplet-scale remains a research challenge. This study simulates industrially relevant moderate-inertia collisions for which a high degree of droplet deformation occurs. A hybrid front-tracking/level-set approach is used to automatically account for interface merging without the need for `bookkeeping' of interface connectivity. The model is implemented in Code BLUE using a parallel multi-grid solver, allowing both film and droplet-scale dynamics to be resolved efficiently. Droplet interaction simulations are validated using experimental sequences from the literature in the presence and absence of background turbulence. The framework is readily extensible for modelling the influence of surfactants and non-Newtonian fluids on droplet interaction processes. EPSRC, UK, MEMPHIS program Grant (EP/K003976/1), RAEng Research Chair (OKM), PETRONAS.

Universal fluid droplet ejector

DOEpatents

Lee, E.R.; Perl, M.L.

1999-08-24

A droplet generator comprises a fluid reservoir having a side wall made of glass or quartz, and an end cap made from a silicon plate. The end cap contains a micromachined aperture through which the fluid is ejected. The side wall is thermally fused to the end cap, and no adhesive is necessary. This means that the fluid only comes into contact with the side wall and the end cap, both of which are chemically inert. Amplitudes of drive pulses received by reservoir determine the horizontal displacements of droplets relative to the ejection aperture. The drive pulses are varied such that the dropper generates a two-dimensional array of vertically-falling droplets. Vertical and horizontal inter-droplet spacings may be varied in real time. Applications include droplet analysis experiments such as Millikan fractional charge searches and aerosol characterization, as well as material deposition applications. 8 figs.

Solvent electronic polarization effects on a charge transfer excitation studied by the mean-field QM/MM method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakano, Hiroshi; Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Kyoto 615-8245

2015-12-31

Electronic polarization effects of a medium can have a significant impact on a chemical reaction in condensed phases. We discuss the effects on the charge transfer excitation of a chromophore, N,N-dimethyl-4-nitroaniline, in various solvents using the mean-field QM/MM method with a polarizable force field. The results show that the explicit consideration of the solvent electronic polarization effects is important especially for a solvent with a low dielectric constant when we study the solvatochromism of the chromophore.

On-demand Droplet Manipulation via Triboelectrification

NASA Astrophysics Data System (ADS)

Wang, Wei; Vahabi, Hamed; Cackovic, Matthew; Jiang, Rui; Kota, Arun

2017-11-01

Controlled manipulation of liquid droplets has attracted tremendous interest across different scientific fields over the past two decades. To date, a variety of external stimuli-mediated methods such as magnetic field, electric field, and light have been developed for manipulating droplets on surfaces. However, these methods usually have drawbacks such as complex fabrication of manipulation platform, low droplet motility, expensive actuation system and lack of precise control. In this work, we demonstrate the controlled manipulation of liquid droplet with both high (e.g., water) and low (e.g., n-hexadecane) dielectric strengths on a smooth, slippery surface via triboelectric effect. Our highly simple, facile and portable methodology enables on-demand, precise manipulation of droplets using solely the electrostatic attraction or repulsion force, which is exerted on the droplet by a simple charged actuator (e.g., Teflon film). We envision that our triboelectric effect enabled droplet manipulation methodology will open a new avenue for droplet based lab-on-a-chip systems, energy harvesting devices and biomedical applications.

Theoretical evidence of charge transfer interaction between SO₂ and deep eutectic solvents formed by choline chloride and glycerol.

PubMed

Li, Hongping; Chang, Yonghui; Zhu, Wenshuai; Wang, Changwei; Wang, Chao; Yin, Sheng; Zhang, Ming; Li, Huaming

2015-11-21

The nature of the interaction between deep eutectic solvents (DESs), formed by ChCl and glycerol, and SO2 has been systematically investigated using the M06-2X density functional combined with cluster models. Block-localized wave function energy decomposition (BLW-ED) analysis shows that the interaction between SO2 and DESs is dominated by a charge transfer interaction. After this interaction, the SO2 molecule becomes negatively charged, whereas the ChCl-glycerol molecule is positively charged, which is the result of Lewis acid-base interaction. The current result affords a theoretical proof that it is highly useful and efficient to manipulate the Lewis acidity of absorbents for SO2 capture. Moreover, hydrogen bonding as well as electrostatic interactions may also contribute to the stability of the complex. Structure analysis shows that solvent molecules will adjust their geometries to interact with SO2. In addition, the structure of SO2 is barely changed after interaction. The interaction energy between different cluster models and SO2 ranges from -6.8 to -14.4 kcal mol(-1). It is found that the interaction energy is very sensitive to the solvent structure. The moderate interaction between ChCl-glycerol and SO2 is consistent with the concept that highly efficient solvents for SO2 absorption should not only be solvable but also regenerable.

Droplet microfluidics with a nanoemulsion continuous phase.

PubMed

Gu, Tonghan; Yeap, Eunice W Q; Somasundar, Ambika; Chen, Ran; Hatton, T Alan; Khan, Saif A

2016-07-05

We present the first study of a novel, generalizable method that uses a water-in-oil nanoemulsion as the continuous phase to generate uniform aqueous micro-droplets in a capillary-based microfluidic system. We first study the droplet generation mechanism in this system and compare it to the more conventional case where a simple oil/solvent (with surfactant) is used as the continuous phase. Next, we present two versatile methods - adding demulsifying chemicals and heat treatment - to allow active online chemical interaction between the continuous and dispersed phases. These methods allow each generated micro-droplet to act as a well-mixed micro-reactor with walls that are 'permeable' to the nanoemulsion droplets and their contents. Finally, we demonstrate an application of this system in the fabrication of uniform hydrogel (alginate) micro-beads with control over particle properties such as size and swelling. Our work expands the toolbox of droplet-based microfluidics, enabling new opportunities and applications involving active colloidal continuous phases carrying chemical payloads, both in advanced materials synthesis and droplet-based screening and diagnostic methods.

Universal fluid droplet ejector

DOEpatents

Lee, Eric R.; Perl, Martin L.

1999-08-24

A droplet generator comprises a fluid reservoir having a side wall made of glass or quartz, and an end cap made from a silicon plate. The end cap contains a micromachined aperture through which the fluid is ejected. The side wall is thermally fused to the end cap, and no adhesive is necessary. This means that the fluid only comes into contact with the side wall and the end cap, both of which are chemically inert. Amplitudes of drive pulses received by reservoir determine the horizontal displacements of droplets relative to the ejection aperture. The drive pulses are varied such that the dropper generates a two-dimensional array of vertically-falling droplets. Vertical and horizontal interdroplet spacings may be varied in real time. Applications include droplet analysis experiments such as Millikan fractional charge searches and aerosol characterization, as well as material deposition applications.

Treatment of charge singularities in implicit solvent models.

PubMed

Geng, Weihua; Yu, Sining; Wei, Guowei

2007-09-21

This paper presents a novel method for solving the Poisson-Boltzmann (PB) equation based on a rigorous treatment of geometric singularities of the dielectric interface and a Green's function formulation of charge singularities. Geometric singularities, such as cusps and self-intersecting surfaces, in the dielectric interfaces are bottleneck in developing highly accurate PB solvers. Based on an advanced mathematical technique, the matched interface and boundary (MIB) method, we have recently developed a PB solver by rigorously enforcing the flux continuity conditions at the solvent-molecule interface where geometric singularities may occur. The resulting PB solver, denoted as MIBPB-II, is able to deliver second order accuracy for the molecular surfaces of proteins. However, when the mesh size approaches half of the van der Waals radius, the MIBPB-II cannot maintain its accuracy because the grid points that carry the interface information overlap with those that carry distributed singular charges. In the present Green's function formalism, the charge singularities are transformed into interface flux jump conditions, which are treated on an equal footing as the geometric singularities in our MIB framework. The resulting method, denoted as MIBPB-III, is able to provide highly accurate electrostatic potentials at a mesh as coarse as 1.2 A for proteins. Consequently, at a given level of accuracy, the MIBPB-III is about three times faster than the APBS, a recent multigrid PB solver. The MIBPB-III has been extensively validated by using analytically solvable problems, molecular surfaces of polyatomic systems, and 24 proteins. It provides reliable benchmark numerical solutions for the PB equation.

Treatment of charge singularities in implicit solvent models

NASA Astrophysics Data System (ADS)

Geng, Weihua; Yu, Sining; Wei, Guowei

2007-09-01

This paper presents a novel method for solving the Poisson-Boltzmann (PB) equation based on a rigorous treatment of geometric singularities of the dielectric interface and a Green's function formulation of charge singularities. Geometric singularities, such as cusps and self-intersecting surfaces, in the dielectric interfaces are bottleneck in developing highly accurate PB solvers. Based on an advanced mathematical technique, the matched interface and boundary (MIB) method, we have recently developed a PB solver by rigorously enforcing the flux continuity conditions at the solvent-molecule interface where geometric singularities may occur. The resulting PB solver, denoted as MIBPB-II, is able to deliver second order accuracy for the molecular surfaces of proteins. However, when the mesh size approaches half of the van der Waals radius, the MIBPB-II cannot maintain its accuracy because the grid points that carry the interface information overlap with those that carry distributed singular charges. In the present Green's function formalism, the charge singularities are transformed into interface flux jump conditions, which are treated on an equal footing as the geometric singularities in our MIB framework. The resulting method, denoted as MIBPB-III, is able to provide highly accurate electrostatic potentials at a mesh as coarse as 1.2Å for proteins. Consequently, at a given level of accuracy, the MIBPB-III is about three times faster than the APBS, a recent multigrid PB solver. The MIBPB-III has been extensively validated by using analytically solvable problems, molecular surfaces of polyatomic systems, and 24 proteins. It provides reliable benchmark numerical solutions for the PB equation.

Understanding the influence of solvent field and fluctuations on the stability of photo-induced charge-separated state in molecular triad

NASA Astrophysics Data System (ADS)

Balamurugan, D.; Aquino, Adelia; Lischka, Hans; Dios, Francis; Flores, Lionel; Cheung, Margaret

2013-03-01

Molecular triad composed of fullerene, porphyrin, and carotene is an artificial analogue of natural photosynthetic system and is considered for applications in solar energy conversion because of its ability to produce long-lived photo-induced charge separated state. The goal of the present multiscale simulation is to understand how the stability of photo-induced charge-separated state in molecular triad is influenced by a polar organic solvent, namely tetrahydrofuran (THF). The multiscale approach is based on combined quantum, classical molecular dynamics, and statistical physics calculations. The quantum chemical calculations were performed on the triad using the second order algebraic diagrammatic perturbation and time-dependent density functional theory. Molecular dynamics simulations were performed on triad in a box of THF solvent with the replica exchange method. The two methods on different length and time scales are bridged through an important sampling technique. We have analyzed the free energy landscape, structural fluctuations, and the long- range electrostatic interactions between triad and solvent molecules. The results suggest that the polarity and re-organization of the solvent is critical in stabilization of charge-separated state in triad. Supported by DOE (DE-FG02-10ER16175)

Surface tension driven aggregation of organic nanowires via lab in a droplet.

PubMed

Gu, Jianmin; Yin, Baipeng; Fu, Shaoyan; Feng, Man; Zhang, Ziming; Dong, Haiyun; Gao, Faming; Zhao, Yong Sheng

2018-06-05

Directing the architecture of complex organic nanostructures is desirable and still remains a challenge in areas of materials science due to their structure-dependent collective optoelectronic properties. Herein, we demonstrate a simple and versatile solution strategy that allows surface tension to drive low-dimensional nanostructures to aggregate into complex structures via a lab in a droplet technique. By selecting a suitable combination of a solvent and an anti-solvent with controllable surface tension difference, the droplets can be automatically cracked into micro-droplets, which provides an aggregation force directed toward the centre of the droplet to drive the low-dimensional building blocks to form the special aggregations during the self-assembly process. This synthetic strategy has been shown to be universal for organic materials, which is beneficial for further optimizing the optoelectronic properties. These results contribute to gaining an insightful understanding on the detailed growth mechanism of complex organic nanostructures and greatly promoting the development of organic nanophotonics.

Discrete and continuum modeling of solvent effects in a twisted intramolecular charge transfer system: The 4-N,N-dimethylaminobenzonitrile (DMABN) molecule.

PubMed

Modesto-Costa, Lucas; Borges, Itamar

2018-08-05

The 4-N,N-dimethylaminobenzonitrile (DMABN) molecule is a prototypical system displaying twisted intramolecular (TICT) charge transfer effects. The ground and the first four electronic excited states (S 1 -S 4 ) in gas phase and upon solvation were studied. Charge transfer values as function of the torsion angle between the donor group (dimethylamine) and the acceptor moiety (benzonitrile) were explicitly computed. Potential energy curves were also obtained. The algebraic diagrammatic construction method at the second-order [ADC(2)] ab initio wave function was employed. Three solvents of increased polarities (benzene, DMSO and water) were investigated using discrete (average solvent electrostatic configuration - ASEC) and continuum (conductor-like screening model - COSMO) models. The results for the S 3 and S 4 excited states and the S 1 -S 4 charge transfer curves were not previously available in the literature. Electronic gas phase and solvent vertical spectra are in good agreement with previous theoretical and experimental results. In the twisted (90°) geometry the optical oscillator strengths have negligible values even for the S 2 bright state. Potential energy curves show two distinct pairs of curves intersecting at decreasing angles or not crossing in the more polar solvents. Charge transfer and electric dipole values allowed the rationalization of these results. The former effects are mostly independent of the solvent model and polarity. Although COSMO and ASEC solvent models mostly lead to similar results, there is an important difference: some crossings of the excitation energy curves appear only in the ASEC solvation model, which has important implications to the photochemistry of DMABN. Copyright © 2018 Elsevier B.V. All rights reserved.

Electrophoretic manipulation of multiple-emulsion droplets

NASA Astrophysics Data System (ADS)

Schoeler, Andreas M.; Josephides, Dimitris N.; Chaurasia, Ankur S.; Sajjadi, Shahriar; Mesquida, Patrick

2014-02-01

Electrophoretic manipulation of multiple-emulsion oil-in-water-in-oil (O/W)/O and water-in-oil-in-water-in-oil (W/O/W)/O core-shell droplets is shown. It was found that the electrophoretic mobility of the droplets is determined solely by the outer water shell, regardless of size or composition of the inner droplets. It was observed that the surface charge of the outer water shell can be changed and the polarity can be reversed through contact with a biased electrode in a similar way as with simple W/O droplets. Furthermore, addition of the anionic surfactant, sodium dodecyl sulfate to the outer water shell reverses the initial polarity and hence, electrophoretic mobility of the core-shell droplets before contact with an electrode. The results have practical implications for the manipulation of oil droplets in a continuous oil phase.

Toward Femtosecond Time-Resolved Studies of Solvent-Solute Energy Transfer in Doped Helium Nanodroplets

NASA Astrophysics Data System (ADS)

Bacellar, C.; Ziemkiewicz, M. P.; Leone, S. R.; Neumark, D. M.; Gessner, O.

2015-05-01

Superfluid helium nanodroplets provide a unique cryogenic matrix for high resolution spectroscopy and ultracold chemistry applications. With increasing photon energy and, in particular, in the increasingly important Extreme Ultraviolet (EUV) regime, the droplets become optically dense and, therefore, participate in the EUV-induced dynamics. Energy- and charge-transfer mechanisms between the host droplets and dopant atoms, however, are poorly understood. Static energy domain measurements of helium droplets doped with noble gas atoms (Xe, Kr) indicate that Penning ionization due to energy transfer from the excited droplet to dopant atoms may be a significant relaxation channel. We have set up a femtosecond time-resolved photoelectron imaging experiment to probe these dynamics directly in the time-domain. Droplets containing 104 to 106 helium atoms and a small percentage (<10-4) of dopant atoms (Xe, Kr, Ne) are excited to the 1s2p Rydberg band by 21.6 eV photons produced by high harmonic generation (HHG). Transiently populated states are probed by 1.6 eV photons, generating time-dependent photoelectron kinetic energy distributions, which are monitored by velocity map imaging (VMI). The results will provide new information about the dynamic timescales and the different relaxation channels, giving access to a more complete physical picture of solvent-solute interactions in the superfluid environment. Prospects and challenges of the novel experiment as well as preliminary experimental results will be discussed.

Spectroscopy and optical imaging of coalescing droplets

NASA Astrophysics Data System (ADS)

Ivanov, Maksym; Viderström, Michel; Chang, Kelken; Ramírez Contreras, Claudia; Mehlig, Bernhard; Hanstorp, Dag

2016-09-01

We report on experimental investigations of the dynamics of colliding liquid droplets by combining optical trapping, spectroscopy and high-speed color imaging. Two droplets with diameters between 5 and 50 microns are suspended in quiescent air by optical traps. The traps allows us to control the initial positions, and hence the impact parameter and the relative velocity of the colliding droplets. Movies of the droplet dynamics are recorded using high-speed digital movie cameras at a frame rate of up to 63000 frames per second. A fluorescent dye is added to one of the colliding droplets. We investigate the temporal evolution of the scattered and fluorescence light from the colliding droplets with concurrent spectroscopy and color imaging. This technique can be used to detect the exchange of molecules between a pair of neutral or charged droplets.

Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion

DOE PAGES

Chaudhari, Mangesh I.; Nair, Jijeesh R.; Pratt, Lawrence R.; ...

2016-10-21

Lithium-ion solvation and diffusion properties in ethylene carbonate (EC) and propylene carbonate (PC) were studied by molecular simulation, experiments, and electronic structure calculations. Studies carried out in water provide a reference for interpretation. Classical molecular dynamics simulation results are compared to ab initio molecular dynamics to assess nonpolarizable force field parameters for solvation structure of the carbonate solvents. Quasi-chemical theory (QCT) was adapted to take advantage of fourfold occupancy of the near-neighbor solvation structure observed in simulations and used to calculate solvation free energies. The computed free energy for transfer of Li + to PC from water, based on electronicmore » structure calculations with cluster-QCT, agrees with the experimental value. The simulation-based direct-QCT results with scaled partial charges agree with the electronic structure-based QCT values. The computed Li +/PF 6 - transference numbers of 0.35/0.65 (EC) and 0.31/0.69 (PC) agree well with NMR experimental values of 0.31/0.69 (EC) and 0.34/0.66 (PC) and similar values obtained here with impedance spectroscopy. These combined results demonstrate that solvent partial charges can be scaled in systems dominated by strong electrostatic interactions to achieve trends in ion solvation and transport properties that are comparable to ab initio and experimental results. Thus, the results support the use of scaled partial charges in simple, nonpolarizable force fields in future studies of these electrolyte solutions.« less

Modeling Evaporation and Particle Assembly in Colloidal Droplets.

PubMed

Zhao, Mingfei; Yong, Xin

2017-06-13

Evaporation-induced assembly of nanoparticles in a drying droplet is of great importance in many engineering applications, including printing, coating, and thin film processing. The investigation of particle dynamics in evaporating droplets can provide fundamental hydrodynamic insight for revealing the processing-structure relationship in the particle self-organization induced by solvent evaporation. We develop a free-energy-based multiphase lattice Boltzmann method coupled with Brownian dynamics to simulate evaporating colloidal droplets on solid substrates with specified wetting properties. The influence of interface-bound nanoparticles on the surface tension and evaporation of a flat liquid-vapor interface is first quantified. The results indicate that the particles at the interface reduce surface tension and enhance evaporation flux. For evaporating particle-covered droplets on substrates with different wetting properties, we characterize the increase of evaporate rate via measuring droplet volume. We find that droplet evaporation is determined by the number density and circumferential distribution of interfacial particles. We further correlate particle dynamics and assembly to the evaporation-induced convection in the bulk and on the surface of droplet. Finally, we observe distinct final deposits from evaporating colloidal droplets with bulk-dispersed and interface-bound particles. In addition, the deposit pattern is also influenced by the equilibrium contact angle of droplet.

Water Entry by a Train of Droplets

NASA Astrophysics Data System (ADS)

Ohl, Claus-Dieter; Huang, Xin; Chan, Chon U.; Frommhold, Philipp Erhard; Lippert, Alexander

2014-11-01

The impact of single droplets on a deep pool is a well-studied phenomenon which reveals reach fluid mechanics. Lesser studied is the impact of a train of droplet and the accompanied formation of largely elongated cavities, in particular for well controlled droplets. The droplets with diameters of 20-40 μm and velocities of approx. 20 m/s are generated with a piezo-actuated nozzle at rates of 200-300 kHz. Individual droplets are selected by electric charging and deflection and the impact is visualized with stroboscopic photography and high-speed videos. We study in particular the formation and shape of the cavity as by varying the number of droplets from one to 64. The cavities reach centimetres in length with lateral diameters of the order of 100 of micrometres.

Effect of solvent hydrogen bonding on the photophysical properties of intramolecular charge transfer probe trans-ethyl p-(dimethylamino) cinamate and its derivative

NASA Astrophysics Data System (ADS)

Singh, T. Sanjoy; Moyon, N. S.; Mitra, Sivaprasad

2009-08-01

Intramolecular charge transfer (ICT) behavior of trans-ethyl p-(dimethylamino) cinamate (EDAC) and 4-(dimethylamino) cinnamic acid (DMACA) were studied by steady state absorption and emission, picosecond time-resolved fluorescence experiments in various pure and mixed solvent systems. The large fluorescence spectral shift in more polar solvents indicates an efficient charge transfer from the donor site to the acceptor moiety in the excited state compared to the ground state. The energy for 0,0 transition ( ν0,0) for EDAC shows very good linear correlation with static solvent dielectric property; however, fluorescence emission maximum, stokes shift and fluorescence quantum yield show significant deviation from linearity in polar protic solvents, indicating a large contribution of solvent hydrogen bonding on the excited state relaxation mechanism. A quantitative estimation of contribution from different solvatochromic parameters was made using linear free energy relationship based on Kamlet-Taft equation.

Solvent Reaction Field Potential inside an Uncharged Globular Protein: A Bridge between Implicit and Explicit Solvent Models?

PubMed Central

Baker, Nathan A.; McCammon, J. Andrew

2008-01-01

The solvent reaction field potential of an uncharged protein immersed in Simple Point Charge/Extended (SPC/E) explicit solvent was computed over a series of molecular dynamics trajectories, intotal 1560 ns of simulation time. A finite, positive potential of 13 to 24 kbTec−1 (where T = 300K), dependent on the geometry of the solvent-accessible surface, was observed inside the biomolecule. The primary contribution to this potential arose from a layer of positive charge density 1.0 Å from the solute surface, on average 0.008 ec/Å3, which we found to be the product of a highly ordered first solvation shell. Significant second solvation shell effects, including additional layers of charge density and a slight decrease in the short-range solvent-solvent interaction strength, were also observed. The impact of these findings on implicit solvent models was assessed by running similar explicit-solvent simulations on the fully charged protein system. When the energy due to the solvent reaction field in the uncharged system is accounted for, correlation between per-atom electrostatic energies for the explicit solvent model and a simple implicit (Poisson) calculation is 0.97, and correlation between per-atom energies for the explicit solvent model and a previously published, optimized Poisson model is 0.99. PMID:17949217

Solvent reaction field potential inside an uncharged globular protein: A bridge between implicit and explicit solvent models?

NASA Astrophysics Data System (ADS)

Cerutti, David S.; Baker, Nathan A.; McCammon, J. Andrew

2007-10-01

The solvent reaction field potential of an uncharged protein immersed in simple point charge/extended explicit solvent was computed over a series of molecular dynamics trajectories, in total 1560ns of simulation time. A finite, positive potential of 13-24 kbTec-1 (where T =300K), dependent on the geometry of the solvent-accessible surface, was observed inside the biomolecule. The primary contribution to this potential arose from a layer of positive charge density 1.0Å from the solute surface, on average 0.008ec/Å3, which we found to be the product of a highly ordered first solvation shell. Significant second solvation shell effects, including additional layers of charge density and a slight decrease in the short-range solvent-solvent interaction strength, were also observed. The impact of these findings on implicit solvent models was assessed by running similar explicit solvent simulations on the fully charged protein system. When the energy due to the solvent reaction field in the uncharged system is accounted for, correlation between per-atom electrostatic energies for the explicit solvent model and a simple implicit (Poisson) calculation is 0.97, and correlation between per-atom energies for the explicit solvent model and a previously published, optimized Poisson model is 0.99.

Spontaneous Droplet Jump with Electro-Bouncing

NASA Astrophysics Data System (ADS)

Schmidt, Erin; Weislogel, Mark

2016-11-01

We investigate the dynamics of water droplet jumps from superhydrophobic surfaces in the presence of an electric field during a step reduction in gravity level. In the brief free-fall environment of a drop tower, when a strong non-homogeneous electric field (with a measured strength between 0 . 39 and 2 . 36 kV/cm) is imposed, body forces acting on the jumped droplets are primarily supplied by polarization stress and Coulombic attraction instead of gravity. The droplet charge, measured to be on the order of 2 . 3 . (10-11) C, originates by electro-osmosis of charged species at the (PTFE coated) hydrophobic surface interface. This electric body force leads to a droplet bouncing behavior similar to well-known phenomena in 1-g, though occurring for larger drops 0.1 mL for a given range of impact Weber numbers, We < 20 . In 1-g, for We > 0 . 4 , impact recoil behavior on a super-hydrophobic surface is normally dominated by damping from contact line hysteresis and by air-layer interactions. However, in the strong electric field, the droplet bounce dynamics additionally include electrohydrodynamic effects on wettability and Cassie-Wenzel transition. This is qualitatively discussed in terms of coefficients of restitution and trends in contact time. This work was supported primarily by NASA Cooperative Agreement NNX12A047A.

The roles of the solute and solvent cavities in charge-transfer-to-solvent dynamics: Ultrafast studies of potasside and sodide in diethyl ether

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cavanagh, Molly C.; Young, Ryan M.; Schwartz, Benjamin J.

2008-10-07

Although electron transfer reactions are among the most fundamental in chemistry, it is still not clear how to isolate the roles of the solute and solvent in moving charge between reactants in solution. In this paper, we address this question by comparing the ultrafast charge-transfer-to-solvent (CTTS) dynamics of potasside (K{sup -}) in diethyl ether (DEE) to those of sodide (Na{sup -}) in both DEE and tetrahydrofuran (THF). We find that for sodide in both DEE and THF, CTTS excitation leads to delayed ejection of a solvated electron that appears with its equilibrium absorption spectrum. This indicates that the ejected electronsmore » are localized in pre-existing solvent traps, suggesting that the structure of liquid DEE is characterized by cavities that are favorably polarized to localize an excess electron, as has been previously shown is the case for liquid THF. We also find that the geminate recombination dynamics following CTTS excitation of sodide in THF and DEE are similar, suggesting that the nature of the CTTS excited states and their coupling to the electronic states supported by the naturally occurring solvent cavities are similar in the two solvents. In contrast, the geminate recombination dynamics of potasside and sodide in DEE are different, with red-edge excitation of the K{sup -} CTTS band producing a greater number of long-lived electrons than is seen following the corresponding red-edge excitation of the Na{sup -} CTTS band. This indicates that the CTTS excited states of K{sup -} are better able to couple to the electronic states supported by the naturally occurring solvent cavities, allowing us to compare the energetic positions of the potasside and sodide ground and CTTS excited states on a common absolute scale. Finally, we also observe a strong transient absorption following the CTTS excitation of potasside in DEE that correlates well with the 766 nm position of the gas-phase potassium D-line. The data indicate that CTTS excitation of

An Instrument Employing a Coronal Discharge for the Determination of Droplet-Size Distribution in Clouds

NASA Technical Reports Server (NTRS)

Brun, Rinaldo J.; Levine, Joseph; Kleinknecht, Kenneth S.

1951-01-01

A flight instrument that uses electric means for measuring the droplet-size distribution in above-freezing clouds has been devised and given preliminary evaluation in flight. An electric charge is placed on the droplets and they are separated aerodynamically according to their mass. Because the charge placed on the droplets is a. function of the droplet size, the size spectrum can 'be determined by measurement of the charge deposited on cylinders of several different sizes placed to intercept the charged droplets. An expression for the rate of charge acquisition by a water droplet in a field of coronal discharge is derived. The results obtained in flight with an instrument based on the method described indicate that continuous records of droplet-size spectrum variations in clouds can be obtained. The experimental instrument was used to evaluate the method and was not refined to the extent necessary for obtaining conclusive meteorological data. The desirable features of an instrument based on the method described are (i) The instrument can be used in clouds with temperatures above freezing; (2) the size and the shape of the cylinders do not change during the exposure time; (3) the readings are instantaneous and continuous; (4) the available sensitivity permits the study of variations in cloud structures of less than 200 feet in extent.

Effect of Viscosity and Polar Properties of Solvent on Dynamics of Photoinduced Charge Transfer in BTA-1 Cation — Derivative of Thioflavin T

NASA Astrophysics Data System (ADS)

Gogoleva, S. D.; Stsiapura, V. I.

2018-05-01

It was found that the spectral and fluorescent properties of BTA-1C cation in protic and aprotic solvents differ. It was shown that for solutions in long-chain alcohols viscosity is the main factor that determines the dynamics of intramolecular charge transfer in the excited state of the BTA-1C molecule. In the case of aprotic solvents a correlation was found between the rate constant of twisted intramolecular charge transfer (TICT) during rotation of fragments of the molecule in relation to each other in the excited state and the solvent relaxation rate: k TICT 1/τ S .

Solidification of floating organic droplet in dispersive liquid-liquid microextraction as a green analytical tool.

PubMed

Mansour, Fotouh R; Danielson, Neil D

2017-08-01

Dispersive liquid-liquid microextraction (DLLME) is a special type of microextraction in which a mixture of two solvents (an extracting solvent and a disperser) is injected into the sample. The extraction solvent is then dispersed as fine droplets in the cloudy sample through manual or mechanical agitation. Hence, the sample is centrifuged to break the formed emulsion and the extracting solvent is manually separated. The organic solvents commonly used in DLLME are halogenated hydrocarbons that are highly toxic. These solvents are heavier than water, so they sink to the bottom of the centrifugation tube which makes the separation step difficult. By using solvents of low density, the organic extractant floats on the sample surface. If the selected solvent such as undecanol has a freezing point in the range 10-25°C, the floating droplet can be solidified using a simple ice-bath, and then transferred out of the sample matrix; this step is known as solidification of floating organic droplet (SFOD). Coupling DLLME to SFOD combines the advantages of both approaches together. The DLLME-SFOD process is controlled by the same variables of conventional liquid-liquid extraction. The organic solvents used as extractants in DLLME-SFOD must be immiscible with water, of lower density, low volatility, high partition coefficient and low melting and freezing points. The extraction efficiency of DLLME-SFOD is affected by types and volumes of organic extractant and disperser, salt addition, pH, temperature, stirring rate and extraction time. This review discusses the principle, optimization variables, advantages and disadvantages and some selected applications of DLLME-SFOD in water, food and biomedical analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Charged Nanowire-Directed Growth of Amorphous Calcium Carbonate Nanosheets in a Mixed Solvent for Biomimetic Composite Films.

PubMed

Liu, Yang-Yi; Liu, Lei; Chen, Si-Ming; Chang, Fu-Jia; Mao, Li-Bo; Gao, Huai-Ling; Ma, Tao; Yu, Shu-Hong

2018-05-22

Bio-inspired mineralization is an effective way for fabricating complex inorganic materials, which inspires us to develop new methods to synthesize materials with fascinating properties. In this article, we report that the charged tellurium nanowires (TeNWs) can be used as biomacromolecule analogues to direct the formation of amorphous calcium carbonate (ACC) nanosheets (ACCNs) in a mixed solvent. The effects of surface charges and the concentration of the TeNWs on the formation of ACCNs have been investigated. Particularly, the produced ACCNs can be functionalized by Fe 3 O 4 nanoparticles to produce magnetic ACC/Fe 3 O 4 hybrid nanosheets that can be used to construct ACC/Fe 3 O 4 composite films through a self-evaporation process. Moreover, sodium alginate-ACC nanocomposite films with remarkable toughness and good transmittance can also be fabricated by using such ACCNs as nanoscale building blocks. This mineralization approach in a mixed solvent using charged TeNWs as biomacromolecule analogues provides a new way for the synthesis of ACCNs, which can be used as nanoscale building blocks for the fabrication of biomimetic composite films.

Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2'-bipyridine)(CN) 4] 2-

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kjær, Kasper S.; Kunnus, Kristjan; Harlang, Tobias C. B.

The excited state dynamics of solvated [Fe(bpy)(CN) 4] 2-, where bpy = 2,2'-bipyridine, show significant sensitivity to the solvent Lewis acidity. Using a combination of optical absorption and X-ray emission transient spectroscopies, we have previously shown that the metal to ligand charge transfer (MLCT) excited state of [Fe(bpy)(CN) 4] 2- has a 19 picosecond lifetime and no discernable contribution from metal centered (MC) states in weak Lewis acid solvents, such as dimethyl sulfoxide and acetonitrile. Here, in the present work, we use the same combination of spectroscopic techniques to measure the MLCT excited state relaxation dynamics of [Fe(bpy)(CN) 4] 2-more » in water, a strong Lewis acid solvent. The charge-transfer excited state is now found to decay in less than 100 femtoseconds, forming a quasi-stable metal centered excited state with a 13 picosecond lifetime. We find that this MC excited state has triplet ( 3MC) character, unlike other reported six-coordinate Fe(II)-centered coordination compounds, which form MC quintet ( 5MC) states. The solvent dependent changes in excited state non-radiative relaxation for [Fe(bpy)(CN) 4] 2- allows us to infer the influence of the solvent on the electronic structure of the complex. Lastly, the robust characterization of the dynamics and optical spectral signatures of the isolated 3MC intermediate provides a strong foundation for identifying 3MC intermediates in the electronic excited state relaxation mechanisms of similar Fe-centered systems being developed for solar applications.« less

Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2'-bipyridine)(CN) 4] 2-

DOE PAGES

Kjær, Kasper S.; Kunnus, Kristjan; Harlang, Tobias C. B.; ...

2018-01-19

The excited state dynamics of solvated [Fe(bpy)(CN) 4] 2-, where bpy = 2,2'-bipyridine, show significant sensitivity to the solvent Lewis acidity. Using a combination of optical absorption and X-ray emission transient spectroscopies, we have previously shown that the metal to ligand charge transfer (MLCT) excited state of [Fe(bpy)(CN) 4] 2- has a 19 picosecond lifetime and no discernable contribution from metal centered (MC) states in weak Lewis acid solvents, such as dimethyl sulfoxide and acetonitrile. Here, in the present work, we use the same combination of spectroscopic techniques to measure the MLCT excited state relaxation dynamics of [Fe(bpy)(CN) 4] 2-more » in water, a strong Lewis acid solvent. The charge-transfer excited state is now found to decay in less than 100 femtoseconds, forming a quasi-stable metal centered excited state with a 13 picosecond lifetime. We find that this MC excited state has triplet ( 3MC) character, unlike other reported six-coordinate Fe(II)-centered coordination compounds, which form MC quintet ( 5MC) states. The solvent dependent changes in excited state non-radiative relaxation for [Fe(bpy)(CN) 4] 2- allows us to infer the influence of the solvent on the electronic structure of the complex. Lastly, the robust characterization of the dynamics and optical spectral signatures of the isolated 3MC intermediate provides a strong foundation for identifying 3MC intermediates in the electronic excited state relaxation mechanisms of similar Fe-centered systems being developed for solar applications.« less

Colloidal transport phenomena of milk components during convective droplet drying.

PubMed

Fu, Nan; Woo, Meng Wai; Chen, Xiao Dong

2011-10-15

Material segregation has been reported for industrial spray-dried milk powders, which indicates potential material migration during drying process. The relevant colloidal transport phenomenon and the underlying mechanism are still under debate. This study extended the glass-filament single droplet drying technique to observe not only the drying behaviour but also the dissolution behaviour of the correspondingly dried single particle. At progressively longer drying stage, a solvent droplet (water or ethanol) was attached to the semi-dried milk particle and the interaction between the solvent and the particle was video-recorded. Based on the different dissolution and wetting behaviours observed, material migration during milk drying was studied. Fresh skim milk and fresh whole milk were investigated using water and ethanol as solvents. Fat started to accumulate on the surface as soon as drying was started. At the initial stage of drying, the fat layer remained thin and the solubility of the semi-dried milk particle was much affected by lactose and protein present underneath the fat layer. Fat kept accumulating at the surface as drying progressed and the accumulation was completed by the middle stage of drying. The results from drying of model milk materials (pure sodium caseinate solution and lactose/sodium caseinate mixed solution) supported the colloidal transport phenomena observed for the milk drying. When mixed with lactose, sodium caseinate did not form an apparent solvent-resistant protein shell during drying. The extended technique of glass-filament single droplet approach provides a powerful tool in examining the solubility of individual particle after drying. Copyright © 2011 Elsevier B.V. All rights reserved.

Raman study of bulk-heterojunction morphology in photoactive layers treated with solvent-vapor annealing

NASA Astrophysics Data System (ADS)

Onojima, Norio; Ishima, Yasuhisa; Izumi, Daisuke; Takahashi, Kazuyuki

2018-03-01

The effect of solvent-vapor annealing (SVA) on bulk-heterojunction morphology in photoactive layers composed of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) was analyzed using Raman spectroscopy. We prepared the photoactive layers by electrostatic spray deposition (ESD) and fabricated organic photovoltaic devices with a conventional cell structure. Although postdeposition annealing can be omitted when the photoactive layer is deposited using ESD under dry condition, the surface is relatively rough owing to the existence of a number of droplet traces. The SVA treatment can eliminate such droplet traces, while excessive SVA resulted in a significant decrease in open-circuit voltage. The Raman study of the bulk-heterojunction morphology demonstrated the accumulation of P3HT molecules on the surface during SVA, which induced the recombination of photogenerated charges at the interface of the cathode/photoactive layer and thereby decreased the open-circuit voltage.

Liquid droplet radiator development status

NASA Technical Reports Server (NTRS)

White, K. Alan, III

1987-01-01

Development of the Liquid Droplet Radiator (LDR) is described. Significant published results of previous investigators are presented, and work currently in progress is discussed. Several proposed LDR configurations are described, and the rectangular and triangular configurations currently of most interest are examined. Development of the droplet generator, collector, and auxiliary components are discussed. Radiative performance of a droplet sheet is considered, and experimental results are seen to be in very good agreement with analytical predictions. The collision of droplets in the droplet sheet, the charging of droplets by the space plasma, and the effect of atmospheric drag on the droplet sheet are shown to be of little consequence, or can be minimized by proper design. The LDR is seen to be less susceptible than conventional technology to the effects of micrometeoroids or hostile threats. The identification of working fluids which are stable in the orbital environments of interest is also made. Methods for reducing spacecraft contamination from an LDR to an acceptable level are discussed. Preliminary results of microgravity testing of the droplet generator are presented. Possible future NASA and Air Force missions enhanced or enabled by a LDR are also discussed. System studies indicate that the LDR is potentially less massive than heat pipe radiators. Planned microgravity testing aboard the Shuttle or space station is seen to be a logical next step in LDR development.

Electrically Controllable Microparticle Synthesis and Digital Microfluidic Manipulation by Electric-Field-Induced Droplet Dispensing into Immiscible Fluids

PubMed Central

Um, Taewoong; Hong, Jiwoo; Im, Do Jin; Lee, Sang Joon; Kang, In Seok

2016-01-01

The dispensing of tiny droplets is a basic and crucial process in a myriad of applications, such as DNA/protein microarray, cell cultures, chemical synthesis of microparticles, and digital microfluidics. This work systematically demonstrates droplet dispensing into immiscible fluids through electric charge concentration (ECC) method. It exhibits three main modes (i.e., attaching, uniform, and bursting modes) as a function of flow rates, applied voltages, and gap distances between the nozzle and the oil surface. Through a conventional nozzle with diameter of a few millimeters, charged droplets with volumes ranging from a few μL to a few tens of nL can be uniformly dispensed into the oil chamber without reduction in nozzle size. Based on the features of the proposed method (e.g., formation of droplets with controllable polarity and amount of electric charge in water and oil system), a simple and straightforward method is developed for microparticle synthesis, including preparation of colloidosomes and fabrication of Janus microparticles with anisotropic internal structures. Finally, a combined system consisting of ECC-induced droplet dispensing and electrophoresis of charged droplet (ECD)-driven manipulation systems is constructed. This integrated platform will provide increased utility and flexibility in microfluidic applications because a charged droplet can be delivered toward the intended position by programmable electric control. PMID:27534580

Cyclic variations of fuel-droplet distribution during the early intake stroke of a lean-burn stratified-charge spark-ignition engine

NASA Astrophysics Data System (ADS)

Aleiferis, P. G.; Hardalupas, Y.; Taylor, A. M. K. P.; Ishii, K.; Urata, Y.

2005-11-01

Lean-burn spark-ignition engines exhibit higher efficiency and lower specific emissions in comparison with stoichiometrically charged engines. However, as the air-to-fuel (A/F) ratio of the mixture is made leaner than stoichiometric, cycle-by-cycle variations in the early stages of in-cylinder combustion, and subsequent indicated mean effective pressure (IMEP), become more pronounced and limit the range of lean-burn operation. Viable lean-burn engines promote charge stratification, the mixture near the spark plug being richer than the cylinder volume averaged value. Recent work has shown that cycle-by-cycle variations in the early stages of combustion in a stratified-charge engine can be associated with variations in both the local value of A/F ratio near the spark plug around ignition timing, as well as in the volume averaged value of the A/F ratio. The objective of the current work was to identify possible sources of such variability in A/F ratio by studying the in-cylinder field of fuel-droplet distribution during the early intake stroke. This field was visualised in an optical single-cylinder 4-valve pentroof-type spark-ignition engine by means of laser-sheet illumination in planes parallel to the cylinder head gasket 6 and 10 mm below the spark plug. The engine was run with port-injected isooctane at 1500 rpm with 30% volumetric efficiency and air-to-fuel ratio corresponding to both stoichiometric firing (A/F=15, Φ =1.0) and mixture strength close to the lean limit of stable operation (A/F=22, Φ =0.68). Images of Mie intensity scattered by the cloud of fuel droplets were acquired on a cycle-by-cycle basis. These were studied in order to establish possible correlations between the cyclic variations in size, location and scattered-light intensity of the cloud of droplets with the respective variations in IMEP. Because of the low level of Mie intensity scattered by the droplets and because of problems related to elastic scattering on the walls of the combustion

Droplet breakup dynamics of weakly viscoelastic fluids

NASA Astrophysics Data System (ADS)

Marshall, Kristin; Walker, Travis

2016-11-01

The addition of macromolecules to solvent, even in dilute quantities, can alter a fluid's response in an extensional flow. For low-viscosity fluids, the presence of elasticity may not be apparent when measured using a standard rotational rheometer, yet it may still alter the response of a fluid when undergoing an extensional deformation, especially at small length scales where elastic effects are enhanced. Applications such as microfluidics necessitate investigating the dynamics of fluids with elastic properties that are not pronounced at large length scales. In the present work, a microfluidic cross-slot configuration is used to study the effects of elasticity on droplet breakup. Droplet breakup and the subsequent iterated-stretching - where beads form along a filament connecting two primary droplets - were observed for a variety of material and flow conditions. We present a relationship on the modes of bead formation and how and when these modes will form based on key parameters such as the properties of the outer continuous-phase fluid. The results are vital not only for simulating the droplet breakup of weakly viscoelastic fluids but also for understanding how the droplet breakup event can be used for characterizing the extensional properties of weakly-viscoelastic fluids.

Quantitative Raman microspectroscopy for water permeability parameters at a droplet interface bilayer.

PubMed

Braziel, S; Sullivan, K; Lee, S

2018-01-29

Using confocal Raman microspectroscopy, we derive parameters for bilayer water transport across an isolated nanoliter aqueous droplet pair. For a bilayer formed with two osmotically imbalanced and adherent nanoliter aqueous droplets in a surrounding oil solvent, a droplet interface bilayer (DIB), the water permeability coefficient across the lipid bilayer was determined from monitoring the Raman scattering from the C[triple bond, length as m-dash]N stretching mode of K 3 Fe(CN) 6 as a measure of water uptake into the swelling droplet of a DIB pair. We also derive passive diffusional permeability coefficient for D 2 O transport across a droplet bilayer using O-D Raman signal. This method provides a significant methodological advance in determining water permeability coefficients in a convenient and reliable way.

Exploring Chemistry in Microcompartments Using Guided Droplet Collisions in a Branched Quadrupole Trap Coupled to a Single Droplet, Paper Spray Mass Spectrometer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacobs, Michael I.; Davies, James F.; Lee, Lance

Recent studies suggest that reactions in aqueous microcompartments can occur at significantly different rates than those in the bulk. Most studies have used electrospray to generate a polydisperse source of highly charged microdroplets, leading to multiple confounding factors potentially influencing reaction rates (e.g., evaporation, charge, and size). Thus, the underlying mechanism for the observed enhancement remains unclear. We present a new type of electrodynamic balance - the branched quadrupole trap (BQT) - which can be used to study reactions in microdroplets in a controlled environment. The BQT allows for condensed phase chemical reactions to be initiated by colliding droplets withmore » different reactants and levitating the merged droplet indefinitely. The performance of the BQT is characterized in several ways. Sub-millisecond mixing times as fast as ~400 μs are measured for low velocity (~0.1 m/s) collisions of droplets with <40 μm diameters. The reaction of o-phthalaldehyde (OPA) with alanine in the presence of dithiolthreitol is measured using both fluorescence spectroscopy and single droplet paper spray mass spectrometry. The bimolecular rate constant for reaction of alanine with OPA is found to be 84 ± 10 and 67 ± 6 M -1s -1 in a 30 μm radius droplet and bulk solution, respectively, which demonstrates that bimolecular reaction rate coefficients can be quantified using merged microdroplets and that merged droplets can be used to study rate enhancements due to compartmentalization. Products of the reaction of OPA with alanine are detected in single droplets using paper spray mass spectrometry. Finally, we demonstrate that single droplets with <100 pg of analyte can easily be studied using single droplet mass spectrometry.« less

Exploring Chemistry in Microcompartments Using Guided Droplet Collisions in a Branched Quadrupole Trap Coupled to a Single Droplet, Paper Spray Mass Spectrometer

DOE PAGES

Jacobs, Michael I.; Davies, James F.; Lee, Lance; ...

2017-10-19

Recent studies suggest that reactions in aqueous microcompartments can occur at significantly different rates than those in the bulk. Most studies have used electrospray to generate a polydisperse source of highly charged microdroplets, leading to multiple confounding factors potentially influencing reaction rates (e.g., evaporation, charge, and size). Thus, the underlying mechanism for the observed enhancement remains unclear. We present a new type of electrodynamic balance - the branched quadrupole trap (BQT) - which can be used to study reactions in microdroplets in a controlled environment. The BQT allows for condensed phase chemical reactions to be initiated by colliding droplets withmore » different reactants and levitating the merged droplet indefinitely. The performance of the BQT is characterized in several ways. Sub-millisecond mixing times as fast as ~400 μs are measured for low velocity (~0.1 m/s) collisions of droplets with <40 μm diameters. The reaction of o-phthalaldehyde (OPA) with alanine in the presence of dithiolthreitol is measured using both fluorescence spectroscopy and single droplet paper spray mass spectrometry. The bimolecular rate constant for reaction of alanine with OPA is found to be 84 ± 10 and 67 ± 6 M -1s -1 in a 30 μm radius droplet and bulk solution, respectively, which demonstrates that bimolecular reaction rate coefficients can be quantified using merged microdroplets and that merged droplets can be used to study rate enhancements due to compartmentalization. Products of the reaction of OPA with alanine are detected in single droplets using paper spray mass spectrometry. Finally, we demonstrate that single droplets with <100 pg of analyte can easily be studied using single droplet mass spectrometry.« less

Charge-induced secondary atomization in diffusion flames of electrostatic sprays

NASA Technical Reports Server (NTRS)

Gomez, Alessandro; Chen, Gung

1994-01-01

The combustion of electrostatic sprays of heptane in laminar counterflow diffusion flames was experimentally studied by measuring droplet size and velocity distributions, as well as the gas-phase temperature. A detailed examination of the evolution of droplet size distribution as droplets approach the flame shows that, if substantial evaporation occurs before droplets interact with the flame, an initially monodisperse size distribution becomes bimodal. A secondary sharp peak in the size histogram develops in correspondence of diameters about one order of magnitude smaller than the mean. No evaporation mechanism can account for the development of such bimodality, that can be explained only in terms of a disintegration of droplets into finer fragments of size much smaller than that of the parent. Other evidence in support of this interpretation is offered by the measurements of droplet size-velocity correlation and velocity component distributions, showing that, as a consequence of the ejection process, the droplets responsible for the secondary peak have velocities uncorrelated with the mean flow. The fission is induced by the electric charge. When a droplet evaporates, in fact, the electric charge density on the droplet surface increases while the droplet shrinks, until the so-called Rayleigh limit is reached at which point the repulsion of electric charges overcomes the surface tension cohesive force, ultimately leading to a disintegraton into finer fragments. We report on the first observation of such fissions in combustion environments. If, on the other hand, insufficient evaporation has occurred before droplets enter the high temperature region, there appears to be no significant evidence of bimodality in their size distribution. In this case, in fact, the concentration of flame chemi-ions or, in the case of positively charged droplets, electrons may be sufficient for them to neutralize the charge on the droplets and to prevent disruption.

Directional Electrostatic Accretion Process Employing Acoustic Droplet Formation

NASA Technical Reports Server (NTRS)

Oeftering, Richard (Inventor)

1998-01-01

The present invention is directed to an apparatus for manufacturing a free standing solid metal part. In the present invention, metal droplets are ejected in a nozzleless fashion from a free surface pool of molten metal by applying focused acoustic radiation pressure. The acoustic radiation pressure is produced by high intensity acoustic tone bursts emitted from an acoustic source positioned at the bottom of the pool which directs the acoustic energy at the pool surface. The metal droplets are electrostatically charged so their trajectory can be controlled by electric fields that guide the droplets to predetermined points on a target. The droplets impinge upon the target and solidify with the target material. The accretion of the electrostatically directed solidified droplets forms the free standing metal part.

Increasing Protein Charge State When Using Laser Electrospray Mass Spectrometry

NASA Astrophysics Data System (ADS)

Karki, Santosh; Flanigan, Paul M.; Perez, Johnny J.; Archer, Jieutonne J.; Levis, Robert J.

2015-05-01

Femtosecond (fs) laser vaporization is used to transfer cytochrome c, myoglobin, lysozyme, and ubiquitin from the condensed phase into an electrospray (ES) plume consisting of a mixture of a supercharging reagent, m-nitrobenzyl alcohol ( m-NBA), and trifluoroacetic acid (TFA), acetic acid (AA), or formic acid (FA). Interaction of acid-sensitive proteins like cytochrome c and myoglobin with the highly charged ES droplets resulted in a shift to higher charge states in comparison with acid-stable proteins like lysozyme and ubiquitin. Laser electrospray mass spectrometry (LEMS) measurements showed an increase in both the average charge states (Zavg) and the charge state with maximum intensity (Zmode) for acid-sensitive proteins compared with conventional electrospray ionization mass spectrometry (ESI-MS) under equivalent solvent conditions. A marked increase in ion abundance of higher charge states was observed for LEMS in comparison with conventional electrospray for cytochrome c (ranging from 19+ to 21+ versus 13+ to 16+) and myoglobin (ranging from 19+ to 26+ versus 18+ to 21+) using an ES solution containing m-NBA and TFA. LEMS measurements as a function of electrospray flow rate yielded increasing charge states with decreasing flow rates for cytochrome c and myoglobin.

Control of aqueous droplets using magnetic and electrostatic forces.

PubMed

Ohashi, Tetsuo; Kuyama, Hiroki; Suzuki, Koichi; Nakamura, Shin

2008-04-07

Basic control operations were successfully performed on an aqueous droplet using both magnetic and electrostatic forces. In our droplet-based microfluidics, magnetic beads were incorporated in an aqueous droplet as a force mediator. This report describes droplet anchoring and separation of the beads from the droplet using a combination of magnetic and electrostatic forces. When an aqueous droplet is placed in an oil-filled reservoir, the droplet sinks to the bottom, under which an electrode had been placed. The droplet was adsorbed (or anchored) to the bottom surface on the electrode when a DC voltage was applied to the electrode. The magnetic beads were removed with magnetic force after the droplet had been anchored. Surfactant addition into droplet solution was very effective for the elimination of electric charge, which resulted in the stable adsorption of a droplet to hydrophobic substrate under an applied voltage of DC 0.5-3 kV. In a sequential process, small volume of aqueous liquid was successfully transferred using both magnetic and electrostatic forces.

Probing Ion Transfer across Liquid-Liquid Interfaces by Monitoring Collisions of Single Femtoliter Oil Droplets on Ultramicroelectrodes.

PubMed

Deng, Haiqiang; Dick, Jeffrey E; Kummer, Sina; Kragl, Udo; Strauss, Steven H; Bard, Allen J

2016-08-02

We describe a method of observing collisions of single femtoliter (fL) oil (i.e., toluene) droplets that are dispersed in water on an ultramicroelectrode (UME) to probe the ion transfer across the oil/water interface. The oil-in-water emulsion was stabilized by an ionic liquid, in which the oil droplet trapped a highly hydrophobic redox probe, rubrene. The ionic liquid also functions as the supporting electrolyte in toluene. When the potential of the UME was biased such that rubrene oxidation would be possible when a droplet collided with the electrode, no current spikes were observed. This implies that the rubrene radical cation is not hydrophilic enough to transfer into the aqueous phase. We show that current spikes are observed when tetrabutylammonium trifluoromethanesulfonate or tetrahexylammonium hexafluorophosphate are introduced into the toluene phase and when tetrabutylammonium perchlorate is introduced into the water phase, implying that the ion transfer facilitates electron transfer in the droplet collisions. The current (i)-time (t) behavior was evaluated quantitatively, which indicated the ion transfer is fast and reversible. Furthermore, the size of these emulsion droplets can also be calculated from the electrochemical collision. We further investigated the potential dependence on the electrochemical collision response in the presence of tetrabutylammonium trifluoromethanesulfonate in toluene to obtain the formal ion transfer potential of tetrabutylammonium across the toluene/water interface, which was determined to be 0.754 V in the inner potential scale. The results yield new physical insights into the charge balance mechanism in emulsion droplet collisions and indicate that the electrochemical collision technique can be used to probe formal ion transfer potentials between water and solvents with very low (ε < 5) dielectric constants.

Particle formation in the emulsion-solvent evaporation process.

PubMed

Staff, Roland H; Schaeffel, David; Turshatov, Andrey; Donadio, Davide; Butt, Hans-Jürgen; Landfester, Katharina; Koynov, Kaloian; Crespy, Daniel

2013-10-25

The mechanism of particle formation from submicrometer emulsion droplets by solvent evaporation is revisited. A combination of dynamic light scattering, fluorescence resonance energy transfer, zeta potential measurements, and fluorescence cross-correlation spectroscopy is used to analyze the colloids during the evaporation process. It is shown that a combination of different methods yields reliable and quantitative data for describing the fate of the droplets during the process. The results indicate that coalescence plays a minor role during the process; the relatively large size distribution of the obtained polymer colloids can be explained by the droplet distribution after their formation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modified two-step emulsion solvent evaporation technique for fabricating biodegradable rod-shaped particles in the submicron size range.

PubMed

Safari, Hanieh; Adili, Reheman; Holinstat, Michael; Eniola-Adefeso, Omolola

2018-05-15

Though the emulsion solvent evaporation (ESE) technique has been previously modified to produce rod-shaped particles, it cannot generate small-sized rods for drug delivery applications due to the inherent coupling and contradicting requirements for the formation versus stretching of droplets. The separation of the droplet formation from the stretching step should enable the creation of submicron droplets that are then stretched in the second stage by manipulation of the system viscosity along with the surface-active molecule and oil-phase solvent. A two-step ESE protocol is evaluated where oil droplets are formed at low viscosity followed by a step increase in the aqueous phase viscosity to stretch droplets. Different surface-active molecules and oil phase solvents were evaluated to optimize the yield of biodegradable PLGA rods. Rods were assessed for drug loading via an imaging agent and vascular-targeted delivery application via blood flow adhesion assays. The two-step ESE method generated PLGA rods with major and minor axis down to 3.2 µm and 700 nm, respectively. Chloroform and sodium metaphosphate was the optimal solvent and surface-active molecule, respectively, for submicron rod fabrication. Rods demonstrated faster release of Nile Red compared to spheres and successfully targeted an inflamed endothelium under shear flow in vitro and in vivo. Copyright © 2018 Elsevier Inc. All rights reserved.

Monodisperse hydrogel microspheres by forced droplet formation in aqueous two-phase systems.

PubMed

Ziemecka, Iwona; van Steijn, Volkert; Koper, Ger J M; Rosso, Michel; Brizard, Aurelie M; van Esch, Jan H; Kreutzer, Michiel T

2011-02-21

This paper presents a method to form micron-sized droplets in an aqueous two-phase system (ATPS) and to subsequently polymerize the droplets to produce hydrogel beads. Owing to the low interfacial tension in ATPS, droplets do not easily form spontaneously. We enforce the formation of drops by perturbing an otherwise stable jet that forms at the junction where the two aqueous streams meet. This is done by actuating a piezo-electric bending disc integrated in our device. The influence of forcing amplitude and frequency on jet breakup is described and related to the size of monodisperse droplets with a diameter in the range between 30 and 60 μm. Rapid on-chip polymerization of derivatized dextran inside the droplets created monodisperse hydrogel particles. This work shows how droplet-based microfluidics can be used in all-aqueous, surfactant-free, organic-solvent-free biocompatible two-phase environment.

An evaporation model of colloidal suspension droplets

NASA Astrophysics Data System (ADS)

Sartori, Silvana; Li\\ Nán, Amable; Lasheras, Juan C.

2009-11-01

Colloidal suspensions of polymers in water or other solvents are widely used in the pharmaceutical industry to coat tablets with different agents. These allow controlling the rate at which the drug is delivered, taste or physical appearance. The coating is performed by simultaneously spraying and drying the tablets with the colloidal suspension at moderately high temperatures. The spreading of the coating on the pills surface depends on the droplet Webber and Reynolds numbers, angle of impact, but more importantly on the rheological properties of the drop. We present a model for the evaporation of a colloidal suspension droplet in a hot air environment with temperatures substantially lower than the boiling temperature of the carrier fluid. As the liquid vaporizes from the surface, a compacting front advances into the droplet faster than the liquid surface regresses, forming a shell of a porous medium where the particles reach their maximum packing density. While the surface regresses, the evaporation rate is determined by both the rate at which heat is transported to the droplet surface and the rate at which liquid vapor is diffused away from it. This regime continues until the compacting front reaches the center of the droplet, at which point the evaporation rate is drastically reduced.

Enhancing droplet deposition through in-situ precipitation

NASA Astrophysics Data System (ADS)

Damak, Maher; Mahmoudi, Seyed Reza; Hyder, Md Nasim; Varanasi, Kripa K.

2016-08-01

Retention of agricultural sprays on plant surfaces is an important challenge. Bouncing of sprayed pesticide droplets from leaves is a major source of soil and groundwater pollution and pesticide overuse. Here we report a method to increase droplet deposition through in-situ formation of hydrophilic surface defects that can arrest droplets during impact. Defects are created by simultaneously spraying oppositely charged polyelectrolytes that induce surface precipitation when two droplets come into contact. Using high-speed imaging, we study the coupled dynamics of drop impact and surface precipitate formation. We develop a physical model to estimate the energy dissipation by the defects and predict the transition from bouncing to sticking. We demonstrate macroscopic enhancements in spray retention and surface coverage for natural and synthetic non-wetting surfaces and provide insights into designing effective agricultural sprays.

Two-dimensional fluid droplet arrays generated using a single nozzle

DOEpatents

Lee, Eric R.; Perl, Martin L.

1999-11-02

Amplitudes of drive pulses received by a horizontally-placed dropper determine the horizontal displacements of droplets relative to an ejection aperture of the dropper. The drive pulses are varied such that the dropper generates a two-dimensional array of vertically-falling droplets. Vertical and horizontal interdroplet spacings may be varied in real time. Applications include droplet analysis experiments such as Millikan fractional charge searches and aerosol characterization, as well as material deposition applications.

Absorption of charged particulate surfactants in microfluidics

NASA Astrophysics Data System (ADS)

Kong, Tiantian; Liu, Zhou; Yao, Xiaoxue; Liu, Yaming

2017-11-01

We use microfluidics to uncouple the generation of Pickering emulsion droplets and stability analysis against coalescence. By designing the microchannels, we control the packing time for charged particles arriving at the droplet interfaces, and subsequently test the droplet stability in a coalescence chamber. The critical particle coverage on interfaces that prevents coalescence are estimated by an adsorption model. We further investigate the dependence of the critical particle coverage on its properties such as particle sizes, surface charge densities, and bulk concentrations. Our studies are potentially beneficial to the applications involving particle-stabilized droplets including cosmetics, food products, and oil recovery. NSFC 11504238,JCYJ20160308092144035,2016A050503048.

Solvent-based and solvent-free characterization of low solubility and low molecular weight polyamides by mass spectrometry: a complementary approach.

PubMed

Barrère, Caroline; Hubert-Roux, Marie; Lange, Catherine M; Rejaibi, Majed; Kebir, Nasreddine; Désilles, Nicolas; Lecamp, Laurence; Burel, Fabrice; Loutelier-Bourhis, Corinne

2012-06-15

Polyamides (PA) belong to the most used classes of polymers because of their attractive chemical and mechanical properties. In order to monitor original PA design, it is essential to develop analytical methods for the characterization of these compounds that are mostly insoluble in usual solvents. A low molecular weight polyamide (PA11), synthesized with a chain limiter, has been used as a model compound and characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). In the solvent-based approach, specific solvents for PA, i.e. trifluoroacetic acid (TFA) and hexafluoroisopropanol (HFIP), were tested. Solvent-based sample preparation methods, dried-droplet and thin layer, were optimized through the choice of matrix and salt. Solvent-based (thin layer) and solvent-free methods were then compared for this low solubility polymer. Ultra-high-performance liquid chromatography/electrospray ionization (UHPLC/ESI)-TOF-MS analyses were then used to confirm elemental compositions through accurate mass measurement. Sodium iodide (NaI) and 2,5-dihydroxybenzoic acid (2,5-DHB) are, respectively, the best cationizing agent and matrix. The dried-droplet sample preparation method led to inhomogeneous deposits, but the thin-layer method could overcome this problem. Moreover, the solvent-free approach was the easiest and safest sample preparation method giving equivalent results to solvent-based methods. Linear as well as cyclic oligomers were observed. Although the PA molecular weights obtained by MALDI-TOF-MS were lower than those obtained by (1)H NMR and acido-basic titration, this technique allowed us to determine the presence of cyclic and linear species, not differentiated by the other techniques. TFA was shown to induce modification of linear oligomers that permitted cyclic and linear oligomers to be clearly highlighted in spectra. Optimal sample preparation conditions were determined for the MALDI-TOF-MS analysis of PA11, a

Interdroplet attractive forces in AOT water-in-oil microemulsions formed in subcritical and supercritical solvents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tingey, J.M.; Fulton, J.L.; Smith, R.D.

1990-03-08

The van der Waals attractive interactions between aqueous droplets in water-in-oil type microemulsions have been investigated for a range of continuous-phase solvents including the alkanes from methane to isooctane and the noble gases, krypton and xenon. Hamaker constants for water droplets with surfactant shells of the sodium bis(2-ethylhexyl) sulfosuccinate (AOT) in subcritical and supercritical solvents were calculated by using Lifshitz theory and the resulting interaction potential calculations qualitatively account for many features of the phase behavior of these systems.

Material forming apparatus using a directed droplet stream

DOEpatents

Holcomb, David E.; Viswanathan, Srinath; Blue, Craig A.; Wilgen, John B.

2000-01-01

Systems and methods are described for rapidly forming precision metallic and intermetallic alloy net shape parts directly from liquid metal droplets. A directed droplet deposition apparatus includes a crucible with an orifice for producing a jet of material, a jet destabilizer, a charging structure, a deflector system, and an impact zone. The systems and methods provide advantages in that fully dense, microstructurally controlled parts can be fabricated at moderate cost.

Enhancing droplet deposition through in-situ precipitation

PubMed Central

Damak, Maher; Mahmoudi, Seyed Reza; Hyder, Md Nasim; Varanasi, Kripa K.

2016-01-01

Retention of agricultural sprays on plant surfaces is an important challenge. Bouncing of sprayed pesticide droplets from leaves is a major source of soil and groundwater pollution and pesticide overuse. Here we report a method to increase droplet deposition through in-situ formation of hydrophilic surface defects that can arrest droplets during impact. Defects are created by simultaneously spraying oppositely charged polyelectrolytes that induce surface precipitation when two droplets come into contact. Using high-speed imaging, we study the coupled dynamics of drop impact and surface precipitate formation. We develop a physical model to estimate the energy dissipation by the defects and predict the transition from bouncing to sticking. We demonstrate macroscopic enhancements in spray retention and surface coverage for natural and synthetic non-wetting surfaces and provide insights into designing effective agricultural sprays. PMID:27572948

Explicit Solvent Simulations of Friction between Brush Layers of Charged and Neutral Bottle-Brush Macromolecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carrillo, Jan-Michael; Brown, W Michael; Dobrynin, Andrey

2012-01-01

We study friction between charged and neutral brush layers of bottle-brush macromolecules using molecular dynamics simulations. In our simulations the solvent molecules were treated explicitly. The deformation of the bottle-brush macromolecules under the shear were studied as a function of the substrate separation and shear stress. For charged bottle-brush layers we study effect of the added salt on the brush lubricating properties to elucidate factors responsible for energy dissipation in charged and neutral brush systems. Our simulations have shown that for both charged and neutral brush systems the main deformation mode of the bottle-brush macromolecule is associated with the backbonemore » deformation. This deformation mode manifests itself in the backbone deformation ratio, , and shear viscosity, , to be universal functions of the Weissenberg number W. The value of the friction coefficient, , and viscosity, , are larger for the charged bottle-brush coatings in comparison with those for neutral brushes at the same separation distance, D, between substrates. The additional energy dissipation generated by brush sliding in charged bottle-brush systems is due to electrostatic coupling between bottle-brush and counterion motion. This coupling weakens as salt concentration, cs, increases resulting in values of the viscosity, , and friction coefficient, , approaching corresponding values obtained for neutral brush systems.« less

High-throughput controllable generation of droplet arrays with low consumption

NASA Astrophysics Data System (ADS)

Lin, Yinyin; Wu, Zhongsheng; Gao, Yibo; Wu, Jinbo; Wen, Weijia

2018-06-01

We describe a controllable sliding method for fabricating millions of isolated femto- to nanoliter-sized droplets with defined volume, geometry and position and a speed of up to 375 kHz. In this work, without using a superhydrophobic or superoleophobic surface, arrays of droplets are instantly formed on the patterned substrate by sliding a strip of liquid, including water, low-surface-tension organic solvents and solution, along the substrate. To precisely control the volume of the droplets, we systemically investigate the effects of the size of the wettable pattern, the viscosity of the liquid and sliding speed, which were found to vary independently to tune the height and volume of the droplets. Through this method, we successfully fabricated an oriented single metal-organic framework crystal array with control over their XY positioning on the surface, as characterized by microscopy and X-ray diffraction (XRD) techniques.

Spectrophotometric and spectroscopic studies of charge transfer complex of 1-Naphthylamine as an electron donor with picric acid as an electron acceptor in different polar solvents

NASA Astrophysics Data System (ADS)

Singh, Neeti; Ahmad, Afaq

2010-08-01

The charge transfer complex of 1-Naphthylamine as a donor with π-acceptor picric acid has been studied spectrophotometrically in different solvents at room temperature. The results indicate that the formation of charge transfer complex is high in less polar solvent. The stoichiometry of the complex was found to be 1:1 by straight line method. The data are analysed in terms of formation constant ( KCT), molar extinction coefficient ( ɛCT), standard free energy (Δ G o), oscillator strength ( ƒ), transition dipole moment ( μ EN), resonance energy ( R N) and ionization potential ( I D). It is concluded that the formation constant ( KCT) of the complex is found to be depends upon the nature of both electron acceptor and donor and also on the polarity of solvents. Further the charge transfer molecular complex between picric acid and 1-Naphthylamine is stabilized by hydrogen bonding.

Energy gap law of electron transfer in nonpolar solvents.

PubMed

Tachiya, M; Seki, Kazuhiko

2007-09-27

We investigate the energy gap law of electron transfer in nonpolar solvents for charge separation and charge recombination reactions. In polar solvents, the reaction coordinate is given in terms of the electrostatic potentials from solvent permanent dipoles at solutes. In nonpolar solvents, the energy fluctuation due to solvent polarization is absent, but the energy of the ion pair state changes significantly with the distance between the ions as a result of the unscreened strong Coulomb potential. The electron transfer occurs when the final state energy coincides with the initial state energy. For charge separation reactions, the initial state is a neutral pair state, and its energy changes little with the distance between the reactants, whereas the final state is an ion pair state and its energy changes significantly with the mutual distance; for charge recombination reactions, vice versa. We show that the energy gap law of electron-transfer rates in nonpolar solvents significantly depends on the type of electron transfer.

Time dependent charging of layer clouds in the global electric circuit

NASA Astrophysics Data System (ADS)

Zhou, Limin; Tinsley, Brian A.

2012-09-01

There is much observational data consistent with the hypothesis that the ionosphere-earth current density (Jz) in the global electric circuit, which is modulated by both solar activity and thunderstorm activity, affects atmospheric dynamics and cloud cover. One candidate mechanism involves Jz causing the accumulation of space charge on droplets and aerosol particles, that affects the rate of scavenging of the latter, notably those of Cloud Condensation Nuclei (CCN) and Ice Forming Nuclei (IFN) (Tinsley, 2008, 2010). Space charge is the difference, per unit volume, between total positive and total negative electrical charge that is on droplets, aerosol particles (including the CCN and IFN) and air ions. The cumulative effects of the scavenging in stratiform clouds and aerosol layers in an air mass over the lifetime of the aerosol particles of 1-10 days affects the concentration and size distribution of the CCN, so that in subsequent episodes of cloud formation (including deep convective clouds) there can be effects on droplet size distribution, coagulation, precipitation processes, and even storm dynamics.Because the time scales for charging for some clouds can be long compared to cloud lifetimes, the amount of charge at a given time, and its effect on scavenging, depend more on the charging rate than on the equilibrium charge that would eventually be attained. To evaluate this, a new time-dependent charging model has been developed. The results show that for typical altostratus clouds with typical droplet radii 10 μm and aerosol particles of radius of 0.04 μm, the time constant for charging in response to a change in Jz is about 800 s, which is comparable to cloud formation and dissipation timescales for some cloud situations. The charging timescale is found to be strong functions of altitude and aerosol concentration, with the time constant for droplet charging at 2 km in air with a high concentration of aerosols being about an hour, and for clouds at 10 km in

The role of interfacial water layer in atmospherically relevant charge separation

NASA Astrophysics Data System (ADS)

Bhattacharyya, Indrani

Charge separation at interfaces is important in various atmospheric processes, such as thunderstorms, lightning, and sand storms. It also plays a key role in several industrial processes, including ink-jet printing and electrostatic separation. Surprisingly, little is known about the underlying physics of these charging phenomena. Since thin films of water are ubiquitous, they may play a role in these charge separation processes. This talk will focus on the experimental investigation of the role of a water adlayer in interfacial charging, with relevance to meteorologically important phenomena, such as atmospheric charging due to wave actions on oceans and sand storms. An ocean wave generates thousands of bubbles, which upon bursting produce numerous large jet droplets and small film droplets that are charged. In the 1960s, Blanchard showed that the jet droplets are positively charged. However, the charge on the film droplets was not known. We designed an experiment to exclusively measure the charge on film droplets generated by bubble bursting on pure water and aqueous salt solution surfaces. We measured their charge to be negative and proposed a model where a slight excess of hydroxide ions in the interfacial water layer is responsible for generating these negatively charged droplets. The findings from this research led to a better understanding of the ionic disposition at the air-water interface. Sand particles in a wind-blown sand layer, or 'saltation' layer, become charged due to collisions, so much so, that it can cause lightning. Silica, being hydrophilic, is coated with a water layer even under low-humidity conditions. To investigate the importance of this water adlayer in charging the silica surfaces, we performed experiments to measure the charge on silica surfaces due to contact and collision processes. In case of contact charging, the maximum charge separation occurred at an optimum relative humidity. On the contrary, in collisional charging process, no

Comparison of RESP and IPolQ-Mod Partial Charges for Solvation Free Energy Calculations of Various Solute/Solvent Pairs.

PubMed

Mecklenfeld, Andreas; Raabe, Gabriele

2017-12-12

The calculation of solvation free energies ΔG solv by molecular simulations is of great interest as they are linked to other physical properties such as relative solubility, partition coefficient, and activity coefficient. However, shortcomings in molecular models can lead to ΔG solv deviations from experimental data. Various studies have demonstrated the impact of partial charges on free energy results. Consequently, calculation methods for partial charges aimed at more accurate ΔG solv predictions are the subject of various studies in the literature. Here we compare two methods to derive partial charges for the general AMBER force field (GAFF), i.e. the default RESP as well as the physically motivated IPolQ-Mod method that implicitly accounts for polarization costs. We study 29 solutes which include characteristic functional groups of drug-like molecules, and 12 diverse solvents were examined. In total, we consider 107 solute/solvent pairs including two water models TIP3P and TIP4P/2005. Comparison with experimental results yields better agreement for TIP3P, regardless of the partial charge scheme. The overall performance of GAFF/RESP and GAFF/IPolQ-Mod is similar, though specific shortcomings in the description of ΔG solv for both RESP and IPolQ-Mod can be identified. However, the high correlation between free energies obtained with GAFF/RESP and GAFF/IPolQ-Mod demonstrates the compatibility between the modified charges and remaining GAFF parameters.

Characterization and application of droplet spray ionization for real-time reaction monitoring.

PubMed

Zhang, Hong; Li, Na; Li, Xiao-di; Jiang, Jie; Zhao, Dan-Dan; You, Hong

2016-08-01

The ionization source for real-time reaction monitoring has attracted tremendous interest in recent years. We have previously reported a reliable approach in which droplet spray ionization (DSI) was used for monitoring chemical reactions in real-time. Herein, we systematically investigated the characterization and application of DSI for real-time reaction monitoring. Analyte ions are generated by loading a sample solution onto a corner of a microscope cover glass positioned in front of the MS inlet and applying a high voltage to the sample. The tolerance to positioning, solvent effect, spray angle and spray time were investigated. Extension to real-time monitoring of macromolecule reactions was also demonstrated by the charge state change of cytochrome c in the presence of acetic acid. The corner could be positioned within an area of approximately 10 × 6 × 5 mm (x, y, z) in front of the MS inlet. The broad polarities of solvents from methanol to PhF were suitable for DSI. It featured monitoring real-time changes in reactions on the time scale of seconds to minutes. A real-time charge state change of cytochrome c was captured. DSI-MS features ease of use, durability of the spray platform and reusability of the ion source. Eliminating the need for a sample transport capillary, DSI opens a new avenue for the in situ analysis and real-time monitoring of short-lived key reaction intermediates even at subsecond dead times. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Insight into nanoparticle charging mechanism in nonpolar solvents to control the formation of Pt nanoparticle monolayers by electrophoretic deposition

DOE PAGES

Cernohorsky, Ondrej; Grym, Jan; Yatskiv, Roman; ...

2016-08-13

We report on the formation of Pt nanoparticle monolayers by electrophoretic deposition from nonpolar solvents. First, the growth kinetics of Pt nanoparticles prepared by the reverse micelle technique are described in detail. Second, a model of nanoparticle charging in nonpolar media is discussed and methods to control the nanoparticle charging are proposed. Lastly, essential parameters of the electrophoretic deposition process to control the deposition of nanoparticle monolayers are discussed and mechanisms of their formation are analyzed.

Insight into nanoparticle charging mechanism in nonpolar solvents to control the formation of Pt nanoparticle monolayers by electrophoretic deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cernohorsky, Ondrej; Grym, Jan; Yatskiv, Roman

We report on the formation of Pt nanoparticle monolayers by electrophoretic deposition from nonpolar solvents. First, the growth kinetics of Pt nanoparticles prepared by the reverse micelle technique are described in detail. Second, a model of nanoparticle charging in nonpolar media is discussed and methods to control the nanoparticle charging are proposed. Lastly, essential parameters of the electrophoretic deposition process to control the deposition of nanoparticle monolayers are discussed and mechanisms of their formation are analyzed.

Bioreactor droplets from liposome-stabilized all-aqueous emulsions

NASA Astrophysics Data System (ADS)

Dewey, Daniel C.; Strulson, Christopher A.; Cacace, David N.; Bevilacqua, Philip C.; Keating, Christine D.

2014-08-01

Artificial bioreactors are desirable for in vitro biochemical studies and as protocells. A key challenge is maintaining a favourable internal environment while allowing substrate entry and product departure. We show that semipermeable, size-controlled bioreactors with aqueous, macromolecularly crowded interiors can be assembled by liposome stabilization of an all-aqueous emulsion. Dextran-rich aqueous droplets are dispersed in a continuous polyethylene glycol (PEG)-rich aqueous phase, with coalescence inhibited by adsorbed ~130-nm diameter liposomes. Fluorescence recovery after photobleaching and dynamic light scattering data indicate that the liposomes, which are PEGylated and negatively charged, remain intact at the interface for extended time. Inter-droplet repulsion provides electrostatic stabilization of the emulsion, with droplet coalescence prevented even for submonolayer interfacial coatings. RNA and DNA can enter and exit aqueous droplets by diffusion, with final concentrations dictated by partitioning. The capacity to serve as microscale bioreactors is established by demonstrating a ribozyme cleavage reaction within the liposome-coated droplets.

Bioreactor droplets from liposome-stabilized all-aqueous emulsions.

PubMed

Dewey, Daniel C; Strulson, Christopher A; Cacace, David N; Bevilacqua, Philip C; Keating, Christine D

2014-08-20

Artificial bioreactors are desirable for in vitro biochemical studies and as protocells. A key challenge is maintaining a favourable internal environment while allowing substrate entry and product departure. We show that semipermeable, size-controlled bioreactors with aqueous, macromolecularly crowded interiors can be assembled by liposome stabilization of an all-aqueous emulsion. Dextran-rich aqueous droplets are dispersed in a continuous polyethylene glycol (PEG)-rich aqueous phase, with coalescence inhibited by adsorbed ~130-nm diameter liposomes. Fluorescence recovery after photobleaching and dynamic light scattering data indicate that the liposomes, which are PEGylated and negatively charged, remain intact at the interface for extended time. Inter-droplet repulsion provides electrostatic stabilization of the emulsion, with droplet coalescence prevented even for submonolayer interfacial coatings. RNA and DNA can enter and exit aqueous droplets by diffusion, with final concentrations dictated by partitioning. The capacity to serve as microscale bioreactors is established by demonstrating a ribozyme cleavage reaction within the liposome-coated droplets.

Electrically Controllable Microparticle Synthesis and Digital Microfluidic Manipulation by Electric-Field-Induced Droplet Dispensing into Immiscible Fluids

NASA Astrophysics Data System (ADS)

Um, Taewoong; Hong, Jiwoo; Kang, In Seok

2016-11-01

The dispensing of tiny droplets is a basic and crucial process in a myriad of applications, such as DNA/protein microarray, cell cultures, chemical synthesis of microparticles, and digital microfluidics. This work demonstrates the droplet dispensing into immiscible fluids through electric charge concentration (ECC) method. Three main modes (i.e., attaching, uniform and bursting modes) are exhibited as a function of flow rates, applied voltage and gap distance between the nozzle and the oil surface. Through a conventional nozzle with diameter of a few millimeters, charged droplets with volumes ranging from a few μL to a few tens of nL can be uniformly dispensed into the oil chamber without reduction in nozzle size. Based on the features of the proposed method (e.g., formation of droplets with controllable polarity and amount of electric charge in water and oil system), a simple and straightforward method is developed for microparticle synthesis, including preparation for colloidosomes and fabrication of Janus microparticles with anisotropic internal structures. Finally, a combined system consisting of ECC-induced droplet dispensing and electrophoresis of charged droplet (ECD)-driven manipulation systems is constructed. This work was supported by the BK21Plus Program for advanced education of creative chemical engineers of the National Research Foundation of Korea (NRF) Grant funded by the Korea government (MSIP).

Compressed air-assisted solvent extraction (CASX) for metal removal.

PubMed

Li, Chi-Wang; Chen, Yi-Ming; Hsiao, Shin-Tien

2008-03-01

A novel process, compressed air-assisted solvent extraction (CASX), was developed to generate micro-sized solvent-coated air bubbles (MSAB) for metal extraction. Through pressurization of solvent with compressed air followed by releasing air-oversaturated solvent into metal-containing wastewater, MSAB were generated instantaneously. The enormous surface area of MSAB makes extraction process extremely fast and achieves very high aqueous/solvent weight ratio (A/S ratio). CASX process completely removed Cr(VI) from acidic electroplating wastewater under A/S ratio of 115 and extraction time of less than 10s. When synthetic wastewater containing Cd(II) of 50mgl(-1) was treated, A/S ratios of higher than 714 and 1190 could be achieved using solvent with extractant/diluent weight ratio of 1:1 and 5:1, respectively. Also, MSAB have very different physical properties, such as size and density, compared to the emulsified solvent droplets, making separation and recovery of solvent from treated effluent very easy.

A hemispherical Langmuir probe array detector for angular resolved measurements on droplet-based laser-produced plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gambino, Nadia, E-mail: gambinon@ethz.ch; Brandstätter, Markus; Rollinger, Bob

2014-09-15

In this work, a new diagnostic tool for laser-produced plasmas (LPPs) is presented. The detector is based on a multiple array of six motorized Langmuir probes. It allows to measure the dynamics of a LPP in terms of charged particles detection with particular attention to droplet-based LPP sources for EUV lithography. The system design permits to temporally resolve the angular and radial plasma charge distribution and to obtain a hemispherical mapping of the ions and electrons around the droplet plasma. The understanding of these dynamics is fundamental to improve the debris mitigation techniques for droplet-based LPP sources. The device hasmore » been developed, built, and employed at the Laboratory for Energy Conversion, ETH Zürich. The experimental results have been obtained on the droplet-based LPP source ALPS II. For the first time, 2D mappings of the ion kinetic energy distribution around the droplet plasma have been obtained with an array of multiple Langmuir probes. These measurements show an anisotropic expansion of the ions in terms of kinetic energy and amount of ion charge around the droplet target. First estimations of the plasma density and electron temperature were also obtained from the analysis of the probe current signals.« less

Influence of droplet charge on the chemical stability of citral in oil-in-water emulsions.

PubMed

Choi, Seung Jun; Decker, Eric Andrew; Henson, Lulu; Popplewell, L Michael; McClements, David Julian

2010-08-01

The chemical stability of citral, a flavor component widely used in beverage, food, and fragrance products, in oil-in-water emulsions stabilized by surfactants with different charge characteristics was investigated. Emulsions were prepared using cationic (lauryl alginate, LAE), non-ionic (polyoxyethylene (23) lauryl ether, Brij 35), and anionic (sodium dodecyl sulfate, SDS) surfactants at pH 3.5. The citral concentration decreased over time in all the emulsions, but the rate of decrease depended on surfactant type. After 7 d storage, the citral concentrations remaining in the emulsions were around 60% for LAE- or Brij 35-stabilized emulsions and 10% for SDS-stabilized emulsions. An increase in the local proton (H(+)) concentration around negatively charged droplet surfaces may account for the more rapid citral degradation observed in SDS-stabilized emulsions. A strong metal ion chelator (EDTA), which has previously been shown to be effective at increasing the oxidative stability of labile components, had no effect on citral stability in LAE- or Brij 35-stabilized emulsions, but it slightly decreased the initial rate of citral degradation in SDS-stabilized emulsions. These results suggest the surfactant type used to prepare emulsions should be controlled to improve the chemical stability of citral in emulsion systems.

A simple method for the fast calculation of charge redistribution of solutes in an implicit solvent model

NASA Astrophysics Data System (ADS)

Dias, L. G.; Shimizu, K.; Farah, J. P. S.; Chaimovich, H.

2002-09-01

We propose and demonstrate the usefulness of a method, defined as generalized Born electronegativity equalization method (GBEEM) to estimate solvent-induced charge redistribution. The charges obtained by GBEEM, in a representative series of small organic molecules, were compared to PM3-CM1 charges in vacuum and in water. Linear regressions with appropriate correlation coefficients and standard deviations between GBEEM and PM3-CM1 methods were obtained ( R=0.94,SD=0.15, Ftest=234, N=32, in vacuum; R=0.94,SD=0.16, Ftest=218, N=29, in water). In order to test the GBEEM response when intermolecular interactions are involved we calculated a water dimer in dielectric water using both GBEEM and PM3-CM1 and the results were similar. Hence, the method developed here is comparable to established calculation methods.

Spectroscopic studies of multiple charge transfer complexes of p-toluidine with π-acceptor picric acid in different polar solvents

NASA Astrophysics Data System (ADS)

Singh, Neeti; Ahmad, Afaq

2010-04-01

The charge transfer complexes of the donor p-toluidine with π-acceptor picric acid have been studied spectrophotometrically in various solvents such as acetone, ethanol, and methanol at room temperature using absorption spectrophotometer. The results indicate that formation of CTC in less polar solvent is high. The stoichiometry of the complex was found to be 1: 1 ratio by straight line method between donor and acceptor with maximum absorption bands. The data are discussed in terms of formation constant ( K CT), molar extinction coefficient (ɛCT), standard free energy (Δ G°), oscillator strength ( f), transition dipole moment (μEN), resonance energy ( R N) and ionization potential ( I D). The results indicate that the formation constant ( K CT) for the complex were shown to be dependent upon the nature of electron acceptor, donor and polarity of solvents which were used.

Direct current dielectrophoretic manipulation of the ionic liquid droplets in water.

PubMed

Zhao, Kai; Li, Dongqing

2018-07-13

The ionic liquids (ILs) as the environmentally benign solvents show great potentials in microemulsion carrier systems and have been widely used in the biochemical and pharmaceutical fields. In the work, the ionic liquid-in-water microemulsions were fabricated by using two kinds of hydrophobic ionic liquid, 1-Butyl-3-methylimidazolium hexafluorophosphate [Bmim][PF 6 ] and 1-Hexyl-3-methylimidazolium hexafluorophosphate [Hmim][PF 6 ] with Tween 20. The ionic liquid droplets in water experience the dielectrophoretic (DEP) forces induced by applying electrical field via a nano-orifice and a micron orifice on the opposite channel walls of a microchannel. The dielectrophoretic behaviors of the ionic liquid-in-water emulsion droplets were investigated under direct current (DC) electric field. The positive and negative DEP behaviors of the ionic liquid-in-water droplets varying with the electrical conductivity of the suspending medium were investigated and two kinds of the ionic liquid droplets of similar sizes were separated by their different DEP behaviors. In addition, the separation of the ionic liquid-in-water droplets by size was conducted. This paper, for the first time to our knowledge, presents the DC-DEP manipulation of the ionic liquid-in-water emulsion droplets by size and by type. This method provides a platform to manipulate the ionic liquid droplets individually. Copyright © 2018 Elsevier B.V. All rights reserved.

Solute-Solvent Charge-Transfer Excitations and Optical Absorption of Hydrated Hydroxide from Time-Dependent Density-Functional Theory.

PubMed

Opalka, Daniel; Sprik, Michiel

2014-06-10

The electronic structure of simple hydrated ions represents one of the most challenging problems in electronic-structure theory. Spectroscopic experiments identified the lowest excited state of the solvated hydroxide as a charge-transfer-to-solvent (CTTS) state. In the present work we report computations of the absorption spectrum of the solvated hydroxide ion, treating both solvent and solute strictly at the same level of theory. The average absorption spectrum up to 25 eV has been computed for samples taken from periodic ab initio molecular dynamics simulations. The experimentally observed CTTS state near the onset of the absorption threshold has been analyzed at the generalized-gradient approximation (GGA) and with a hybrid density-functional. Based on results for the lowest excitation energies computed with the HSE hybrid functional and a Davidson diagonalization scheme, the CTTS transition has been found 0.6 eV below the first absorption band of liquid water. The transfer of an electron to the solvent can be assigned to an excitation from the solute 2pπ orbitals, which are subject to a small energetic splitting due to the asymmetric solvent environment, to the significantly delocalized lowest unoccupied orbital of the solvent. The distribution of the centers of the excited state shows that CTTS along the OH(-) axis of the hydroxide ion is avoided. Furthermore, our simulations indicate that the systematic error arising in the calculated spectrum at the GGA originates from a poor description of the valence band energies in the solution.

Performance of droplet generator and droplet collector in liquid droplet radiator under microgravity

NASA Astrophysics Data System (ADS)

Totani, T.; Itami, M.; Nagata, H.; Kudo, I.; Iwasaki, A.; Hosokawa, S.

2002-06-01

The Liquid Droplet Radiator (LDR) has an advantage over comparable conventional radiators in terms of the rejected heat power-weight ratio. Therefore, the LDR has attracted attention as an advanced radiator for high-power space systems that will be prerequisite for large space structures. The performance of the LDR under microgravity condition has been studied from the viewpoint of operational space use of the LDR in the future. In this study, the performances of a droplet generator and a droplet collector in the LDR are investigated using drop shafts in Japan: MGLAB and JAMIC. As a result, it is considered that (1) the droplet generator can produce uniform droplet streams in the droplet diameter range from 200 to 280 [µm] and the spacing range from 400 to 950 [µm] under microgravity condition, (2) the droplet collector with the incidence angle of 35 degrees can prevent a uniform droplet stream, in which droplet diameter is 250 [µm] and the velocity is 16 [m/s], from splashing under microgravity condition, whereas splashes may occur at the surface of the droplet collector in the event that a nonuniform droplet stream collides against it.

Thermophoresis in nanoliter droplets to quantify aptamer binding.

PubMed

Seidel, Susanne A I; Markwardt, Niklas A; Lanzmich, Simon A; Braun, Dieter

2014-07-21

Biomolecule interactions are central to pharmacology and diagnostics. These interactions can be quantified by thermophoresis, the directed molecule movement along a temperature gradient. It is sensitive to binding induced changes in size, charge, or conformation. Established capillary measurements require at least 0.5 μL per sample. We cut down sample consumption by a factor of 50, using 10 nL droplets produced with acoustic droplet robotics (Labcyte). Droplets were stabilized in an oil-surfactant mix and locally heated with an IR laser. Temperature increase, Marangoni flow, and concentration distribution were analyzed by fluorescence microscopy and numerical simulation. In 10 nL droplets, we quantified AMP-aptamer affinity, cooperativity, and buffer dependence. Miniaturization and the 1536-well plate format make the method high-throughput and automation friendly. This promotes innovative applications for diagnostic assays in human serum or label-free drug discovery screening. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular Dynamics Simulation Study of Solvent and State of Charge Effects on Solid-Phase Structure and Counterion Binding in a Nitroxide Radical Containing Polymer Energy Storage Material

DOE PAGES

Kemper, Travis W.; Gennett, Thomas; Larsen, Ross E.

2016-10-19

Here we performed molecular dynamics simulations to understand the effects of solvent swelling and state of charge (SOC) on the redox active, organic radical cathode material poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PTMA). We show that the polar solvent acetonitrile primarily solvates the nitroxide radical without disrupting the packing of the (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) pendant groups of PTMA. We also simulated bulk PTMA in different SOC, 25%, 50%, 75%, and 100%, by converting the appropriate number of TEMPO groups to the cation charge state and adding BF 4 - counterions to the simulation. At each SOC the packing of PTMA, the solvent, and the counterionsmore » were examined. The binding of the anion to the nitroxide cation site was examined using the potential of mean force and found to be on the order of tens of meV, with a binding energy that decreased with increasing SOC. Additionally, we found that the cation state is stabilized by the presence of a nearby anion by more than 1 eV, and the implications of this stabilization on charge transport are discussed. Finally, we describe the implications of our results for how the SOC of an organic electrode affects electron and anion charge transport during the charging and discharging processes.« less

Effect of viscosity on droplet-droplet collisional interaction

NASA Astrophysics Data System (ADS)

Finotello, Giulia; Padding, Johan T.; Deen, Niels G.; Jongsma, Alfred; Innings, Fredrik; Kuipers, J. A. M.

2017-06-01

A complete knowledge of the effect of droplet viscosity on droplet-droplet collision outcomes is essential for industrial processes such as spray drying. When droplets with dispersed solids are dried, the apparent viscosity of the dispersed phase increases by many orders of magnitude, which drastically changes the outcome of a droplet-droplet collision. However, the effect of viscosity on the droplet collision regime boundaries demarcating coalescence and reflexive and stretching separation is still not entirely understood and a general model for collision outcome boundaries is not available. In this work, the effect of viscosity on the droplet-droplet collision outcome is studied using direct numerical simulations employing the volume of fluid method. The role of viscous energy dissipation is analysed in collisions of droplets with different sizes and different physical properties. From the simulations results, a general phenomenological model depending on the capillary number (Ca, accounting for viscosity), the impact parameter (B), the Weber number (We), and the size ratio (Δ) is proposed.

Understanding Solvent Manipulation of Morphology in Bulk-Heterojunction Organic Solar Cells.

PubMed

Chen, Yuxia; Zhan, Chuanlang; Yao, Jiannian

2016-10-06

Film morphology greatly influences the performance of bulk-heterojunction (BHJ)-structure-based solar cells. It is known that an interpenetrating bicontinuous network with nanoscale-separated donor and acceptor phases for charge transfer, an ordered molecular packing for exciton diffusion and charge transport, and a vertical compositionally graded structure for charge collection are prerequisites for achieving highly efficient BHJ organic solar cells (OSCs). Therefore, control of the morphology to obtain an ideal structure is a key problem. For this solution-processing BHJ system, the solvent participates fully in film processing. Its involvement is critical in modifying the nanostructure of BHJ films. In this review, we discuss the effects of solvent-related methods on the morphology of BHJ films, including selection of the casting solvent, solvent mixture, solvent vapor annealing, and solvent soaking. On the basis of a discussion on interaction strength and time between solvent and active materials, we believe that the solvent-morphology-performance relationship will be clearer and that solvent selection as a means to manipulate the morphology of BHJ films will be more rational. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrostatic charge characteristics of jet nebulized aerosols.

PubMed

Kwok, Philip Chi Lip; Trietsch, Sebastiaan J; Kumon, Michiko; Chan, Hak-Kim

2010-06-01

Liquid droplets can be spontaneously charged in the absence of applied electric fields by spraying. It has been shown by computational simulation that charges may influence particle deposition in the airways. The electrostatic properties of jet nebulized aerosols and their potential effects on lung deposition have hardly been studied. A modified electrical low pressure impactor (ELPI) was employed to characterize the aerosol charges generated from jet nebulized commercial products. The charge and size measurements were conducted at 50% RH and 22 degrees C with a modified ELPI. Ventolin, Bricanyl, and Atrovent were nebulized using PARI LC Plus jet nebulizers coupled to a DeVilbiss Pulmo-Aide compressor. The aerosols were sampled in 30-sec durations. The drug deposits on the impactor stages were assayed chemically using high-performance liquid chromatography (HPLC). The charges of nebulized deionized water, isotonic saline, and the three commercial products diluted with saline were also measured to analyze the contributions of the major nebule ingredients on charging. No mass assays were performed on these runs. All three commercial nebules generated net negative charges. The magnitude of the charges reduced over the period of nebulization. Ventolin and Bricanyl yielded similar charge profiles. Highly variable charges were produced from deionized water. On the other hand, nebulized saline reproducibly generated net positive charges. Diluted commercial nebules showed charge polarity inversion. The charge profiles of diluted salbutamol and terbutaline solutions resembled those of saline, while the charges from diluted ipratropium solutions fluctuated near neutrality. The charge profiles were shown to be influenced by the concentration and physicochemical properties of the drugs, as well as the history of nebulization. The drugs may have unique isoelectric concentrations in saline at which the nebulized droplets would carry near-zero charges. According to results from

Evaluating stratiform cloud base charge remotely

NASA Astrophysics Data System (ADS)

Harrison, R. Giles; Nicoll, Keri A.; Aplin, Karen L.

2017-06-01

Stratiform clouds acquire charge at their upper and lower horizontal boundaries due to vertical current flow in the global electric circuit. Cloud charge is expected to influence microphysical processes, but understanding is restricted by the infrequent in situ measurements available. For stratiform cloud bases below 1 km in altitude, the cloud base charge modifies the surface electric field beneath, allowing a new method of remote determination. Combining continuous cloud height data during 2015-2016 from a laser ceilometer with electric field mill data, cloud base charge is derived using a horizontal charged disk model. The median daily cloud base charge density found was -0.86 nC m-2 from 43 days' data. This is consistent with a uniformly charged region 40 m thick at the cloud base, now confirming that negative cloud base charge is a common feature of terrestrial layer clouds. This technique can also be applied to planetary atmospheres and volcanic plumes.