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Sample records for charged solvent droplets

  1. Reactions of Microsolvated Organic Compounds at Ambient Surfaces: Droplet Velocity, Charge State, and Solvent Effects

    NASA Astrophysics Data System (ADS)

    Badu-Tawiah, Abraham K.; Campbell, Dahlia I.; Cooks, R. Graham

    2012-06-01

    The exposure of charged microdroplets containing organic ions to solid-phase reagents at ambient surfaces results in heterogeneous ion/surface reactions. The electrosprayed droplets were driven pneumatically in ambient air and then electrically directed onto a surface coated with reagent. Using this reactive soft landing approach, acid-catalyzed Girard condensation was achieved at an ambient surface by directing droplets containing Girard T ions onto a dry keto-steroid. The charged droplet/surface reaction was much more efficient than the corresponding bulk solution-phase reaction performed on the same scale. The increase in product yield is ascribed to solvent evaporation, which causes moderate pH values in the starting droplet to reach extreme values and increases reagent concentrations. Comparisons are made with an experiment in which the droplets were pneumatically accelerated onto the ambient surface (reactive desorption electrospray ionization, DESI). The same reaction products were observed but differences in spatial distribution were seen associated with the "splash" of the high velocity DESI droplets. In a third type of experiment, the reactions of charged droplets with vapor phase reagents were examined by allowing electrosprayed droplets containing a reagent to intercept the headspace vapor of an analyte. Deposition onto a collector surface and mass analysis showed that samples in the vapor phase were captured by the electrospray droplets, and that instantaneous derivatization of the captured sample is possible in the open air. The systems examined under this condition included the derivatization of cortisone vapor with Girard T and that of 4-phenylpyridine N-oxide and 2-phenylacetophenone vapors with ethanolamine.

  2. Electrostatic charging of jumping droplets

    NASA Astrophysics Data System (ADS)

    Miljkovic, Nenad; Preston, Daniel J.; Enright, Ryan; Wang, Evelyn N.

    2013-09-01

    With the broad interest in and development of superhydrophobic surfaces for self-cleaning, condensation heat transfer enhancement and anti-icing applications, more detailed insights on droplet interactions on these surfaces have emerged. Specifically, when two droplets coalesce, they can spontaneously jump away from a superhydrophobic surface due to the release of excess surface energy. Here we show that jumping droplets gain a net positive charge that causes them to repel each other mid-flight. We used electric fields to quantify the charge on the droplets and identified the mechanism for the charge accumulation, which is associated with the formation of the electric double layer at the droplet-surface interface. The observation of droplet charge accumulation provides insight into jumping droplet physics as well as processes involving charged liquid droplets. Furthermore, this work is a starting point for more advanced approaches for enhancing jumping droplet surface performance by using external electric fields to control droplet jumping.

  3. Electrostatic charging of jumping droplets.

    PubMed

    Miljkovic, Nenad; Preston, Daniel J; Enright, Ryan; Wang, Evelyn N

    2013-01-01

    With the broad interest in and development of superhydrophobic surfaces for self-cleaning, condensation heat transfer enhancement and anti-icing applications, more detailed insights on droplet interactions on these surfaces have emerged. Specifically, when two droplets coalesce, they can spontaneously jump away from a superhydrophobic surface due to the release of excess surface energy. Here we show that jumping droplets gain a net positive charge that causes them to repel each other mid-flight. We used electric fields to quantify the charge on the droplets and identified the mechanism for the charge accumulation, which is associated with the formation of the electric double layer at the droplet-surface interface. The observation of droplet charge accumulation provides insight into jumping droplet physics as well as processes involving charged liquid droplets. Furthermore, this work is a starting point for more advanced approaches for enhancing jumping droplet surface performance by using external electric fields to control droplet jumping.

  4. Charged Slurry Droplet Research

    DTIC Science & Technology

    1989-02-20

    Spectrometer 14 3.3 Charge Detection Assembly 15 3.4 Experimental Procedure 16 Chapter IV Data Analysis and Discussion 17 4.1 Introduction 17 4.2 Experimental... Data 17 4.3 Comparison with Published Work 18 4.4 Size Distribution 19 4.5 Regression Analysis Results 20 4.6 Multiple Charging Characteristics 21 4.7...This processed data is then sent to the Princeton University mainframe IBM 3081 computer for regression analysis . The purpose of the regression

  5. Interaction between electrically charged droplets in microgravity

    NASA Astrophysics Data System (ADS)

    Brandenbourger, Martin; Caps, Herve; Hardouin, Jerome; Vitry, Youen; Boigelot, Bernard; Dorbolo, Stephane; Grasp Team; Beams Collaboration

    2015-11-01

    The past ten years, electrically charged droplets have been studied tremendously for their applications in industry (electrospray, electrowetting,...). However, charged droplets are also present in nature. Indeed, it has been shown that the droplets falling from thunderclouds possess an excess of electric charges. Moreover, some research groups try to use the electrical interaction between drops in order to control the coalescence between cloud droplets and control rain generation. The common way to study this kind of system is to make hypothesis on the interaction between two charged drops. Then, these hypothesis are extended to a system of thousands of charged droplets. Thanks to microgravity conditions, we were able to study the interaction between two electrically charged droplets. In practice, the charged droplets were propelled one in front of the other at low speed (less than 1 m/s). The droplets trajectory is studied for various charges and volumes. The repulsion between two charged drops is correctly fitted by a simple Coulomb repulsion law. In the case of attractive interactions, we discuss the collisions observed as a function of the droplets speed, volume and electric charges. Thanks to FNRS for financial support.

  6. Droplet Charging Effects in the Space Environment

    SciTech Connect

    Joslyn, Thomas B.; Ketsdever, Andrew D.

    2011-05-20

    Several applications exist for transiting liquid droplets through the near-Earth space environment. Numerical results are presented for the charging of liquid droplets of trimethyl pentaphenyl siloxane (DC705) in three different plasma environments: ionosphere, auroral, and geosynchronous Earth orbit (GEO). Nominal and high geomagnetic activity cases are investigated. In general, high levels of droplet charging (>100 V) exist only in GEO during periods of high geomagnetic or solar activity. An experiment was conducted to assess the charging of silicon-oil droplets due to photoemission. The photoemission yield in the 120-200 nm wavelength range was found to be approximately 0.06.

  7. Characterization of "Star" Droplet Morphologies Induced by Charged Macromolecules.

    PubMed

    Sharawy, Mahmoud; Consta, Styliani

    2016-11-10

    "Star" morphologies of charged liquid droplets are distinct droplet conformations that, for a certain charge squared to volume ratio, have lower energy than their spherically shaped analogues. For these shapes to appear, the charge should be carried by a single ionic species. A typical example of a charge carrier that we employ in this study is a fully charged double-stranded oligodeoxynucleotide (dsDNA) in an aqueous and an acetonitrile droplet. We characterize the structure and dynamics of the star-shaped droplets. We find that by increasing the charge squared to volume ratio, the droplet evolves from spherical to "spiky" shapes, by first passing from droplet sizes that undergo enhanced shape fluctuations relative to those of the larger spherical droplets. These fluctuations mark the onset of the instability. We also find that in the spiky droplet, the orientation of the solvent molecules in the first shell about the dsDNA is very close to that in the bulk solution. However, this orientation is substantially different farther away from the dsDNA. With regards to dynamics, the motion of the spikes is reflected in the autocorrelation functions of rotationally invariant order parameters that show a damped oscillator form of decay, indicative of the elastic motion of the spikes. We compare the formation of spikes with that of the ferrofluids and the dielectric materials in an electric field, and we conclude that they represent a different entity that deserves its own characterization. The study provides insight into the manner in which the charge distribution may give rise to well-controlled droplet morphologies and calls for experiments in this direction.

  8. Nucleation of electrically charged droplets

    NASA Technical Reports Server (NTRS)

    De, B. R.

    1979-01-01

    The nucleating droplets or clusters in many nucleation environments (various colloidal plasmas in laboratory and technological applications, astrophysical condensation environments, etc.) are likely to be at a finite electric potential. This may be due either to the presence of electrons and ions in the gas phase or to the thermal ionization or photoionization of the droplets. The paper demonstrates that this potential may introduce a nontrivial modification in the conventional nucleation theory. Some results for the typical case of nucleation of water droplets are presented. The general conclusion is that the electric potential makes nucleation harder to achieve, thereby demonstrating the importance of a finite droplet potential in the theory of nucleation.

  9. A pipette dispenses a charged droplet

    NASA Astrophysics Data System (ADS)

    Choi, Dongwhi; Lee, Horim; Im, Do Jin; Kang, In Seok; Kang, Kwan Hyoung

    2012-11-01

    Micropipettes are widely used in many scientific and engineering fields. However, it is hardly known that a droplet dispensed from a plastic pipette tip has a considerable amount of charges (order of 10-10 C). Here we report that the charged droplet is dispensed from a commercial and disposable plastic pipette tip and this charge is originated from the natural electrification between a solution and the inner surface of the pipette tip. The charge amount is dependent on not only the physicochemical properties of a solution (e.g., pH and a concentration) but also dispensing environments (e.g., atmospheric humidity and type of commercial pipette tip). To investigate the effects of the charge on the droplet dispensing, we calculate the electrical force between the droplet and the pipette tip though numerical simulation. The micropipette users especially, who are dealing with discrete droplets in their experiments, should consider this charge effect in their dispensing of a droplet. This work was supported by the National Research Foundation of Korea (NRF) Grant No. R0A-2007-000-20098-0 funded by the Korea government (MEST) and No. 20090083510 through Multiphenomena CFD Engineering Research Center.

  10. Evaporation and discharge dynamics of highly charged multicomponent droplets generated by electrospray ionization.

    PubMed

    Grimm, Ronald L; Beauchamp, J L

    2010-01-28

    We investigate the Rayleigh discharge and evaporation dynamics of highly charged two-component droplets consisting principally of methanol with 2-methoxyethanol, tert-butanol, or m-nitrobenzyl alcohol. A phase Doppler anemometer (PDA) characterizes droplets generated by electrospray ionization (ESI) according to size, velocity, and charge as they move through a uniform electric field within an ion mobility spectrometer (IMS). Repeated field reversals result in droplet "ping-pong" through the PDA. This generates individual droplet histories of solvent evaporation behavior and the dynamics of charge loss to progeny droplets during Rayleigh discharge events. On average, methanol droplets discharge at 127% their Rayleigh limit of charge, q(R), and release 25% of the net charge. Charge loss from methanol/2-methoxyethanol droplets behaves similarly to pure 2-methoxyethanol droplets which release approximately 28% of their net charge. Binary methanol droplets containing up to 50% tert-butanol discharge at a lower percent q(R) than pure methanol and release a greater fraction of their net charge. Mixed 99% methanol/1% m-nitrobenzyl alcohol droplets possess discharge characteristics similar to those of methanol. However, droplets of methanol containing 2% m-nitrobenzyl evaporate down to a fixed size and charge that remains constant with no observable discharges. Quasi-steady-state evaporation models accurately describe observed evaporation phenomena in which methanol/tert-butanol droplets evaporate at a rate similar to that of pure methanol and methanol/2-methoxyethanol droplets evaporate at a rate similar to that of 2-methoxyethanol. We compare these results to previous Rayleigh discharge experiments and discuss the implications for binary solvents in electrospray mass spectrometry (ESI-MS) and field-induced droplet ionization mass spectrometry (FIDI-MS).

  11. Classification of the ejection mechanisms of charged macromolecules from liquid droplets

    NASA Astrophysics Data System (ADS)

    Consta, Styliani; Malevanets, Anatoly

    2013-01-01

    The relation between the charge state of a macromolecule and its ejection mechanism from droplets is one of the important questions in electrospray ionization methods. In this article, effects of solvent-solute interaction on the manifestation of the charge induced instability in a droplet are examined. We studied the instabilities in a prototype system of a droplet comprised of charged poly(ethylene glycol) and methanol, acetonitrile, and water solvents. We observed instances of three, previously only conjectured, [S. Consta, J. Phys. Chem. B 114, 5263 (2010), 10.1021/jp912119v] mechanisms of macroion ejection. The mechanism of ejection of charged macroion in methanol is reminiscent of "pearl" model in polymer physics. In acetonitrile droplets, the instability manifests through formation of solvent spines around the solvated macroion. In water, we find that the macroion is ejected from the droplet through contiguous extrusion of a part of the chain. The difference in the morphology of the instabilities is attributed to the interplay between forces arising from the macroion solvation energy and the surface energy of the droplet interface. For the contiguous extrusion of a charged macromolecule from a droplet, we demonstrate that the proposed mechanism leads to ejection of the macromolecule from droplets with sizes well below the Rayleigh limit. The ejected macromolecule may hold charge significantly higher than that suggested by prevailing theories. The simulations reveal new mechanisms of macroion evaporation that differ from conventional charge residue model and ion evaporation mechanisms.

  12. Electrostatic charging and control of droplets in microfluidic devices.

    PubMed

    Zhou, Hongbo; Yao, Shuhuai

    2013-03-07

    Precharged droplets can facilitate manipulation and control of low-volume liquids in droplet-based microfluidics. In this paper, we demonstrate non-contact electrostatic charging of droplets by polarizing a neutral droplet and splitting it into two oppositely charged daughter droplets in a T-junction microchannel. We performed numerical simulation to analyze the non-contact charging process and proposed a new design with a notch at the T-junction in aid of droplet splitting for more efficient charging. We experimentally characterized the induced charge in droplets in microfabricated devices. The experimental results agreed well with the simulation. Finally, we demonstrated highly effective droplet manipulation in a path selection unit appending to the droplet charging. We expect our work could enable precision manipulation of droplets for more complex liquid handling in microfluidics and promote electric-force based manipulation in 'lab-on-a-chip' systems.

  13. Droplet-model predictions of charge moments

    SciTech Connect

    Myers, W.D.

    1982-04-01

    The Droplet Model expressions for calculating various moments of the nuclear charge distribution are given. There are contributions to the moments from the size and shape of the system, from the internal redistribution induced by the Coulomb repulsion, and from the diffuseness of the surface. A case is made for the use of diffuse charge distributions generated by convolution as an alternative to Fermi-functions.

  14. Coalescence and Breakup of Oppositely Charged Droplets

    PubMed Central

    Wang, Junfeng; Wang, Bin; Qiu, Huihe

    2014-01-01

    The coalescence process of oppositely charged drops for different electrical conductivities of liquids is presented. When the electrical conductivity was relatively low, oppositely charged drops failed to coalesce under sufficiently high electrical fields and capillary ripples were formed on the surfaces of droplets after rebound. For a high electrically conductive liquid, it was found that a crown profile of drop fission always appeared on the top surface of negatively charged drops after the two charged drops contacted and bounced off. Furthermore, we report here, for the first time, the newly found phenomenon and argue that the break up might be caused by Rayleigh instability, a form of Coulomb fission. The different mobility of positive and negative ions is the underlying mechanism that explains why the break up always happened on the negative side of charged drops. PMID:25410022

  15. Retreat behavior of a charged droplet for electrohydrodynamic inkjet printing

    NASA Astrophysics Data System (ADS)

    Yudistira, Hadi Teguh; Nguyen, Vu Dat; Tran, Si Bui Quang; Kang, Tae Sam; Park, Jung Keun; Byun, Doyoung

    2011-02-01

    The charged droplet retreat phenomenon in electrohydrodynamic inkjet printing is experimentally observed and theoretically explained. If the charge concentration of a droplet generated from a nozzle is high enough, Coulomb fission is generated a second time and the main droplet retreats to the meniscus on the nozzle. The retreat phenomenon is due to interactions between the charged droplet, the meniscus, and charges on the substrate. The Rayleigh limit is used to give a theoretical estimate of the amount of charge on the droplet and the meniscus during the retreat.

  16. Retreating behavior of a charged ionic liquid droplet in a dielectric liquid under electric field

    NASA Astrophysics Data System (ADS)

    Ahn, Myung Mo; Im, Do Jin; Kang, In Seok

    2013-11-01

    Ionic liquids show great promise as excellent solvents or catalysts in energy and biological fields due to their unique chemical and physical properties. The ionic liquid droplets in microfluidic systems can also be used as a potential platform for chemical biological reactions. In order to control electrically the ionic liquid droplets in a microfluidic device, the charging characteristics of ionic liquid droplets need to be understood. In this work, the charging characteristics of various ionic liquids are investigated by using the parallel plate electrodes system. Under normal situation, a charged droplet shows bouncing motion between electrodes continuously. However, for some special ionic liquids, interesting retreating behavior of charged ionic liquid droplet has been observed. This retreating behavior of ionic liquid droplet has been analyzed experimentally by the image analysis and the electrometer signal analysis. Based on the hypothesis of charge leakage of the retreating ionic liquid droplets, FT-IR spectroscopy analysis has also been performed. The retreating behavior of ionic liquid droplet is discussed from the intermolecular point of view according to the species of ionic liquids. This research was supported by grant No. 2013R1A1A2011956 funded by the Ministry of Science, ICT and Future Planning (MSIP) and by grant No. 2013R1A1A2010483 funded by the Ministry of Education, Science and Technology (MEST) through the NRF.

  17. Spontaneous electrical charging of droplets by conventional pipetting

    PubMed Central

    Choi, Dongwhi; Lee, Horim; Im, Do Jin; Kang, In Seok; Lim, Geunbae; Kim, Dong Sung; Kang, Kwan Hyoung

    2013-01-01

    We report that a droplet dispensed from a micropipette almost always has a considerable electrical charge of a magnitude dependent on the constituents of the droplet, on atmospheric humidity and on the coating material of pipette tip. We show that this natural electrification of a droplet originates from the charge separation between a droplet and pipette tip surface by contact with water due to the ionization of surface chemical groups. Charge on a droplet can make it difficult to detach the droplet from the pipette tip, can decrease its surface tension, can affect the chemical characteristics of solutions due to interactions with charged molecules, and can influence the combination and localization of charged bio-molecules; in all cases, the charge may affect results of experiments in which any of these factors is important. Thus, these findings reveal experimental parameters that should be controlled in experiments that use micropipettes. PMID:23784001

  18. Electrically Charged Droplets in Microgravity. Impact and Trajectories

    NASA Astrophysics Data System (ADS)

    Brandenbourger, Martin; Caps, Hervé; Vitry, Youen; Dorbolo, Stéphane

    2017-06-01

    In this work, the interaction between electrically charged droplets in microgravity is considered. During the 22 s of microgravity brought by a parabolic flight, water droplets with a radius r ∈ [0.41 - 0.97] mm were released one in front of the other. A high-speed camera allowed studying their interaction in the focal plane. The trajectories of the droplets are well adjusted by a punctual charge model. In some experiments, a physical contact between the charged droplets was observed. These collisions are studied via a phase diagram comparing the droplet Weber number, We, and the collision parameter, χ. By comparing these collisions to experiments involving neutral droplets, we deduce how the collision diagram is affected by electric charges. In particular, we show that the criterion for an impact between two droplets is no more χ < 1.

  19. Electrically Charged Droplets in Microgravity - Impact and Trajectories

    NASA Astrophysics Data System (ADS)

    Brandenbourger, Martin; Caps, Hervé; Vitry, Youen; Dorbolo, Stéphane

    2017-03-01

    In this work, the interaction between electrically charged droplets in microgravity is considered. During the 22 s of microgravity brought by a parabolic flight, water droplets with a radius r ∈ [0.41 - 0.97] mm were released one in front of the other. A high-speed camera allowed studying their interaction in the focal plane. The trajectories of the droplets are well adjusted by a punctual charge model. In some experiments, a physical contact between the charged droplets was observed. These collisions are studied via a phase diagram comparing the droplet Weber number, We, and the collision parameter, χ. By comparing these collisions to experiments involving neutral droplets, we deduce how the collision diagram is affected by electric charges. In particular, we show that the criterion for an impact between two droplets is no more χ < 1.

  20. 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.

  1. Discrete electrostatic charge transfer by the electrophoresis of a charged droplet in a dielectric liquid.

    PubMed

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

    2012-08-14

    We have experimentally investigated the electrostatic charging of a water droplet on an electrified electrode surface to explain the detailed inductive charging processes and use them for the detection of droplet position in a lab-on-a-chip system. The periodic bouncing motion of a droplet between two planar electrodes has been examined by using a high-resolution electrometer and an image analysis method. We have found that this charging process consists of three steps. The first step is inductive charge accumulation on the opposite electrode by the charge of a droplet. This induction process occurs while the droplet approaches the electrode, and it produces an induction current signal at the electrometer. The second step is the discharging of the droplet by the accumulated induced charge at the moment of contact. For this second step, there is no charge-transfer detection at the electrometer. The third step is the charging of the neutralized droplet to a certain charged state while the droplet is in contact with the electrode. The charge transfer of the third step is detected as the pulse-type signal of an electrometer. The second and third steps occur simultaneously and rapidly. We have found that the induction current by the movement of a charged droplet can be accurately used to measure the charge of the droplet and can also be used to monitor the position of a droplet under actuation. The implications of the current findings for understanding and measuring the charging process are discussed.

  2. Charging and Release Mechanisms of Flexible Macromolecules in Droplets

    NASA Astrophysics Data System (ADS)

    Oh, Myong In; Consta, Styliani

    2017-08-01

    We study systematically the charging and release mechanisms of a flexible macromolecule, modeled by poly(ethylene glycol) (PEG), in a droplet by using molecular dynamics simulations. We compare how PEG is solvated and charged by sodium Na+ ions in a droplet of water (H2O), acetonitrile (MeCN), and their mixtures. Initially, we examine the location and the conformation of the macromolecule in a droplet bearing no net charge. It is revealed that the presence of charge carriers do not affect the location of PEG in aqueous and MeCN droplets compared with that in the neutral droplets, but the location of the macromolecule and the droplet size do affect the PEG conformation. PEG is charged on the surface of a sodiated aqueous droplet that is found close to the Rayleigh limit. Its charging is coupled to the extrusion mechanism, where PEG segments leave the droplet once they coordinate a Na+ ion or in a correlated motion with Na+ ions. In contrast, as PEG resides in the interior of a MeCN droplet, it is sodiated inside the droplet. The compact macro-ion transitions through partially unwound states to an extended conformation, a process occurring during the final stage of desolvation and in the presence of only a handful of MeCN molecules. For charged H2O/MeCN droplets, the sodiation of PEG is determined by the H2O component, reflecting its slower evaporation and preference over MeCN for solvating Na+ ions. We use the simulation data to construct an analytical model that suggests that the droplet surface electric field may play a role in the macro-ion-droplet interactions that lead to the extrusion of the macro-ion. This study provides the first evidence of the effect of the surface electric field by using atomistic simulations. [Figure not available: see fulltext.

  3. Flight behavior of charged droplets in electrohydrodynamic inkjet printing

    NASA Astrophysics Data System (ADS)

    Yudistira, Hadi Teguh; Nguyen, Vu Dat; Dutta, Prashanta; Byun, Doyoung

    2010-01-01

    Flight behaviors of charged droplets are presented for electrohydrodynamic (EHD) inkjet printing. Three different kinds of EHD spraying techniques, pulsed dc, ac, and single potential (SP) ac, have been investigated and both conductive and dielectric target surfaces were considered. Experimental results show that the flight paths of charged droplets may deviate from their regular straight route, i.e., directly from the nozzle to the substrate. Depending on the droplet charge and applied electric field, droplets may deflect, reflect, or retreat to the meniscus. We can solve these drawbacks by SP EHD printing.

  4. Evidence of molecular fragmentation inside the charged droplets produced by electrospray process.

    PubMed

    Banerjee, Shibdas; Prakash, Halan; Mazumdar, Shyamalava

    2011-10-01

    The behavior of the analyte molecules inside the neutral core of the charged droplet produced by the electrospray (ES) process is not unambiguously known to date. We have identified interesting molecular transformations of two suitably chosen analytes inside the ES droplets. The highly stable Ni(II) complex of 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane (1) that consists of a positive charge at the metal center, and the allyl pendant armed tertiary amine containing macrocycle 3,4,5:12,13,14-dipyridine-2,6,11,15-tetramethyl-1,7,10,16-tetraallyl-1,4,7,10,13,16-hexaazacyclooctadeca-3,13-diene (M(4p)) have been studied by ESI mass spectrometry as the model analytes. We have shown that these two molecules are not representatively transferred from solution to gas phase by ESI; rather, they undergo fragmentation inside the charged droplets. The results indicated that a charged analyte such as 1 was possibly unstable inside the neutral core of the ES droplet and undergoes fragmentation due to the Coulombic repulsion imparted by the surface protons. Brownian motion of the neutral analyte such as M(4p) inside the droplet, on the other hand, may lead to proton attachment on interaction with the charged surface causing destabilization that leads to fragmentation of M(4p) and release of resonance stabilized allyl cations from the core of the droplet. Detailed solvent dependence and collision-induced dissociation (CID) studies provided compelling evidences that the fragmentation of the analytes indeed occurs inside the charged ES droplets. A viable model of molecular transformations inside the ES droplet was proposed based on these results to rationalize the behavior of the analyte molecules inside the charged ES droplets.

  5. The Orbit of Water Droplets around Charged Rod

    ERIC Educational Resources Information Center

    Ferstl, Andrew; Burns, Andrew

    2013-01-01

    The motion of charges around a centrally charged object is often compared to gravitational orbits (such as satellites around planets). Recently, a video taken by astronaut Don Pettit onboard the International Space Station shows water droplets orbiting a charged knitting needle. Here we attempt to model this motion and estimate the charges on the…

  6. The Orbit of Water Droplets around Charged Rod

    ERIC Educational Resources Information Center

    Ferstl, Andrew; Burns, Andrew

    2013-01-01

    The motion of charges around a centrally charged object is often compared to gravitational orbits (such as satellites around planets). Recently, a video taken by astronaut Don Pettit onboard the International Space Station shows water droplets orbiting a charged knitting needle. Here we attempt to model this motion and estimate the charges on the…

  7. Characterization of electrode alignment for optimal droplet charging and actuation in droplet-based microfluidic system.

    PubMed

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

    2015-09-01

    The actuation method using electric force as a driving force is utilized widely in droplet-based microfluidic systems. In this work, the effects of charging electrode alignment on direct charging of a droplet on electrified electrodes and a subsequent electrophoretic control of the droplet are investigated. The charging characteristics of a droplet according to different electrode alignments are quantitatively examined through experiments and systematic numerical simulations with varying distances and angles between the two electrodes. The droplet charge acquired from the electrified electrode is directly proportional to the distance and barely affected by the angle between the two electrodes. This implies that the primary consideration of electrode alignment in microfluidic devices is the distance between electrodes and the insignificant effect of angle provides a great degree of freedom in designing such devices. Not only the droplet charge acquired from the electrode but also the force exerted on the droplet is analyzed. Finally, the implications and design guidance for microfluidic systems are discussed with an electrophoresis of a charged droplet method-based digital microfluidic device. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Electrostatic stability and encapsidation of charged nano-droplets

    NASA Astrophysics Data System (ADS)

    Javidpour, Leili; Božič, Anže Lošdorfer; Naji, Ali; Podgornik, Rudolf

    We investigate electrostatic stability of charged droplets, modeled as permeable, charged spheres, and their encapsidation in thin, arbitrarily charged nano-shells, immersed in a neutralizing asymmetric electrolyte background. The latter consists of a small concentration of mobile multivalent counterions in a bathing solution of monovalent (positive and negative) ions. We use extensive Monte-Carlo simulations to investigate the spatial distribution of multivalent counterions and the electrostatic component of their osmotic pressure on the bounding surface of the spherical nano-shell. The osmotic pressure can be negative (inward pressure), positive (outward pressure) or zero, depending on the system parameters such as the charge density of the droplet, the charge density of the shell, and the electrolyte screening, which thus determine the stability of the nano-container. The counter-intuitive effects of multivalent counterions comprise the increased stability of the charged droplet with larger charge density, increased stability in the case of encapsidating shell of charge density of the same sign as the charged droplet, as well as the possibility to dispense altogether with the encapsidating shell, its confining effect taken over by the multivalent counterions. These dramatic effects are in stark contrast to the conventional mean-field picture, which in particular implies that a more highly charged spherical droplet should be electrostatically less stable because of its larger (repulsive) self-energy.

  9. Quadrupole electromagnetic radiation of an oscillating charged droplet

    NASA Astrophysics Data System (ADS)

    Grigor'ev, A. I.; Kolbneva, N. Yu.; Shiryaeva, S. O.

    2017-06-01

    Analytical calculations using the first order of smallness with respect to dimensionless amplitude of oscillations show that the intensity of electromagnetic radiation of a charged droplet is determined by time-dependent quadrupole moment.

  10. Spontaneous charging and crystallization of water droplets in oil.

    PubMed

    de Graaf, Joost; Zwanikken, Jos; Bier, Markus; Baarsma, Arjen; Oloumi, Yasha; Spelt, Mischa; van Roij, René

    2008-11-21

    We study the spontaneous charging and the crystallization of spherical micron-sized water droplets dispersed in oil by numerically solving, within a Poisson-Boltzmann theory in the geometry of a spherical cell, for the density profiles of the cations and anions in the system. We take into account screening, ionic Born self-energy differences between oil and water, and partitioning of ions over the two media. We find that the surface charge density of the droplet as induced by the ion partitioning is significantly affected by the droplet curvature and by the finite density of the droplets. We also find that the salt concentration and the dielectric constant regime in which crystallization of the water droplets is predicted is enhanced substantially compared to results based on the planar oil-water interface, thereby improving quantitative agreement with recent experiments.

  11. Charge Spreading in Deep Eutectic Solvents.

    PubMed

    Zahn, Stefan; Kirchner, Barbara; Mollenhauer, Doreen

    2016-11-04

    Ab initio molecular dynamic simulations reveal significantly reduced ion charges in several choline-based deep eutectic solvents, which are cheap and eco-friendly alternatives to ionic liquids. Increasing hydrogen bond strength between the anion and the organic compound enhances charge spreading from the anion to the organic compound while the positive charge is stronger located at the cation. Nonetheless, the negative charge transferred from chloride to urea in choline chloride urea mixtures is negligible. Thus, it seems questionable if charge delocalization occurring through hydrogen bonding between the halide anion and the organic compound is responsible for the deep eutectic melting point. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Apparatus for the Study of Charged Particles and Droplets

    ERIC Educational Resources Information Center

    Berg, T. G. Owe; Gaulkler, T. A.

    1969-01-01

    Describes the construction and use of an apparatus for the free suspension of charged particles and droplets in the range 5-200u and for their study with respect to charge and mass and their variations with time in various gaseous environments. High-speed photography is used to determine the motion of particles. (LC)

  13. Charge Assisted Laser Desorption/Ionization Mass Spectrometry of Droplets

    PubMed Central

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

    2008-01-01

    We propose and evaluate a new mechanism to account for analyte ion signal enhancement in ultraviolet-laser desorption mass spectrometry of droplets in the presence of corona ions. Our new insights are based on timing control of corona ion production, laser desorption, and peptide ion extraction achieved by a novel pulsed corona apparatus. We demonstrate that droplet charging rather than gas-phase ion-neutral reactions is the major contributor to analyte ion generation from an electrically isolated droplet. Implications of the new mechanism, termed charge assisted laser desorption/ionization (CALDI), are discussed and contrasted to those of the laser desorption atmospheric pressure chemical ionization method (LD-APCI). It is also demonstrated that analyte ion generation in CALDI occurs with external electric fields about one order of magnitude lower than those needed for atmospheric pressure matrix assisted laser desorption/ionization or electrospray ionization of droplets. PMID:18387311

  14. Release of Native-like Gaseous Proteins from Electrospray Droplets via the Charged Residue Mechanism: Insights from Molecular Dynamics Simulations.

    PubMed

    McAllister, Robert G; Metwally, Haidy; Sun, Yu; Konermann, Lars

    2015-10-07

    The mechanism whereby gaseous protein ions are released from charged solvent droplets during electrospray ionization (ESI) remains a matter of debate. Also, it is unclear to what extent electrosprayed proteins retain their solution structure. Molecular dynamics (MD) simulations offer insights into the temporal evolution of protein systems. Surprisingly, there have been no all-atom simulations of the protein ESI process to date. The current work closes this gap by investigating the behavior of protein-containing aqueous nanodroplets that carry excess positive charge. We focus on "native ESI", where proteins initially adopt their biologically active solution structures. ESI proceeds while the protein remains entrapped within the droplet. Protein release into the gas phase occurs upon solvent evaporation to dryness. Droplet shrinkage is accompanied by ejection of charge carriers (Na(+) for the conditions chosen here), keeping the droplet at ∼85% of the Rayleigh limit throughout its life cycle. Any remaining charge carriers bind to the protein as the final solvent molecules evaporate. The outcome of these events is largely independent of the initial protein charge and the mode of charge carrier binding. ESI charge states and collision cross sections of the MD structures agree with experimental data. Our results confirm the Rayleigh/charged residue model (CRM). Field emission of excess Na(+) plays an ancillary role by governing the net charge of the shrinking droplet. Models that envision protein ejection from the droplet are not supported. Most nascent CRM ions retain native-like conformations. For unfolded proteins ESI likely proceeds along routes that are different from the native state mechanism explored here.

  15. Surface area generation and droplet size control in solvent extraction systems utilizing high intensity electric fields

    DOEpatents

    Scott, Timothy C.; Wham, Robert M.

    1988-01-01

    A method and system for solvent extraction where droplets are shattered by a high intensity electric field. These shattered droplets form a plurality of smaller droplets which have a greater combined surface area than the original droplet. Dispersion, coalescence and phase separation are accomplished in one vessel through the use of the single pulsing high intensity electric field. Electric field conditions are chosen so that simultaneous dispersion and coalescence are taking place in the emulsion formed in the electric field. The electric field creates a large amount of interfacial surface area for solvent extraction when the droplet is disintegrated and is capable of controlling droplet size and thus droplet stability. These operations take place in the presence of a counter current flow of the continuous phase.

  16. 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.

  17. Droplet formation and lateral migration via solvent shifting in a microfluidic setup

    NASA Astrophysics Data System (ADS)

    Hajian, Ramin; Hardt, Steffen

    2014-11-01

    When a non-solvent is added to a solvent/solute mixture and if the solvent and the non-solvent are miscible, a part of the solute transforms to tiny (i.e. micron-/submicron-sized) droplets when the solvent concentration reduces. This phenomenon, resulting from supersaturation, is termed solvent shifting or Ouzo effect. Here we investigate this process in a co-flow microfluidic device. Thanks to the laminar nature of the flow, the mass transfer is mainly diffusive and can be analyzed employing (semi)analytical models. Using the resulting concentration profiles along with the ternary phase diagram (TPD) we analyze droplet formation and their lateral migration in the channel. The ternary system consists of a binary mixture (0.5wt% divinyle benzene (DVB) + 95.5wt% ethanol) and deionized water (non-solvent). Plotting concentration trajectories in the TPD we show that they hit the binodal curve in a region in which droplets of DVB form via nucleation, as opposed to spinodal decomposition. The lateral migration of droplets is partially attributed to the Marangoni effect induced by concentration gradients. However, the main effect governing droplet migration appears to be the phase-separation front (separating the one-phase and two-phase regions) moving toward the center of the channel.

  18. Electrohydrodynamic migration of charged droplets in an insulating fluid

    NASA Technical Reports Server (NTRS)

    Balasubramaniam, R.; Wilkinson, R. A.

    1988-01-01

    The motion of charged, conducting droplets present in an insulating fluid medium is analyzed under the action of an electric field, in microgravity. Previous analyses of this problem have considered the Maxwell stresses as the only driving force. In the present study, arguments from macroscopic thermodynamics and the molecular theory of surface tension are used to show that the surface tension gradients can be induced due to the variation of the electric potential on the interface. In the limit of Reynolds numbers small compared to unity, the terminal velocity of migration of the droplet is calculated under the combined action of the Maxwell stresses and the surface tension gradients. The results show that there are no surface tension gradients (i.e., no electric potential variation at the interface) in a case that is due to the convection of the surface charges, surface tension gradients do exist and tend to reduce the terminal velocity of the droplet. The shape of the droplet altered by the motion was also calculated, when the deformations from the spherical shape are small.

  19. Isolating Protein Charge State Reduction in Electrospray Droplets Using Femtosecond Laser Vaporization

    NASA Astrophysics Data System (ADS)

    Karki, Santosh; Sistani, Habiballah; Archer, Jieutonne J.; Shi, Fengjian; Levis, Robert J.

    2017-01-01

    Charge state distributions are measured using mass spectrometry for both native and denatured cytochrome c and myoglobin after laser vaporization from the solution state into an electrospray (ES) plume consisting of a series of solution additives differing in gas-phase basicity. The charge distribution depends on both the pH of the protein solution prior to laser vaporization and the gas-phase basicity of the solution additive employed in the ES solvent. Cytochrome c (myoglobin) prepared in solutions with pH of 7.0, 2.6, and 2.3 resulted in the average charge state distribution (Zavg) of 7.0 ± 0.1 (8.2 ± 0.1), 9.7 ± 0.2 (14.5 ± 0.3), and 11.6 ± 0.3 (16.4 ± 0.1), respectively, in ammonium formate ES solvent. The charge distribution shifted from higher charge states to lower charge states when the ES solvent contained amines additives with higher gas-phase basicity. In the case of triethyl ammonium formate, Zavg of cytochrome c (myoglobin) prepared in solutions with pH of 7.0, 2.6, and 2.3 decreased to 4.9 (5.7), 7.4 ± 0.2 (9.6 ± 0.3), and 7.9 ± 0.3 (9.8 ± 0.2), respectively. The detection of a charge state distribution corresponding to folded protein after laser vaporized, acid-denatured protein interacts with the ES solvent containing ammonium formate, ammonium acetate, triethyl ammonium formate, and triethyl ammonium acetate suggests that at least a part of protein population folds within the electrospray droplet on a millisecond timescale.

  20. Isolating Protein Charge State Reduction in Electrospray Droplets Using Femtosecond Laser Vaporization

    NASA Astrophysics Data System (ADS)

    Karki, Santosh; Sistani, Habiballah; Archer, Jieutonne J.; Shi, Fengjian; Levis, Robert J.

    2017-03-01

    Charge state distributions are measured using mass spectrometry for both native and denatured cytochrome c and myoglobin after laser vaporization from the solution state into an electrospray (ES) plume consisting of a series of solution additives differing in gas-phase basicity. The charge distribution depends on both the pH of the protein solution prior to laser vaporization and the gas-phase basicity of the solution additive employed in the ES solvent. Cytochrome c (myoglobin) prepared in solutions with pH of 7.0, 2.6, and 2.3 resulted in the average charge state distribution (Zavg) of 7.0 ± 0.1 (8.2 ± 0.1), 9.7 ± 0.2 (14.5 ± 0.3), and 11.6 ± 0.3 (16.4 ± 0.1), respectively, in ammonium formate ES solvent. The charge distribution shifted from higher charge states to lower charge states when the ES solvent contained amines additives with higher gas-phase basicity. In the case of triethyl ammonium formate, Zavg of cytochrome c (myoglobin) prepared in solutions with pH of 7.0, 2.6, and 2.3 decreased to 4.9 (5.7), 7.4 ± 0.2 (9.6 ± 0.3), and 7.9 ± 0.3 (9.8 ± 0.2), respectively. The detection of a charge state distribution corresponding to folded protein after laser vaporized, acid-denatured protein interacts with the ES solvent containing ammonium formate, ammonium acetate, triethyl ammonium formate, and triethyl ammonium acetate suggests that at least a part of protein population folds within the electrospray droplet on a millisecond timescale.

  1. Orientation of charged clay nanotubes in evaporating droplet meniscus.

    PubMed

    Zhao, Yafei; Cavallaro, Giuseppe; Lvov, Yuri

    2015-02-15

    During drying, an aqueous suspension of strongly charged halloysite clay nanotubes concentrates at the edge of the droplet ("coffee-ring" effect) which provides alignment of the tubes along the liquid-substrate contact line. First, the surface charge of the nanotubes was enhanced by polyanion adsorption inside of the lumen to compensate for the internal positive charges. This increased the magnitude of the ξ-potential of the tubes from -36 to -81 mV and stabilized the colloids. Then, colloidal halloysite was dropped onto the substrate, dried at 65 °C and after a concentration of ∼0.05 mg mL(-1) was reached, the alignment of nanotubes occurred starting from the droplet edges. The process was described with Onsager's theory, in which longer nanorods, which have higher surface charge, give better ordering after a critical concentration is reached. This study indicates a new application of halloysite clay nanotubes in polymeric composites with anisotropic properties, microchannel orientation, and production of coatings with aligned nanotubes.

  2. 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

  3. 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.

  4. Droplet charging regimes for ultrasonic atomization of a liquid electrolyte in an external electric field

    NASA Astrophysics Data System (ADS)

    Forbes, Thomas P.; Degertekin, F. Levent; Fedorov, Andrei G.

    2011-01-01

    Distinct regimes of droplet charging, determined by the dominant charge transport process, are identified for an ultrasonic droplet ejector using electrohydrodynamic computational simulations, a fundamental scale analysis, and experimental measurements. The regimes of droplet charging are determined by the relative magnitudes of the dimensionless Strouhal and electric Reynolds numbers, which are a function of the process (pressure forcing), advection, and charge relaxation time scales for charge transport. Optimal (net maximum) droplet charging has been identified to exist for conditions in which the electric Reynolds number is of the order of the inverse Strouhal number, i.e., the charge relaxation time is on the order of the pressure forcing (droplet formation) time scale. The conditions necessary for optimal droplet charging have been identified as a function of the dimensionless Debye number (i.e., liquid conductivity), external electric field (magnitude and duration), and atomization drive signal (frequency and amplitude). The specific regime of droplet charging also determines the functional relationship between droplet charge and charging electric field strength. The commonly expected linear relationship between droplet charge and external electric field strength is only found when either the inverse of the Strouhal number is less than the electric Reynolds number, i.e., the charge relaxation is slower than both the advection and external pressure forcing, or in the electrostatic limit, i.e., when charge relaxation is much faster than all other processes. The analysis provides a basic understanding of the dominant physics of droplet charging with implications to many important applications, such as electrospray mass spectrometry, ink jet printing, and drop-on-demand manufacturing.

  5. Droplet charging regimes for ultrasonic atomization of a liquid electrolyte in an external electric field

    PubMed Central

    Forbes, Thomas P.; Degertekin, F. Levent; Fedorov, Andrei G.

    2011-01-01

    Distinct regimes of droplet charging, determined by the dominant charge transport process, are identified for an ultrasonic droplet ejector using electrohydrodynamic computational simulations, a fundamental scale analysis, and experimental measurements. The regimes of droplet charging are determined by the relative magnitudes of the dimensionless Strouhal and electric Reynolds numbers, which are a function of the process (pressure forcing), advection, and charge relaxation time scales for charge transport. Optimal (net maximum) droplet charging has been identified to exist for conditions in which the electric Reynolds number is of the order of the inverse Strouhal number, i.e., the charge relaxation time is on the order of the pressure forcing (droplet formation) time scale. The conditions necessary for optimal droplet charging have been identified as a function of the dimensionless Debye number (i.e., liquid conductivity), external electric field (magnitude and duration), and atomization drive signal (frequency and amplitude). The specific regime of droplet charging also determines the functional relationship between droplet charge and charging electric field strength. The commonly expected linear relationship between droplet charge and external electric field strength is only found when either the inverse of the Strouhal number is less than the electric Reynolds number, i.e., the charge relaxation is slower than both the advection and external pressure forcing, or in the electrostatic limit, i.e., when charge relaxation is much faster than all other processes. The analysis provides a basic understanding of the dominant physics of droplet charging with implications to many important applications, such as electrospray mass spectrometry, ink jet printing, and drop-on-demand manufacturing. PMID:21301636

  6. Droplet charging regimes for ultrasonic atomization of a liquid electrolyte in an external electric field.

    PubMed

    Forbes, Thomas P; Degertekin, F Levent; Fedorov, Andrei G

    2011-01-01

    Distinct regimes of droplet charging, determined by the dominant charge transport process, are identified for an ultrasonic droplet ejector using electrohydrodynamic computational simulations, a fundamental scale analysis, and experimental measurements. The regimes of droplet charging are determined by the relative magnitudes of the dimensionless Strouhal and electric Reynolds numbers, which are a function of the process (pressure forcing), advection, and charge relaxation time scales for charge transport. Optimal (net maximum) droplet charging has been identified to exist for conditions in which the electric Reynolds number is of the order of the inverse Strouhal number, i.e., the charge relaxation time is on the order of the pressure forcing (droplet formation) time scale. The conditions necessary for optimal droplet charging have been identified as a function of the dimensionless Debye number (i.e., liquid conductivity), external electric field (magnitude and duration), and atomization drive signal (frequency and amplitude). The specific regime of droplet charging also determines the functional relationship between droplet charge and charging electric field strength. The commonly expected linear relationship between droplet charge and external electric field strength is only found when either the inverse of the Strouhal number is less than the electric Reynolds number, i.e., the charge relaxation is slower than both the advection and external pressure forcing, or in the electrostatic limit, i.e., when charge relaxation is much faster than all other processes. The analysis provides a basic understanding of the dominant physics of droplet charging with implications to many important applications, such as electrospray mass spectrometry, ink jet printing, and drop-on-demand manufacturing.

  7. Solvent exchange module for LC-NMR hyphenation using machine vision-controlled droplet evaporation.

    PubMed

    Schoonen, Jan-Willem; Vulto, Paul; de Roo, Niels; van Duynhoven, John; van der Linden, Heiko; Hankemeier, Thomas

    2013-06-18

    We report the use of pendant droplet evaporation for exchange of eluents for (1)H nuclear magnetic resonance ((1)H NMR) purposes. Analytes are fed and retained in 500 nL droplets, which are concentrated by evaporation and subsequently redissolved in deuterated solvent. Droplet size is monitored by machine vision (MV), and heating rates are adjusted concordingly to maintain a stable droplet volume. Evaporation control is independent of solvent properties, and the setup handles feed rates up to 7 μL min(-1). The interface is capable of exchanging up to 90% of solvent for deuterated solvent, with a good recovery and repeatability for tomato extracts (Solanum lycopersicum). The system was capable of handling both polar and nonpolar analytes in one run. Volatiles such as formate, acetate, and lactate and the thermosensitive compound epigallocatechin gallate were recovered without significant losses. Ethanol and propionate were recovered with significant losses due to the formation of a minimum boiling azeotrope. The current setup is ideally suited for on- and off-line hyphenation of liquid chromatography and NMR, as it is comprehensive, fully automated, and easy to operate.

  8. On the theory of the noncoalescence effect for oppositely charged droplets

    SciTech Connect

    Saranin, V. A.

    2011-05-15

    A theory is proposed and numerical simulation is conducted for oppositely charged mutually approaching droplets of an aqueous electrolytic solution in silicon oil. It is shown that at small distances between droplets, a conductive bridge leveling out the potentials of the droplets may form between them due to electrohydrodynamic instability of the equilibrium surface of one of the droplets. As a result, the droplets start to repel each other and may drift apart without coagulation. The proposed theory is confirmed by the effect of nonconfluent droplets observed in experiments [W.D. Ristenpart, J.C. Bird, A. Belmonte, et al., Nature 461, 377 (2009)].

  9. 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

  10. 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.

  11. Influence of relative humidity and ambient temperature on hydrothermal waves (HTWs) of organic solvent volatile droplets

    NASA Astrophysics Data System (ADS)

    Orejon, Daniel; Kita, Yutaku; Okauchi, Yuya; Fukatani, Yuki; Kohno, Masamichi; Takata, Yasuyuki; Sefiane, Khellil; Kim, Jungho

    2016-11-01

    Droplets of organic solvents undergoing evaporation have been found to display distinctive hydrothermal patterns or HTWs at the liquid-vapor interface. Since the evaporation of mentioned organic solvents in ambient conditions is ubiquitous, in this work we investigate the effect of ambient temperature and relative humidity on the self-generated HTWs by means of infrared thermography. The intensity of the HTWs was found to decrease when lowering the ambient temperature due to a reduction in droplet evaporative cooling. On other hand, the enhancement or suppression of the HTWs was also possible by controlling the relative humidity of the system. Absorption and/or condensation of water vapor onto the evaporating droplet was found to be the main cause for the differences observed on the HTWs retrieved at the liquid-vapor interface. To account for the water adsorbed or condensed we perform in-situ gas chromatography analysis at different droplet lifetimes. Experimental results showed an increase in the amount of water condensed when increasing the relative humidity of the system as expected. In addition, for the same ambient temperature ethanol evaporation was enhanced by high relative humidity. The authors acknowledge the support of WPI-I2CNER.

  12. Redistribution of mobile surface charges of an oil droplet in water in applied electric field.

    PubMed

    Li, Mengqi; Li, Dongqing

    2016-10-01

    Most researches on oil droplets immersed in aqueous solutions assume that the surface charges of oil droplets are, similar to that of solid particles, immobile and distributed uniformly under external electric field. However, the surface charges at the liquid-liquid interface are mobile and will redistribute under external electric field. This paper studies the redistribution of surface charges on an oil droplet under the influence of the external electrical field. Analytical expressions of the local zeta potential on the surface of an oil droplet after the charge redistribution in a uniform electrical field were derived. The effects of the initial zeta potential, droplet radius and strength of applied electric field on the surface charge redistribution were studied. In analogy to the mobile surface charges, the redistribution of Al2O3-passivated aluminum nanoparticles on the oil droplet surface was observed under applied electrical field. Experimental results showed that these nanoparticles moved and accumulated towards one side of the oil droplet under electric field. The redistribution of the nanoparticles is in qualitative agreement with the redistribution model of the mobile surface charges developed in this work. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Charge-transfer complexation between naphthalene diimides and aromatic solvents.

    PubMed

    Kulkarni, Chidambar; Periyasamy, Ganga; Balasubramanian, S; George, Subi J

    2014-07-28

    Naphthalene diimides (NDIs) form emissive ground-state charge-transfer (CT) complexes with various electron rich aromatic solvents like benzene, o-xylene and mesitylene. TD-DFT calculation of the complexes suggests CT interaction and accounts for the observed ground-state changes.

  14. Non-coalescence of oppositely charged droplets in pH-sensitive emulsions

    PubMed Central

    Liu, Tingting; Seiffert, Sebastian; Thiele, Julian; Abate, Adam R.; Weitz, David A.; Richtering, Walter

    2012-01-01

    Like charges stabilize emulsions, whereas opposite charges break emulsions. This is the fundamental principle for many industrial and practical processes. Using micrometer-sized pH-sensitive polymeric hydrogel particles as emulsion stabilizers, we prepare emulsions that consist of oppositely charged droplets, which do not coalesce. We observe noncoalescence of oppositely charged droplets in bulk emulsification as well as in microfluidic devices, where oppositely charged droplets are forced to collide within channel junctions. The results demonstrate that electrostatic interactions between droplets do not determine their stability and reveal the unique pH-dependent properties of emulsions stabilized by soft microgel particles. The noncoalescence can be switched to coalescence by neutralizing the microgels, and the emulsion can be broken on demand. This unusual feature of the microgel-stabilized emulsions offers fascinating opportunities for future applications of these systems. PMID:22203968

  15. Crystallization and reentrant melting of charged colloids in nonpolar solvents.

    PubMed

    Kanai, Toshimitsu; Boon, Niels; Lu, Peter J; Sloutskin, Eli; Schofield, Andrew B; Smallenburg, Frank; van Roij, René; Dijkstra, Marjolein; Weitz, David A

    2015-03-01

    We explore the crystallization of charged colloidal particles in a nonpolar solvent mixture. We simultaneously charge the particles and add counterions to the solution with aerosol-OT (AOT) reverse micelles. At low AOT concentrations, the charged particles crystallize into body-centered-cubic (bcc) or face-centered-cubic (fcc) Wigner crystals; at high AOT concentrations, the increased screening drives a thus far unobserved reentrant melting transition. We observe an unexpected scaling of the data with particle size, and account for all behavior with a model that quantitatively predicts both the reentrant melting and the data collapse.

  16. Electrostatic interactions in charged nanoslits within an explicit solvent theory.

    PubMed

    Buyukdagli, Sahin

    2015-11-18

    Within a dipolar Poisson-Boltzmann theory including electrostatic correlations, we consider the effect of explicit solvent structure on solvent and ion partition confined to charged nanopores. We develop a relaxation scheme for the solution of this highly non-linear integro-differential equation for the electrostatic potential. The scheme is an extension of the approach previously introduced for simple planes (Buyukdagli and Blossey 2014 J. Chem. Phys. 140 234903) to nanoslit geometry. We show that the reduced dielectric response of solvent molecules at the membrane walls gives rise to an electric field significantly stronger than the field of the classical Poisson-Boltzmann equation. This peculiarity associated with non-local electrostatic interactions results in turn in an interfacial counterion adsorption layer absent in continuum theories. The observation of this enhanced counterion affinity in the very close vicinity of the interface may have important impacts on nanofluidic transport through charged nanopores. Our results indicate the quantitative inaccuracy of solvent implicit nanofiltration theories in predicting the ionic selectivity of membrane nanopores.

  17. Electrostatic interactions in charged nanoslits within an explicit solvent theory

    NASA Astrophysics Data System (ADS)

    Buyukdagli, Sahin

    2015-11-01

    Within a dipolar Poisson-Boltzmann theory including electrostatic correlations, we consider the effect of explicit solvent structure on solvent and ion partition confined to charged nanopores. We develop a relaxation scheme for the solution of this highly non-linear integro-differential equation for the electrostatic potential. The scheme is an extension of the approach previously introduced for simple planes (Buyukdagli and Blossey 2014 J. Chem. Phys. 140 234903) to nanoslit geometry. We show that the reduced dielectric response of solvent molecules at the membrane walls gives rise to an electric field significantly stronger than the field of the classical Poisson-Boltzmann equation. This peculiarity associated with non-local electrostatic interactions results in turn in an interfacial counterion adsorption layer absent in continuum theories. The observation of this enhanced counterion affinity in the very close vicinity of the interface may have important impacts on nanofluidic transport through charged nanopores. Our results indicate the quantitative inaccuracy of solvent implicit nanofiltration theories in predicting the ionic selectivity of membrane nanopores.

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

    SciTech Connect

    Huo, Yuanping Wang, Junfeng Zuo, Ziwen; Fan, Yajun

    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 different 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.

  19. Exact solutions for the static dewetting of two-dimensional charged conducting droplets on a substrate

    NASA Astrophysics Data System (ADS)

    Crowdy, Darren

    2015-06-01

    A one parameter family of analytical solutions for the equilibrium shapes of two-dimensional charged conducting droplets on a substrate with 90° contact angle is presented. The solutions exhibit the tendency to dewet at the droplet centre as the electrostatic stress increases. Such electrostatic deformations are believed to underlie the recently observed stick-slip dynamics of nanodroplets on substrates. Our theoretical results complement a number of other recent analytical and numerical studies of this phenomenon.

  20. 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.

  1. Apparatus for Suspension of Charged Particles and Droplets

    ERIC Educational Resources Information Center

    Berg, T. G. Owe

    1969-01-01

    Describes an apparatus designed to study the properties of charged particles suspended in an electric field. The apparatus consists of a suspension chamber, an optical system and power supplies and controls. Experiments conducted include determination of particle size, charge-to-mass ratio and particle collisions and exchange. (LC)

  2. Apparatus for Suspension of Charged Particles and Droplets

    ERIC Educational Resources Information Center

    Berg, T. G. Owe

    1969-01-01

    Describes an apparatus designed to study the properties of charged particles suspended in an electric field. The apparatus consists of a suspension chamber, an optical system and power supplies and controls. Experiments conducted include determination of particle size, charge-to-mass ratio and particle collisions and exchange. (LC)

  3. 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

  4. Dynamic corona characteristics of water droplets on charged conductor surface

    NASA Astrophysics Data System (ADS)

    Xu, Pengfei; Zhang, Bo; Wang, Zezhong; Chen, Shuiming; He, Jinliang

    2017-03-01

    The formation of the Taylor cone of a water droplet on the surface of the conductor in a line-ground electrode system is captured using a high-speed camera, while the corona current is synchronously measured using a current measurement system. Repeated Taylor cone deformation is observed, yielding regular groupings of corona current pulses. The underlying mechanism of this deformation is studied and the correlation between corona discharge characteristics and cone deformation is investigated. Depending on the applied voltage and rate of water supply, the Taylor cone may be stable or unstable and has a significant influence on the characteristics of the corona currents. If the rate of water supply is large enough, the Taylor cone tends to be unstable and generates corona-current pulses of numerous induced current pulses with low amplitudes. In consequence, this difference suggests that large rainfall results in simultaneously lower radio interference and higher corona loss.

  5. Producing highly charged ions without solvent using laserspray ionization: a total solvent-free analysis approach at atmospheric pressure.

    PubMed

    Wang, Beixi; Lietz, Christopher B; Inutan, Ellen D; Leach, Samantha M; Trimpin, Sarah

    2011-06-01

    First examples of highly charged ions in mass spectrometry (MS) produced from the solid state without using solvent during either sample preparation or mass measurement are reported. Matrix material, matrix/analyte homogenization time and frequency, atmospheric pressure (AP) to vacuum inlet temperature, and mass analyzer ion trap conditions are factors that influence the abundance of the highly charged ions created by laserspray ionization (LSI). LSI, like matrix-assisted laser desorption/ionization (MALDI), uses laser ablation of a matrix/analyte mixture from a surface to produce ions. Preparing the matrix/analyte sample without the use of solvent provides the ability to perform total solvent-free analysis (TSA) consisting of solvent-free ionization and solvent-free gas-phase separation using ion mobility spectrometry (IMS) MS. Peptides and small proteins such as non-β-amyloid components of Alzheimer's disease and bovine insulin are examples in which LSI and TSA were combined to produce multiply charged ions, similar to electrospray ionization, but without the use of solvent. Advantages using solvent-free LSI and IMS-MS include simplicity, rapid data acquisition, reduction of sample complexity, and the potential for an enhanced effective dynamic range. This is achieved by more inclusive ionization and improved separation of mixture components as a result of multiple charging.

  6. Estimation of droplet charge forming out of an electrified ligament in the presence of a uniform electric field

    NASA Astrophysics Data System (ADS)

    Osman, H.; Castle, G. S. P.; Adamiak, K.; Fan, H. T.; Simmer, J.

    2015-10-01

    The charge on a liquid droplet is a critical parameter that needs to be determined to accurately predict the behaviour of the droplet in many electrostatic applications, for example, electrostatic painting and ink-jet printing. The charge depends on many factors, such as the liquid conductivity, droplet and ligament radii, ligament length, droplet shape, electric field intensity, space charge, the presence of adjacent ligaments and previously formed droplets. In this paper, a 2D axisymmetric model is presented which can be used to predict the electric charge on a conductive spherical droplet ejected from a single ligament directly supplied with high voltage. It was found that the droplet charging levels for the case of isolated electrified ligaments are as much as 60 times higher than that in the case of ligaments connected to a planar high voltage electrode. It is suggested that practical atomization systems lie somewhere between these two extremes and that a better model was achieved by developing a 3D approximation of a linear array of ligaments connected to an electrode having variable width. The effect on droplet charge and its radius was estimated for several cases of different boundary conditions.

  7. Effects of Solvent on the Maximum Charge State and Charge State Distribution of Protein Ions Produced by Electrospray Ionization

    PubMed Central

    Iavarone, Anthony T.; Jurchen, John C.; Williams, Evan R.

    2005-01-01

    The effects of solvent composition on both the maximum charge states and charge state distributions of analyte ions formed by electrospray ionization were investigated using a quadrupole mass spectrometer. The charge state distributions of cytochrome c and myoglobin, formed from 47%/50%/3% water/solvent/acetic acid solutions, shift to lower charge (higher m/z) when the 50% solvent fraction is changed from water to methanol, to acetonitrile, to isopropanol. This is also the order of increasing gas-phase basicities of these solvents, although other physical properties of these solvents may also play a role. The effect is relatively small for these solvents, possibly due to their limited concentration inside the electrospray interface. In contrast, the addition of even small amounts of diethylamine (<0.4%) results in dramatic shifts to lower charge, presumably due to preferential proton transfer from the higher charge state ions to diethylamine. These results clearly show that the maximum charge states and charge state distributions of ions formed by electrospray ionization are influenced by solvents that are more volatile than water. Addition of even small amounts of two solvents that are less volatile than water, ethylene glycol and 2-methoxyethanol, also results in preferential deprotonation of higher charge state ions of small peptides, but these solvents actually produce an enhancement in the higher charge state ions for both cytochrome c and myoglobin. For instruments that have capabilities that improve with lower m/z, this effect could be taken advantage of to improve the performance of an analysis. PMID:11073261

  8. Visualisation of charge dynamics when water droplets move off a hydrophobic surface

    NASA Astrophysics Data System (ADS)

    Helseth, L. E.; Wen, H. Z.

    2017-09-01

    The Kelvin water drop generator is often used for educational purposes to visualise how charge is transferred when water drops separate from a solid. Here, we discuss an alternative and simpler setup, which allows one to visualise the charge transfer that occurs when water drops move off a hydrophobic polymer. One can visualise the charge transfer directly as light pulses from a light emitting diode, or monitor the current pulses generated by the water drops. Further investigation of the current pulses provides information about how single water droplets or fluctuating streams move down the incline.

  9. Electrohydrodynamics of Charge Separation in Droplet-Based Ion Sources with Time-Varying Electrical and Mechanical Actuation

    PubMed Central

    Forbes, Thomas P.; Degertekin, F. Levent; Fedorov, Andrei G.

    2010-01-01

    Charge transport and separation in mechanically-driven, droplet-based ion sources are investigated using computational analysis and supporting experiments. A first-principles model of electrohydrodynamics (EHD) and charge migration is formulated and implemented using FLUENT CFD software for jet/droplet formation. For validation, classical experiments of electrospraying from a thin capillary are simulated, specifically, the transient EHD cone-jet formation of a fluid with finite electrical conductivity, and the Taylor cone formation in a perfectly electrically-conducting fluid. The model is also used to investigate the microscopic physics of droplet charging in mechanically-driven droplet-based ion sources, such as AMUSE (Array of Micromachined UltraSonic Electrospray). Here, AMUSE is subject to DC and AC electric fields of varying amplitude and phase, with respect to a time-varying mechanical force driving the droplet formation. For the DC-charging case, a linear relationship is demonstrated between the charge carried by each droplet and an applied electric field magnitude, in agreement with previously reported experiments. For the AC-charging case, a judiciously-chosen phase-shift in the time-varying mechanical (driving ejection) and electrical (driving charge transport) signals allows for a significantly increased amount of charge, of desired polarity, to be pumped into a droplet upon ejection. Complementary experimental measurements of electrospray electrical current and charge-per-droplet, produced by the AMUSE ion source, are performed and support theoretical predictions for both DC and AC-charging cases. The theoretical model and simulation tools provide a versatile and general analytical framework for fundamental investigations of coupled electrohydrodynamics and charge transport. The model also allows for the exploration of different configurations and operating modes to optimize charge separation in atmospheric pressure electrohydrodynamic ion sources

  10. Promotion of alpha-cyano-4-hydroxycinnamic acid and peptide cocrystallization within levitated droplets with net charge.

    PubMed

    Bogan, Michael J; Bakhoum, Samuel F W; Agnes, George R

    2005-02-01

    Many reactions occur as a result of charge imbalance within or between reactive species in reaction vessels that have zero net charge. Here, chemical processes taking place within reaction vessels having net excess charge were studied. For mass spectroscopists, a familiar example of vessels that defy electroneutrality are the charged droplets produced by an electrospray ion source. Evidence is presented that control of the magnitude of the net charge contained in a reaction vessel, in this case a levitated droplet, can be used to promote nucleation and crystal growth of a mixture of an organic acid, alpha-cyano-4-hydroxycinnamic acid (CHCA), with one or more peptides. This phenomenon was first observed during our ongoing development of wall-less sample preparation (WaSP), electrodynamic charged droplet processing methodology capable of creating micrometer-sized sample spots for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) from subnanoliter volumes of sample material. Peptide ion signal-to-noise (S/N) ratios obtained by MALDI-TOF-MS from sample spots created from droplets that had high relative magnitude of net charge were consistently greater than those detected from sample spots created from droplets that had lower net charge. To study this unexpected phenomenon further, WaSP methodology was developed to process different mass-to-charge (m/z) droplets levitated in an electrodynamic balance (EDB), facilitating their deposition onto different positions of a target to create arrays of droplet residues ordered from highest to lowest m/z. This capability allowed simultaneous levitation with subsequent separation of a population of droplets created from a single starting solution, but the droplets had varied magnitudes of net charge. After the droplets were ejected from the EDB and collected on a glass slide or MALDI plate, the solids contained in the deposited droplets were characterized using microscopy and MALDI

  11. Real-time observation of the charge transfer to solvent dynamics.

    PubMed

    Messina, Fabrizio; Bräm, Olivier; Cannizzo, Andrea; Chergui, Majed

    2013-01-01

    Intermolecular electron-transfer reactions have a crucial role in biology, solution chemistry and electrochemistry. The first step of such reactions is the expulsion of the electron to the solvent, whose mechanism is determined by the structure and dynamical response of the latter. Here we visualize the electron transfer to water using ultrafast fluorescence spectroscopy with polychromatic detection from the ultraviolet to the visible region, upon photo-excitation of the so-called charge transfer to solvent states of aqueous iodide. The initial emission is short lived (~60 fs) and it relaxes to a broad distribution of lower-energy charge transfer to solvent states upon rearrangement of the solvent cage. This distribution reflects the inhomogeneous character of the solvent cage around iodide. Electron ejection occurs from the relaxed charge transfer to solvent states with lifetimes of 100-400 fs that increase with decreasing emission energy.

  12. Charge tuning in [111] grown GaAs droplet quantum dots

    SciTech Connect

    Bouet, L.; Vidal, M.; Marie, X.; Amand, T.; Wang, G.; Urbaszek, B.; Mano, T.; Ha, N.; Kuroda, T.; Sakoda, K.; Durnev, M. V.; Glazov, M. M.; Ivchenko, E. L.

    2014-08-25

    We demonstrate charge tuning in strain free GaAs/AlGaAs quantum dots (QDs) grown by droplet epitaxy on a GaAs(111)A substrate. Application of a bias voltage allows the controlled charging of the QDs from −3|e| to +2|e|. The resulting changes in QD emission energy and exciton fine-structure are recorded in micro-photoluminescence experiments at T = 4 K. We uncover the existence of excited valence and conduction states, in addition to the s-shell-like ground state. We record a second series of emission lines about 25 meV above the charged exciton emission coming from excited charged excitons. For these excited interband transitions, a negative diamagnetic shift of large amplitude is uncovered in longitudinal magnetic fields.

  13. 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.

  14. X-ray photoelectron spectroscopy analysis of organic materials etched by charged water droplet impact

    SciTech Connect

    Sakai, Yuji; Iijima, Yoshitoki; Takaishi, Riou; Asakawa, Daiki; Hiraoka, Kenzo

    2009-07-15

    Electrospray droplet impact (EDI) has been developed for matrix-free secondary ion mass spectrometry for surface analysis. When a target is etched by EDI, the physical etching on the target is suppressed to minimal, i.e., the occurrence of shallow surface etching. A novel approach to shallow surface etching of polystyrene (PS) by EDI was investigated. The charged water droplets were irradiated to a bulk and a spin coated PS. After irradiation, these samples were analyzed by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy. It was found that XPS spectra for PS were independent on the irradiation time by EDI. This indicates that EDI is a unique technique for the surface etching of the organic materials without leaving any damage on the etched surface.

  15. Role of hydrophobicity and solvent-mediated charge-charge interactions in stabilizing alpha-helices.

    PubMed Central

    Vila, J A; Ripoll, D R; Villegas, M E; Vorobjev, Y N; Scheraga, H A

    1998-01-01

    A theoretical study to identify the conformational preferences of lysine-based oligopeptides has been carried out. The solvation free energy and free energy of ionization of the oligopeptides have been calculated by using a fast multigrid boundary element method that considers the coupling between the conformation of the molecule and the ionization equilibria explicitly, at a given pH value. It has been found experimentally that isolated alanine and lysine residues have somewhat small intrinsic helix-forming tendencies; however, results from these simulations indicate that conformations containing right-handed alpha-helical turns are energetically favorable at low values of pH for lysine-based oligopeptides. Also, unusual patterns of interactions among lysine side chains with large hydrophobic contacts and close proximity (5-6 A) between charged NH3+ groups are observed. Similar arrangements of charged groups have been seen for lysine and arginine residues in experimentally determined structures of proteins available from the Protein Data Bank. The lowest-free-energy conformation of the sequence Ac-(LYS)6-NMe from these simulations showed large pKalpha shifts for some of the NH3+ groups of the lysine residues. Such large effects are not observed in the lowest-energy conformations of oligopeptide sequences with two, three, or four lysine residues. Calculations on the sequence Ac-LYS-(ALA)4-LYS-NMe also reveal low-energy alpha-helical conformations with interactions of one of the LYS side chains with the helix backbone in an arrangement quite similar to the one described recently by (Proc. Natl. Acad. Sci. U.S.A. 93:4025-4029). The results of this study provide a sound basis with which to discuss the nature of the interactions, such as hydrophobicity, charge-charge interaction, and solvent polarization effects, that stabilize right-handed alpha-helical conformations. PMID:9826588

  16. Fission of multiply charged alkali clusters in helium droplets - approaching the Rayleigh limit.

    PubMed

    Renzler, Michael; Harnisch, Martina; Daxner, Matthias; Kranabetter, Lorenz; Kuhn, Martin; Scheier, Paul; Echt, Olof

    2016-04-21

    Electron ionization of helium droplets doped with sodium, potassium or cesium results in doubly and, for cesium, triply charged cluster ions. The smallest observable doubly charged clusters are Na9(2+), K11(2+), and Cs9(2+); they are a factor two to three smaller than reported previously. The size of sodium and potassium dications approaches the Rayleigh limit nRay for which the fission barrier is calculated to vanish, i.e. their fissilities are close to 1. Cesium dications are even smaller than nRay, implying that their fissilities have been significantly overestimated. Triply charged cesium clusters as small as Cs19(3+) are observed; they are a factor 2.6 smaller than previously reported. Mechanisms that may be responsible for enhanced formation of clusters with high fissilities are discussed.

  17. 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.

  18. Levitation dynamics of a collection of charged droplets in an electrodynamic balance

    NASA Astrophysics Data System (ADS)

    Singh, Mohit; Mayya, Y. S.; Gaware, Jitendra; Thaokar, Rochish M.

    2017-02-01

    The study explores the stable levitation and self-organization of charged multi-drop assemblies in a large sized quadrupole trap both experimentally and through numerical simulations. The trap is benchmarked by comparing single drop levitation experiments with numerical simulations. Important observation and findings of the study are: (i) long time stabilization and formation of patterns of droplet collections over a range of operating parameters (ii) Numerical prediction of polygonal patterns for few drop (2 to 8) systems and lattice structures for many drop (>10) systems, (iii) Numerical prediction of Non-dependence of the inter-drop spacing on droplet charge for similarly charged drops, consistent with earlier analytical formulations [Aardahl et al., J. Aerosol Sci. 28, 1491-1505 (1997)], (iv) numerical observation of two drops oscillations with a secular frequency distinctly higher than the single drop Dehmelt frequency (v) Simulations of a systematic transition from disordered to coulombic crystals with mean size increasing with the number of levitated drops (N) as ˜N0.29. The experimental observations on different patterns and lattice spacings are closely reproduced by simulations.

  19. Solvent-dependent intramolecular charge transfer delocalization/localization in multibranched push-pull chromophores.

    PubMed

    Li, Yang; Zhou, Meng; Niu, Yingli; Guo, Qianjin; Xia, Andong

    2015-07-21

    The effect of the solvent polarity on excitation delocalization/localization in multibranched push-pull chromophores has been thoroughly explored by combining steady state absorption and fluorescence, as well as femtosecond transient spectral measurements. We found that the excited-state relaxations of the push-pull chromophores are highly dependent on both solvent polarity and the polar degree of the excited intramolecular charge transfer states. The symmetry of multibranched chromophores is preserved in less polar solvents, leading to excitation delocalization over all of the branches because of the negligible solvent reaction field. In contrast, symmetry is broken for multibranched chromophores in more polar solvents because of intense solvent reaction field, and the excitation is consequently localized on one of the dipolar molecular branches. The results provide a fundamental understanding of solvent-dependent excitation delocalization/localization properties of the multibranched chromophores for the potential applications in nonlinear optics and energy-harvesting applications.

  20. A model for the prediction of droplet size in Pickering emulsions stabilized by oppositely charged particles.

    PubMed

    Nallamilli, Trivikram; Mani, Ethayaraja; Basavaraj, Madivala G

    2014-08-12

    Colloidal particles irreversibly adsorb at fluid-fluid interfaces stabilizing what are commonly called "Pickering" emulsions and foams. A simple geometrical model, the limited coalescence model, was earlier proposed to estimate droplet sizes in emulsions. This model assumes that all of the particles are effective in stabilization. The model predicts that the average emulsion drop size scales inversely with the total number of particles, confirmed qualitatively with experimental data on Pickering emulsions. In recent years, there has been an increasing interest in synthesizing emulsions with oppositely charged particles (OCPs). In our experimental study, we observed that the drop size varies nonmonotonically with the number ratio of oppositely charged colloids, even when a fixed total number concentration of colloids is used, showing a minimum. We develop a mathematical model to predict this dependence of drop size on number ratio in such a mixed particle system. The proposed model is based on the hypothesis that oppositely charged colloids form stable clusters due to the strong electrostatic attraction between them and that these clusters are the effective stabilizing agents. The proposed model is a two-parameter model, parameters being the ratio of effective charge of OCPs (denoted as k) and the size of the aggregate containing X particles formed due to aggregation of OCPs. Because the size of aggregates formed during emulsification is not directly measurable, we use suitable values of parameters k and X to best match the experimental observations. The model predictions are in qualitative agreement with experimentally observed nonmonotonic variation of droplet sizes. Using experiments and theory, we present a physical insight into the formation of OCP stabilized Pickering emulsions. Our model upgrades the existing Wiley's limited coalescence model as applied to emulsions containing a binary mixture of oppositely charged particles.

  1. Droplet size and efficacy of an adulticide-larvicide ultralow-volume formulation on Aedes aegypti using different solvents and spray application methods.

    PubMed

    Harburguer, Laura; Seccacini, Emilia; Licastro, Susana; Zerba, Eduardo; Masuh, Héctor

    2012-01-01

    When cases of dengue are reported or the density of adult Aedes aegypti (L.) becomes too high, ultralow-volume (ULV) application of insecticides is the recommended control method. The droplet size of an aerosol insecticide influences its efficiency in killing adult mosquitoes. Many studies have been carried out to determine the optimum droplet size that maximises vector control efforts, but only a few have determined droplet-size spectra for specific equipment using different solvents and comparing thermal and non-thermal aerosols. The present study showed that the droplet size for a water-based adulticide-larvicide formulation was larger than for the same formulation diluted in gasoil or biodiesel. No significant differences in adult mortality were observed between sprayers and solvents, but efficacy decreased with distance from the sprayer nozzle. Adult emergence inhibition was more than 90% when using water as a solvent for both thermal and cold foggers, and the efficacy did not decrease with distance from the sprayer nozzle. On the other hand, oil-based solvents became less effective with distance. The use of water as a solvent with both thermal and cold foggers improves the efficacy of the studied formulation containing permethrin as adulticide and pyriproxyfen as larvicide in scaled-up assays. Moreover, it reduces the environmental impact and costs of spraying by comparison with formulations using oil solvents. Copyright © 2011 Society of Chemical Industry.

  2. Molecular dynamics study of self-agglomeration of charged fullerenes in solvents.

    PubMed

    Banerjee, Soumik

    2013-01-28

    The agglomeration of fullerenes in solvents is an important phenomenon that is relevant to controlled synthesis of fullerene-based nanowires as well as fullerene-based composites. The molecular aggregation in solvents depends on the atomistic interactions of fullerene with the solvent and is made complicated by the fact that fullerenes accrue negative surface charges when present in solvents such as water. In the present work, we simulated fullerenes of varying size and shape (C60, C180, C240, and C540) with and without surface charges in polar protic (water), polar aprotic (acetone), and nonpolar (toluene) solvents using molecular dynamics method. Our results demonstrate that uncharged fullerenes form agglomerates in polar solvents such as water and acetone and remain relatively dispersed in nonpolar toluene. The presence of surface charge significantly reduces agglomerate size in water and acetone. Additionally, the relative influence of surface charge on fullerene agglomeration depends on the size and geometry of the fullerene with larger fullerenes forming relatively smaller agglomerates. We evaluated the diffusion coefficients of solvent molecules within the solvation shell of fullerenes and observed that they are much lower than the bulk solvent and are strongly associated with the fullerenes as seen in the corresponding radial distribution functions. To correlate agglomerate size with the binding energy between fullerenes, we evaluated the potential of mean force between fullerenes in each solvent. Consistent with the solubility of fullerenes, binding energy between fullerenes is the greatest in water followed by acetone and toluene. The presence of charge decreases the binding energy of fullerenes in water and thus results in dispersed fullerenes.

  3. Time-resolved measurements with single droplet introduction to investigate space-charge effects in plasma mass spectrometry.

    PubMed

    Stewart, I I; Olesik, J W

    1999-02-01

    An investigation of the space-charge induced effects of high concentrations of Pb+ matrix ions on Li+ analyte ions in inductively coupled plasma mass spectrometry (ICP-MS) is presented using a vertically oriented mass spectrometer with single droplet introduction. Greater reproducibility and stability in droplet-to-droplet sample introduction using the monodisperse microparticulate injector (MDMI) was achieved with the vertical orientation. Typical variation (%RSD) in the droplet-to-droplet arrival times, and mass spectrometry peak analytical areas are better than 5%. With this precision, a more quantitative description of the space-charge effect on a single cloud of ions is obtained. Both radial and axial space-charge effects were found to occur in the ion beam. Radial effects result in a loss in intensity because of poor transmission or collisions at surfaces within the mass spectrometer. Axial effects modify the kinetic energy distribution of background ion beam components (e.g., 16O+ and 40Ar+) and sampled ion cloud constituents (e.g., 7Li+). However, axial effects do not appear to generate significant broadening of sampled ion clouds within the mass spectrometer. At the point of charge separation and high ion-beam charge density, the ion cloud maxima for Li and Pb are not coincident. This is because of mass dependent diffusion in the ICP as the ion clouds approach the sampling orifice. Space-charge induced ion loss occurs predominantly at a localized region after the Li+ sampled cloud peak maximum. When the Pb concentration in the sample is sufficiently high the 7Li+ sampled signal has a bimodal peak shape. The existence of the dip and its relative location in the bimodal 7Li+ sampled signal suggests that space-charge effects are localized to the region of high charge density occurring just after charge separation.

  4. Searching for solvent cavities via electron photodetachment: The ultrafast charge-transfer-to-solvent dynamics of sodide in a series of ether solvents

    SciTech Connect

    Larsen, Molly C.; Schwartz, Benjamin J.

    2009-10-21

    It was recently predicted by simulations and confirmed by neutron diffraction experiments that the structure of liquid tetrahydrofuran (THF) contains cavities. The cavities can be quite large and have a net positive electrostatic potential, so they can serve as pre-existing traps for excess electrons created via photodetachment from various solutes. In this paper, we use electron photodetachment via charge-transfer-to-solvent (CTTS) excitation of sodide (Na{sup -}) to probe for the presence of pre-existing cavities in a series of ether solvents: THF, diethyl ether, 1,2-dimethoxyethane (DME), and diglyme (DG). We find that electrons photodetached from sodide appear after a time delay with their equilibrium spectrum in all of these solvents, suggesting that the entire series of ethers contains pre-existing solvent cavities. We then use the variation in electron recombination dynamics with CTTS excitation wavelength to probe the nature of the cavities in the different ethers. We find that the cavities that form the deepest electron traps turn on at about the same energy in all four ether solvents investigated, but that the density of cavities is lower in DG and DME than in THF. We also examine the dynamics of the neutral sodium species that remains following CTTS photodetachment of an electron from sodide. We find that the reaction of the initially created gas-phase-like Na atom to form a (Na{sup +},e{sup -}) tight-contact pair occurs at essentially the same rate in all four ether solvents, indicating that only local solvent motions and not bulk solvent rearrangements are what is responsible for driving the partial ejection of the remaining Na valence electron.

  5. Searching for solvent cavities via electron photodetachment: the ultrafast charge-transfer-to-solvent dynamics of sodide in a series of ether solvents.

    PubMed

    Larsen, Molly C; Schwartz, Benjamin J

    2009-10-21

    It was recently predicted by simulations and confirmed by neutron diffraction experiments that the structure of liquid tetrahydrofuran (THF) contains cavities. The cavities can be quite large and have a net positive electrostatic potential, so they can serve as pre-existing traps for excess electrons created via photodetachment from various solutes. In this paper, we use electron photodetachment via charge-transfer-to-solvent (CTTS) excitation of sodide (Na(-)) to probe for the presence of pre-existing cavities in a series of ether solvents: THF, diethyl ether, 1,2-dimethoxyethane (DME), and diglyme (DG). We find that electrons photodetached from sodide appear after a time delay with their equilibrium spectrum in all of these solvents, suggesting that the entire series of ethers contains pre-existing solvent cavities. We then use the variation in electron recombination dynamics with CTTS excitation wavelength to probe the nature of the cavities in the different ethers. We find that the cavities that form the deepest electron traps turn on at about the same energy in all four ether solvents investigated, but that the density of cavities is lower in DG and DME than in THF. We also examine the dynamics of the neutral sodium species that remains following CTTS photodetachment of an electron from sodide. We find that the reaction of the initially created gas-phase-like Na atom to form a (Na(+),e(-)) tight-contact pair occurs at essentially the same rate in all four ether solvents, indicating that only local solvent motions and not bulk solvent rearrangements are what is responsible for driving the partial ejection of the remaining Na valence electron.

  6. Solvent based hydrogen bonding: impact on poly(3-hexylthiophene) nanoscale morphology and charge transport characteristics.

    PubMed

    Chang, Mincheol; Choi, Dalsu; Fu, Boyi; Reichmanis, Elsa

    2013-06-25

    We demonstrate that supramolecular assembly and subsequent enhancement of charge transport characteristics of conjugated polymers can be facilitated simply by adding small amounts of a more volatile poor solvent, which can hydrogen bond with the majority solvent. Addition of up to 2 vol % acetone to a precursor solution of poly(3-hexylthiophene) (P3HT) in chloroform leads to approximately a 4-fold increase in P3HT field-effect mobility. The improvement is associated with hydrogen bonding interactions between acetone and chloroform which decrease the evaporation rate of the mixed solvent. P3HT is less soluble in the binary solvent than in the more readily vaporized chloroform component, and this characteristic enables the supramolecular assembly of P3HT chains at the nanoscale. Two-dimensional molecular ordering of the polymer film was controlled by varying the quantity of poor solvent added to the precursor solution, and the correlation between field-effect mobility and molecular ordering was investigated. Hansen solubility parameters were used to systematically understand how the solvent mixture enhances the alignment and assembly of polymer chains and influences subsequent thin film properties. The value of the relative energy difference (RED) of the solvent with respect to P3HT increased from less than 1 to more than 1 during film formation, which indicates that the solvent characteristics are initially those of a good solvent but transform into those of a poor dissolution medium. A mechanistic illustration of the molecular ordering process during film formation is postulated.

  7. Incorporating the excluded solvent volume and surface charges for computing solvation free energy.

    PubMed

    Yang, Pei-Kun

    2014-01-05

    Gauss's law or Poisson's equation is conventionally used to calculate solvation free energy. However, the near-solute dielectric polarization from Gauss's law or Poisson's equation differs from that obtained from molecular dynamics (MD) simulations. To mimic the near-solute dielectric polarization from MD simulations, the first-shell water was treated as two layers of surface charges, the densities of which are proportional to the electric field at the solvent molecule that is modeled as a hard sphere. The intermediate water was treated as a bulk solvent. An equation describing the solvation free energy of ions using this solvent scheme was derived using the TIP3P water model.

  8. Electric discharges produced by clouds of charged water droplets in the presence of moving conducting object

    NASA Astrophysics Data System (ADS)

    Kostinskiy, Alexander Y.; Syssoev, Vladimir S.; Mareev, Eugene A.; Rakov, Vladimir A.; Andreev, Mikhail G.; Bogatov, Nikolai A.; Makal'sky, Leonid M.; Sukharevsky, Dmitry I.; Aleshchenko, Alexander S.; Kuznetsov, Vladimir E.; Shatalina, Maria V.

    2015-12-01

    The possibility of initiation of electric discharges by a crossbow bolt (projectile) moving in the electric field of a cloud of negatively charged water droplets has been demonstrated for the first time. Over one hundred of discharges have been produced. For each event, a high-speed video camera recorded the images of upward positive leaders developing from both the nearby grounded sphere and the projectile, followed by the return-stroke-like process. Corresponding currents were measured and integrated photos of the events were obtained. The results can help to improve our understanding of lightning initiation by airborne vehicles and by a vertical conductor rapidly extended below the thundercloud in order to trigger lightning with the rocket-and-wire technique.

  9. Energetics of charge transfer reactions in solvents of dipolar and higher order multipolar character. II. Results

    NASA Astrophysics Data System (ADS)

    Perng, Baw-Ching; Newton, Marshall D.; Raineri, Fernando O.; Friedman, Harold L.

    1996-05-01

    We apply the theories developed in the preceding paper (paper I) to calculate various energy quantities of charge transfer (CT) reactions in nine solvents that cover a wide range of polarity, and for which interaction site models (ISM's) may be found in the literature. Besides the two surrogate Hamiltonian theories developed in paper I, the renormalized site-density theory (RST) and the renormalized dielectric theory (RDT), we also investigate a simple harmonic approximation (HXA) for the diabatic free energy profiles, whose characteristic parameters are calculated taking specific advantage of the expression given by the extended reference interaction site method (XRISM) for the free energy of solvation. For each CT process we analyze (a) the solvent reorganization energy λ, (b) the shift of the absorption transition energy due to the solvatochromic effect, and (c) the solvent contribution to the free energy change ΔA. In addition, for a few selected examples, we also report the detailed diabatic free energy profiles. The calculations reported rely on solute-solvent and solvent-solvent pair correlation functions obtained with the XRISM integral equation method applied to nonpolarizable (with fixed mean partial charges) ISM representations of the solute and solvent molecules. To rectify the omission of the solvent electronic degrees of freedom, we correct the dielectric part of the solvent reorganization energy with an additive term designed to compensate for the use of fixed charge ISM models. Contact with theories in which the solvent is represented as a dielectric continuum medium (with or without spatial dispersion) and the solute as a set of charges inside spherical cavities carved out of the dielectric is made straightforwardly within the RDT theory by considering a particularly simple form of the solute-solvent RISM site-site direct correlation functions. Using simple ISM models for several solute species, including Reichardt's betaine-30 dye and a

  10. The effect of the charge density of microemulsion droplets on the bending elasticity of their amphiphilic film

    NASA Astrophysics Data System (ADS)

    Farago, B.; Gradzielski, M.

    2001-06-01

    Oil-in-water (O/W) microemulsion droplets have been investigated with respect to the effect of the electric charge density on the bending elasticity of the amphiphilic film. For this an originally uncharged microemulsion system became charged by the substitution of the nonionic by an ionic surfactant (up to 5 mol %). The sum of the bending constants, 2κ+κ¯, has been determined from the polydispersity index p of the droplets and alternatively from the macroscopic interfacial tension γ together with the maximum particle radius Rm. p and Rm were measured by means of small-angle neutron scattering (SANS) experiments in the shell contrast. Neutron spin echo (NSE) has been employed to measure directly the dynamics of the shape fluctuations of the droplets. This method enables a separate determination of κ on its own. It is found that the effect of the increasing charge density leads only to a fairly small increase for the sum of the bending constants 2κ+κ¯. Also the change of the ionic strength for a charged microemulsion system has almost no influence on this sum. NSE measurements show no measurable difference in the dynamics of the charged and uncharged system leading to the conclusion that not only the sum but separately the two bending constants stay within experimental error unchanged. This experimental observation is in contrast to simple electrostatic theories that would predict a much more pronounced influence of the electric charge density on the bending properties of the amphiphilic film.

  11. Finite-size effect on the charging free energy of protein in explicit solvent.

    PubMed

    Ekimoto, Toru; Matubayasi, Nobuyuki; Ikeguchi, Mitsunori

    2015-01-13

    The finite-size effect in periodic system is examined for the charging free energy of protein in explicit solvent over a variety of charged states. The key to the finite-size correction is the self-energy, which is defined as the interaction energy of the solute with its own periodic images and the neutralizing background. By employing the thermodynamic-integration method with systematically varied sizes of the unit cell of molecular dynamics (MD) simulations, we show for ubiquitin that the self-energy corrects the finite-size effect on the charging free energy within 1 kcal/mol at total charges of -5e, -1e, neutral, and +1e and within 5 kcal/mol even for a highly charged state with +8e. We then sought the additional correction from the solvation effect using the numerical solution to the Poisson equation of the protein with implicit solvent. This correction reduces the cell-size dependence of the charging free energy at +8e to 3 kcal/mol and is well expressed as the self-energy divided by the dielectric constant of solvent water.

  12. Ions in mixed dielectric solvents: density profiles and osmotic pressure between charged interfaces.

    PubMed

    Ben-Yaakov, Dan; Andelman, David; Harries, Daniel; Podgornik, Rudi

    2009-04-30

    The forces between charged macromolecules, usually given in terms of osmotic pressure, are highly affected by the intervening ionic solution. While in most theoretical studies the solution is treated as a homogeneous structureless dielectric medium, recent experimental studies concluded that, for a bathing solution composed of two solvents (binary mixture), the osmotic pressure between charged macromolecules is affected by the binary solvent composition. By adding local solvent composition terms to the free energy, we obtain a general expression for the osmotic pressure, in planar geometry and within the mean-field framework. The added effect is due to the permeability inhomogeneity and nonelectrostatic short-range interactions between the ions and solvents (preferential solvation). This effect is mostly pronounced at small distances and leads to a reduction in the osmotic pressure for macromolecular separations of the order 1-2 nm. Furthermore, it leads to a depletion of one of the two solvents from the charged macromolecules (modeled as planar interfaces). Lastly, by comparing the theoretical results with experimental ones, an explanation based on preferential solvation is offered for recent experiments on the osmotic pressure of DNA solutions.

  13. Solvent dependence of structure, charge distribution, and absorption spectrum in the photochromic merocyanine-spiropyran pair.

    PubMed

    Murugan, N Arul; Chakrabarti, Swapan; Ågren, Hans

    2011-04-14

    We have studied the structures and absorption spectra of merocyanine, the photoresponsive isomer of the spiropyran (SP)-merocyanine (MC) pair, in chloroform and in water solvents using a combined hybrid QM/MM Car-Parrinello molecular dynamics (CP-QM/MM) and ZINDO approach. We report remarkable differences in the molecular structure and charge distribution of MC between the two solvents; the molecular structure of MC remains in neutral form in chloroform while it becomes charge-separated, zwitterionic, in water. The dipole moment of MC in water is about 50% larger than in chloroform, while the value for SP in water is in between, suggesting that the solvent is more influential than the conformation itself in deciding the dipole moment for the merocyanine-spiropyran pair. The calculations could reproduce the experimentally reported blue shift in the absorption spectra of MC when going from the nonpolar to the polar solvent, though the actual value of the absorption maximum is overestimated in chloroform solvent. We find that the CP-QM/MM approach is appropriate for structure modeling of solvatochromic and thermochromic molecules as this approach is able to capture the solvent and thermal-induced structural changes within the solute important for an accurate assessment of the properties.

  14. 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.

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

    PubMed

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

    2017-02-08

    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 lB, are strong. We find the existence of several sub-regimes in the dependence of the gyration radius of the chain Rg on lB characterized by Rg ∼ 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.

  16. Stable nonpolar solvent droplet generation using a poly(dimethylsiloxane) microfluidic channel coated with poly-p-xylylene for a nanoparticle growth.

    PubMed

    Lim, Heejin; Moon, SangJun

    2015-08-01

    Applications of microfluidic devices fabricated in poly(dimethylsiloxane) (PDMS) have been limited to water-based analysis rather than nonpolar solvent based chemistry due to a PDMS swelling problem that occurs by the absorption of the solvents. The absorption and swelling causes PDMS channel deformation in shape, and changes the cross sectional area making it difficult to control the flow rate and concentrations of solution in PDMS microfluidic channels. We propose that poly-p-xylylene polymers (parylenes) are chemical vapors deposited on the surfaces of PDMS channels that alleviate the effect of solvents on the absorption and swelling. The parylene coated surface sustains 3 h with a small volumetric change (less than 22 % of PDMS swelling ratio). By generating an air-nonpolar solvent interface based on droplets in PDMS channel, we confirmed poly-p-xylylene coated PDMS microfluidic channels have the potential to be applicable to nanocrystal growth using nonpolar solvents.

  17. Electric double layer force between charged surfaces: Effect of solvent polarization

    NASA Astrophysics Data System (ADS)

    Prasanna Misra, Rahul; Das, Siddhartha; Mitra, Sushanta K.

    2013-03-01

    In this paper, we develop a theory to delineate the consequences of finite solvent polarization in electric double layer interaction or the osmotic pressure between two similar or oppositely charged surfaces. We use previously published Langevin-Bikerman equations to calculate this electric double layer interaction force or the osmotic pressure between the charged surfaces. The osmotic pressure between oppositely charged surfaces is found to be much larger than that between similarly charged surfaces, and for either case, the influence of solvent polarization ensures a larger pressure than that predicted by the Poisson-Boltzmann (PB) model. We derive distinct scaling relationships to explain the increase of the pressure as a function of the separation between the surfaces, the solvent polarizability, and the number density of water molecules. Most importantly, we demonstrate that our theory can successfully reproduce the experimental results of interaction force between similar and oppositely charged surfaces, by accounting for the large under-prediction made by the corresponding PB model.

  18. Rayleigh limit and fragmentation of multiply charged Lennard-Jones clusters: Can charged clusters provide clues to investigate the stability of electrospray droplets?

    PubMed

    Bonhommeau, David A

    2017-03-28

    The fragmentation of multiply charged clusters composed of N≤1000 Lennard-Jones particles augmented with electrostatic interactions is explored by classical Monte Carlo and molecular dynamics simulations with the stated goal of establishing possible analogies with electrospray droplets. Clusters with few charge carriers are shown to be only subject to particle ejection and their Rayleigh limit can be estimated by quantifying the loss of charged particles. On the contrary, uniformly charged clusters can both evaporate particles and undergo fission, making them better candidates to model electrospray droplets. Critical charges delimiting regions of instability of these clusters are defined from the calculation of lower order multipole moments and asymmetry parameters based on the knowledge of moments of inertia. The first discontinuity of quadrupole moments and asymmetry parameters is related to cluster elongation before twofold fission and the corresponding charge is deemed to be a good estimate of the Rayleigh limit. Octopole moments are negligible about this charge, their discontinuities arising at higher charges when threefold fissions are allowed. The size dependence of these critical charges is qualitatively predicted from Rayleigh's formula and the expression of surface energy advocated in liquiddrop models. Deviations below 15% are commonly achieved when comparing Rayleigh limits extracted from experimental data with theoretical predictions based on Monte Carlo simulations or liquiddrop models for a set of eleven atomic and molecular liquid clusters. Although manifold fission of uniformly charged clusters is unlikely close to the Rayleigh limit, successive asymmetric fissions are found to occur in conjunction with other fragmentation mechanisms, including the expansion of ring-shaped structures, at charges more than twice as large as the Rayleigh limit.

  19. The effects of counterion exchange on charge stabilization for anionic surfactants in nonpolar solvents.

    PubMed

    Smith, Gregory N; Brown, Paul; James, Craig; Kemp, Roger; Khan, Asad Muhammad; Plivelic, Tomás S; Rogers, Sarah E; Eastoe, Julian

    2016-03-01

    Sodium dioctylsulfosuccinate (Aerosol OT or NaAOT) is a well-studied charging agent for model poly(methyl methacrylate) (PMMA) latexes dispersed in nonpolar alkane solvents. Despite this, few controlled variations have been made to the molecular structure. A series of counterion-exchanged analogs of NaAOT with other alkali metals (lithium, potassium, rubidium, and cesium) were prepared, and it was expected that this should influence the stabilization of charge on PMMA latexes and the properties of the inverse micelles. The electrophoretic mobilities of PMMA latexes were measured for all the counterion-exchanged AOT analogs, and these values were used to calculate the electrokinetic or ζ potentials. This enabled a comparison of the efficacy of the different surfactants as charging agents. Small-angle scattering measurements (using neutrons and X-rays) were performed to determine the structure of the inverse micelles, and electrical conductivity measurements were performed to determine the ionized fractions and Debye lengths. Sodium AOT is a much more effective charging agent than any of the other alkali metal AOTs. Despite this, the inverse micelle size and electrical conductivity of NaAOT are unremarkable. This shows a significant non-periodicity in the charging efficiency of these surfactants, and it emphasizes that charging particles in nonpolar solvents is a complex phenomenon. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

  20. Study of chemistry in droplets with net charge before and after Coulomb explosion: ion-induced nucleation in solution and implications for ion production in an electrospray.

    PubMed

    Bakhoum, Samuel F W; Agnes, George R

    2005-05-15

    Droplets with net charge are essential intermediaries in the production of gaseous ions in the electrospray (ES) ion source. There could be a wealth of knowledge regarding the chemistry that occurs in such droplets as a result of their violation of electroneutrality. Such information could lead to improved understanding of the ion generation process in an ES along with factors that affect it. The experiments performed involved the levitation of individually charged droplets that were, and were not, allowed to undergo Coulomb explosion while they remained levitated in an electrodynamic balance (EDB). Through examination of precipitates formed within the levitated droplets, it was observed that onset of NaCl precipitation was promoted in droplets (glycerol:water 9:1 v/v) that had mass-to-net-charge (m/z) ratio <-4.8 x 10(9) amu/e. This threshold m/z value is exceeded in essentially all droplets generated in an ES because it is above the calculated threshold for Coulomb explosion. This finding suggests that cluster formation in droplets having net charge could occur at solute concentrations lower than would be anticipated on the basis of homogeneous nucleation. The effect of large entities such as precipitates existing in the droplet on the dynamics of droplet Coulomb explosion was also examined. Using droplets whose initial size and magnitude of net charge were equivalent within experimental error but having different concentration of solutes, we showed that the m/z of their main residues following Coulomb explosion were different. Micrometer-size droplets containing 20 nm fluorescent beads that underwent Coulomb explosion resulted in main residues that had higher m/z for higher initial bead concentration in the starting solution (320 nM) when compared to main residues resultant from starting solutions having lower initial bead concentration (21 nM).

  1. Solvent-tuned intramolecular charge-recombination rates in a conjugated donor-acceptor molecule

    NASA Technical Reports Server (NTRS)

    Khundkar, Lutfur R.; Stiegman, A. E.; Perry, Joseph W.

    1990-01-01

    The nonradiative charge-recombination rates from the charge-transfer state of a new conjugated donor-acceptor molecule (p-cyano-p-prime-methylthiodiphenylacetylene) can be tuned over almost an order of magnitude by varying the polarity of the solvent. These measurements of intramolecular recombination show a turnover of rates as a function of emission energy, consistent with the 'normal' and 'inverted' behavior of Marcus theory. Steady-state spectra and time-resolved measurements make it possible to quantitatively compare thermal and optical electron-transfer rates as a function of driving force and demonstrate their correspondence.

  2. Rotational Diffusion of Charged and Nondipolar Solutes in Ionic Liquid-Organic Solvent Mixtures: Evidence for Stronger Specific Solute-Solvent Interactions in Presence of Organic Solvent.

    PubMed

    Prabhu, Sugosh R; Dutt, G B

    2015-08-20

    Rotational diffusion of a charged solute, rhodamine 110 (R110), and a nondipolar solute, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP), has been investigated in ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][Tf2N]) and 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([BMIM][FAP]), with 0.8 mole fraction of dibenzyl ether (DBE). This study has been undertaken to find out how specific interactions between the solute and the ionic liquid are affected upon dilution with a nondipolar solvent. It has been observed that at a given viscosity (η) and temperature (T), the reorientation times of R110 increase by 40-60% in the ionic liquid-organic solvent mixtures compared to ones in the corresponding neat ionic liquids. In the case of DMDPP, the influence of DBE is less pronounced, and its reorientation times increase by 25-50% at a given η/T. The addition of DBE weakens the numerous interactions prevailing between the cations and the anions of the ionic liquids, which results in stronger specific interactions between the solutes and the constituent ions, consequently leading to slower rotation of the solutes.

  3. Celebrating Soft Matter's 10th Anniversary: Influencing the charge of poly(methyl methacrylate) latexes in nonpolar solvents.

    PubMed

    Smith, Gregory N; Hallett, James E; Eastoe, Julian

    2015-11-07

    Sterically-stabilized poly(methyl methacrylate) (PMMA) latexes dispersed in nonpolar solvents are a classic, well-studied system in colloid science. This is because they can easily be synthesized with a narrow size distribution and because they interact essentially as hard spheres. These PMMA latexes can be charged using several methods (by adding surfactants, incorporating ionizable groups, or dispersing in autoionizable solvents), and due to the low relative permittivity of the solvents (εr ≈ 2 for alkanes to εr ≈ 8 for halogenated solvents), the charges have long-range interactions. The number of studies of these PMMA particles as charged species has increased over the past ten years, after few studies immediately following their discovery. A large number of variations in both the physical and chemical properties of the system (size, concentration, surfactant type, or solvent, as a few examples) have been studied by many groups. By considering the literature on these particles as a whole, it is possible to determine the variables that have an effect on the charge of particles. An understanding of the process of charge formation will add to understanding how to control charge in nonaqueous solvents as well as make it possible to develop improved technologically relevant applications for charged polymer nanoparticles.

  4. Spectrophotometric study of the charge-transfer complexes of iodine with antipyrine in organic solvents

    NASA Astrophysics Data System (ADS)

    Hasani, Masoumeh; Rezaei, Alireza

    2006-12-01

    The charge-transfer complex formation of iodine with antipyrine has been studied spectrophotometrically in chloroform, dichloromethane (DCM) and 1,2-dichloroethane (DCE) solutions at 25 °C. The results indicate the formation of 1:1 charge-transfer complexes. The observed time dependence of the charge-transfer band and subsequent formation of I 3- in solution were related to the slow transformation of the initially formed 1:1 antipyrine:I 2 outer complex to an inner electron donor-acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion. The values of the equilibrium constant, K, are calculated for each complex and the influence of the solvent properties on the formation of EDA complexes and the rates of subsequent reaction is evaluated.

  5. Spectrophotometric study of the charge-transfer complexes of iodine with antipyrine in organic solvents.

    PubMed

    Hasani, Masoumeh; Rezaei, Alireza

    2006-12-01

    The charge-transfer complex formation of iodine with antipyrine has been studied spectrophotometrically in chloroform, dichloromethane (DCM) and 1,2-dichloroethane (DCE) solutions at 25 degrees C. The results indicate the formation of 1:1 charge-transfer complexes. The observed time dependence of the charge-transfer band and subsequent formation of I(3)(-) in solution were related to the slow transformation of the initially formed 1:1 antipyrine:I(2) outer complex to an inner electron donor-acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion. The values of the equilibrium constant, K, are calculated for each complex and the influence of the solvent properties on the formation of EDA complexes and the rates of subsequent reaction is evaluated.

  6. Indirectly suspended droplet microextraction of water-miscible organic solvents by salting-out effect for the determination of polycyclic aromatic hydrocarbons.

    PubMed

    Daneshfar, Ali; Khezeli, Tahere

    2014-12-01

    A simple and low-cost method that indirectly suspended droplet microextraction of water-miscible organic solvents (ISDME) by salting-out effect before high-performance liquid chromatography and ultraviolet (HPLC-UV) detection was used for the determination of polycyclic aromatic hydrocarbons (PAHs) in different samples. The ISDME is a combination of salting-out extraction of water-miscible organic solvent and directly suspended droplet microextraction (DSDME). Ninety-five microliters water-miscible organic solvent (1-propanol) was added to a 500-µL sample. A homogeneous solution was formed immediately. To produce a steady vortex at the top of the solution, the sample was agitated at 700 rpm using a magnetic stirrer. By the addition of ammonium sulfate (saturated solution) to the homogeneous solution, 1-propanol was separated and collected at the bottom of the steady vortex. Finally, 20 µL 1-propanol was injected into HPLC-UV. The effects of important parameters such as water-miscible organic solvent (type and volume), type of salt, and extraction time were evaluated. Under optimum conditions, the method has a good linear calibration range (0.1 µg/L-300 µg/L), coefficients of determination (R(2) > 0.998), low limits of detection (between 0.02 µg/L and 0.27 µg/L), and acceptable recovery (>85.0%).

  7. Plasma charging and electron-based reactions at the plasma-liquid interface of an isolated liquid droplet

    NASA Astrophysics Data System (ADS)

    Maguire, Paul; Mahony, Charles; Kelsey, Colin; Rutherford, David; Mariotti, Davide; Diver, Declan

    2016-09-01

    The study of plasma-liquid interactions opens up exciting new opportunities for applications but numerous investigative challenges remain. The use of isolated and stable spherical liquid microdroplets in a non-thermal equilibrium atmospheric pressure plasma offers a new platform for experimental and theoretical investigations. Since the droplet assumes floating potential, a high flux of electrons with low net energy ( thermal) becomes fixed and solvated within the first monolayers of the liquid leading to highly reactive and rapid chemical reactions. We observe such reactions, e.g. H2 O2 and metal nanoparticle formation, at rates that are much higher than reported elsewhere. Since the isolated droplet radius is greater than Debye lengths and mean free paths, we have an opportunity to directly compare, for the first time, long-standing collisional probe theories in this important regime. We measure a lower bound average charge of >1E5 electrons on a 13um droplet. Simulations of unipolar corona charging for this size predict 1E3 electrons. A Comsol-based drift-diffusion model is currently under development and so far experiment and theory match within 1 order of magnitude but improvements in measurement technique are in progress. Funding from EPSRC acknowledged (Grants EP/K006088/1 and EP/K006142/1).

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

    SciTech Connect

    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 backbone 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.

  9. On the hardness evaluation in solvent for neutral and charged systems.

    PubMed

    De Luca, G; Sicilia, E; Russo, N; Mineva, T

    2002-02-20

    The influence of water on the hardness values of a series of neutral and charged molecules has been studied in the framework of density functional theory using the polarizable continuum model to take into account solvent effects. Three working formulas already widely tested in gas-phase have been used and the results compared. Two of the methods employed going from gas phase to solvent phase give values that do not change, while the results of the third method show remarkable changes. To check the reliability of the hardness behavior found, a test based on the hard-soft/acid-base principle and the calculation of the free energy of reaction has been applied using the adopted procedures.

  10. A comparative study of room temperature ionic liquids and their organic solvent mixtures near charged electrodes

    NASA Astrophysics Data System (ADS)

    Vatamanu, Jenel; Vatamanu, Mihaela; Borodin, Oleg; Bedrov, Dmitry

    2016-11-01

    The structural properties of electrolytes consisting of solutions of ionic liquids in a polar solvent at charged electrode surfaces are investigated using classical atomistic simulations. The studied electrolytes consisted of tetraethylammonium tetrafluoroborate (NEt4-BF4), 1-ethyl-3-methylimidazolium tetrafluoroborate (c2mim-BF4) and 1-octyl-3-methylimidazolium tetrafluoroborate (c8mim-BF4) salts dissolved in acetonitrile solvent. We discuss the influence of electrolyte concentration, chemical structure of the ionic salt, temperature, conducting versus semiconducting nature of the electrode, electrode geometry and surface roughness on the electric double layer structure and capacitance and compare these properties with those obtained for pure room temperature ionic liquids. We show that electrolytes consisting of solutions of ions can behave quite differently from pure ionic liquid electrolytes.

  11. Profiling an electrospray plume by laser-induced fluorescence and Fraunhofer diffraction combined to mass spectrometry: influence of size and composition of droplets on charge-state distributions of electrosprayed proteins.

    PubMed

    Girod, Marion; Dagany, Xavier; Boutou, Véronique; Broyer, Michel; Antoine, Rodolphe; Dugourd, Philippe; Mordehai, Alex; Love, Craig; Werlich, Mark; Fjeldsted, John; Stafford, George

    2012-07-14

    We investigated how physico-chemical properties of charged droplets are affected by the electrospray process, using simultaneous in situ measurements by laser-induced fluorescence (LIF), Fraunhofer diffraction and mass spectrometry. For this purpose, we implemented a laser-induced-fluorescence profiling setup in conjunction with a fast, high-resolution particle sizing scheme on a modified Agilent Jet Stream electrospray source coupled to a single quadrupole mass analyser. The optical setup permits us to profile the solvent fractionation and the size of the droplets as they evaporate in an electrospray plume by measuring both the angular scattering pattern and emission spectra of a solvatochromic fluorescent dye. Mass spectra are recorded simultaneously. These mass spectrometry and optical spectroscopy investigations allow us to study the relation between the observed charge-state distributions of protein anions and physico-chemical properties of evaporating droplets in the spray plume. By mixing water with methanol, a refolding of cytochrome C is observed as the water percentage increases in the plume due to the preponderant evaporation of volatile methanol.

  12. 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 electronic structuremore » 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+/PF6- 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

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

    SciTech Connect

    Chaudhari, Mangesh I.; Nair, Jijeesh R.; Pratt, Lawrence R.; Soto, Fernando A.; Balbuena, Perla B.; Rempe, Susan B.

    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 electronic 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+/PF6- 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.

  14. Extremely supercharged proteins in mass spectrometry: profiling the pH of electrospray generated droplets, narrowing charge state distributions, and increasing ion fragmentation.

    PubMed

    Zenaidee, Muhammad A; Donald, William A

    2015-03-21

    The effects of 12 acids, 4 solvents, and 8 low-volatility additives that increase analyte charging (i.e., superchargers) on the charge state distributions (CSDs) of protein ions in ESI-MS were investigated. We discovered that (i) relatively low concentrations [5% (v/v)] of 1,2-butylene carbonate (and 4-vinyl-1,3-dioxolan-2-one) can be added to ESI solutions to form higher charge states of cytochrome c and myoglobin ions than by using more traditional additives (e.g., propylene carbonate, sulfolane, or m-nitrobenzyl alcohol) under these conditions and (ii) the width of CSDs narrow as the effectiveness of superchargers increase, which concentrates protein ions into fewer detection channels. The use of strong acids (pKa values < 0) results in essentially no protein supercharging, higher adduction of acid molecules, and wider CSDs for many superchargers and proteins, whereas the use of weak acids (pKa > 0) results in significantly higher protein ion charging, less acid adduction, and narrower CSDs, indicating that protein ion supercharging in ESI can be significantly limited by the binding of conjugate base anions of acids that neutralize charge sites and broaden CSDs. The extent of protein charging as a function of acid identity (HA) does not strongly correlate with gas-phase proton transfer data (i.e., gas-phase basicity and proton affinity values for HA and A(-)), solution-phase protein secondary structures (as determined by circular dichroism spectroscopy), and/or acid molecule volatility data. For protein-denaturing solutions, these data were used to infer that the "effective" pH of ESI generated droplets near the moment of ion formation can be ∼0, which is ca. 1 to 3 pH units lower than the pH of the solutions prior to ESI. Electron capture dissociation (ECD) of [ubiquitin, 17H](17+) resulted in the identification of 223 cleavages, 74 of 75 inter-residue sites, and 92% ECD fragmentation efficiency, which correspond to highest of these values that have been

  15. Dual fluorescence and fast intramolecular charge transfer with 4-(diisopropylamino)benzonitrile in alkane solvents

    NASA Astrophysics Data System (ADS)

    Demeter, Attila; Druzhinin, Sergey; George, Mathew; Haselbach, Edwin; Roulin, Jean-Luc; Zachariasse, Klaas A.

    2000-06-01

    Dual fluorescence and fast intramolecular charge transfer (ICT) is observed with 4-(diisopropylamino)benzonitrile (DIABN) in alkane solvents. The rate constant ka for the reaction from the locally excited (LE) to the ICT state has a value of 3.4×10 11 s -1 in n-hexane at 25°C, with an activation energy Ea of 6 kJ mol -1. Efficient intersystem crossing with a yield of 0.94 takes place from the ICT state. With 4-(dimethylamino)benzonitrile, in contrast, dual fluorescence is not observed in alkanes. The charge transfer reaction of DIABN is mainly favoured by its small energy gap Δ E( S1, S2), in accordance with the PICT model for ICT in aminobenzonitriles.

  16. Charge transfer to solvent dynamics in iodide aqueous solution studied at ionization threshold.

    PubMed

    Kothe, Alexander; Wilke, Martin; Moguilevski, Alexandre; Engel, Nicholas; Winter, Bernd; Kiyan, Igor Yu; Aziz, Emad F

    2015-01-21

    We explore the early-time electronic relaxation in NaI aqueous solution exposed to a short UV laser pulse. Rather than initiating the charge transfer reaction by resonant photoexcitation of iodide, in the present time-resolved photoelectron spectroscopy study the charge-transfer-to-solvent (CTTS) states are populated via electronic excitation above the vacuum level. By analyzing the temporal evolution of electron yields from ionization of two transient species, assigned to CTTS and its first excited state, we determine both their ultrafast population and relaxation dynamics. Comparison with resonant-excitation studies shows that the highly excited initial states exhibit similar relaxation characteristics as found for resonant excitation. Implications for structure and dynamical response of the hydration cage are discussed.

  17. Predicting solvent-water partitioning of charged organic species using quantum-chemically estimated Abraham pp-LFER solute parameters.

    PubMed

    Davis, Craig Warren; Di Toro, Dominic M

    2016-12-01

    Methods for obtaining accurate predictions of solvent-water partitioning for neutral organic chemicals (e.g., Kow) are well-established. However, methods that provide comparable accuracy are not available for predicting the solvent-water partitioning of ionic species. Previous methods for addressing charge contributions to solvent-water partitioning rely on charged solute descriptors which are obtained from regressions to neutral species descriptors as well as charged descriptors which are specific to unique charge-functionalities and structural moieties. This paper presents a method for obtaining Abraham poly-parameter linear free energy relationship (pp-LFER) descriptors using quantum chemical calculations and molecular structure, only. The method utilizes a large number of solvent-water systems to overcome large errors in individual quantum chemical computations of ionic solvent-water partition coefficients. The result is a single set of quantum-chemically estimated Abraham solute parameters (QCAP) which are solvent-independent, and can be used to predict the solvent-water partitioning of ionic species. Predictions of solvent-water partition coefficients for ionic species using quantum-chemically estimated Abraham parameters (QCAPs) are shown to provide improved accuracy compared over both existing Absolv-estimated Abraham solute parameters (AAP) as well as direct a priori quantum chemical (QC) calculations for partitioning of anionic solutes in 4 organic solvent-water systems (RMS = 0.740, 2.48 and 0.426 for the Absolv, QC and QCAP methods, respectively). For quaternary amine cations in the octanol-water system the RMS errors of the solvent-water partition coefficients were larger and similar between the two Abraham models (RMSE = 0.997 and 1.16, for the AAP and QCAP methods, respectively). Both methods showed significant improvement over direct QC calculations (RMSE = 2.82). Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. An implicit solvent model for SCC-DFTB with Charge-Dependent Radii

    PubMed Central

    Hou, Guanhua; Zhu, Xiao; Cui, Qiang

    2010-01-01

    Motivated by the need of rapidly exploring the potential energy surface of chemical reactions that involve highly charged species, we have developed an implicit solvent model for the approximate density functional theory, SCC-DFTB. The solvation free energy is calculated using the popular model that employs Poisson-Boltzmann for electrostatics and a surface-area term for non-polar contributions. To balance the treatment of species with different charge distributions, we make the atomic radii that define the dielectric boundary and solute cavity depend on the solute charge distribution. Specifically, the atomic radii are assumed to be linearly dependent on the Mulliken charges and solved self-consistently together with the solute electronic structure. Benchmark calculations indicate that the model leads to solvation free energies of comparable accuracy to the SM6 model (especially for ions), which requires much more expensive DFT calculations. With analytical first derivatives and favorable computational speed, the SCC-DFTB based solvation model can be effectively used, in conjunction with high-level QM calculations, to explore the mechanism of solution reactions. This is illustrated with a brief analysis of the hydrolysis of mono-methyl mono-phosphate ester (MMP) and tri-methyl mono-phosphate ester (TMP). Possible future improvements are also briefly discussed. PMID:20711513

  19. Solvent Role in the Formation of Electric Double Layers with Surface Charge Regulation: A Bystander or a Key Participant?

    NASA Astrophysics Data System (ADS)

    Fleharty, Mark E.; van Swol, Frank; Petsev, Dimiter N.

    2016-01-01

    The charge formation at interfaces involving electrolyte solutions is due to the chemical equilibrium between the surface reactive groups and the potential determining ions in the solution (i.e., charge regulation). In this Letter we report our findings that this equilibrium is strongly coupled to the precise molecular structure of the solution near the charged interface. The neutral solvent molecules dominate this structure due to their overwhelmingly large number. Treating the solvent as a structureless continuum leads to a fundamentally inadequate physical picture of charged interfaces. We show that a proper account of the solvent effect leads to an unexpected and complex system behavior that is affected by the molecular and ionic excluded volumes and van der Waals interactions.

  20. Solvent blends can control cationic reversed micellar interdroplet interactions. The effect of n-heptane:benzene mixture on BHDC reversed micellar interfacial properties: droplet sizes and micropolarity.

    PubMed

    Agazzi, Federico M; Falcone, R Dario; Silber, Juana J; Correa, N Mariano

    2011-10-27

    We have investigated, for the first time, the effect of the composition of the nonpolar organic media on the benzyl-n-hexadecyl-dimethylammonium chloride (BHDC) reversed micelles (RMs) properties at fixed temperature. To achieve this goal we have used the solvatochromic behavior of 1-methyl-8-oxyquinolinium betaine (QB) as absorption probe and dynamic light scattering (DLS), to monitor droplet sizes, interfacial micropolarity, and sequestrated water structure of water/BHDC/n-heptane:benzene RMs. DLS results confirm the formation of the water/BHDC/n-heptane:benzene RMs at every n-heptane mole fraction (X(Hp)) investigated, that is, X(Hp) = 0.00, 0.13, 0.21, 0.30, and 0.38. Also, DLS was used to measure the RMs diffusion coefficient and to calculate the apparent droplet hydrodynamic diameter (d(App)) at different compositions of the nonpolar organic medium. The data suggest that as the n-heptane content increases, the interdroplet attractive interactions also increase with the consequent increment in the droplet size. Moreover, the interdroplet attractive interactions can be "switched on (increased)" or "switched off (decreased)" by formulation of appropriate n-heptane:benzene mixtures. Additionally, QB spectroscopy was used to obtain the "operational" critical micellar concentration (cmc) and to investigate both the RMs interfacial micropolarity and the sequestrated water structure in every RMs studied. The results show that BHDC RMs are formed at lower surfactant concentration when n-heptane or water content increases. When the interdroplet interaction "switches on", the RMs droplet sizes growth expelling benzene molecules from the RMs interface, favoring the water-BHDC interaction at the interface with the consequent increases in the interfacial micropolarity. Therefore, changing the solvent blend is possible to affect dramatically the interfacial micropolarity, the droplet sizes and the structure of the entrapped water.

  1. 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.

  2. Charge Transfer to Solvent Dynamics at the Ambient Water/Air Interface.

    PubMed

    Nowakowski, Paweł J; Woods, David A; Verlet, Jan R R

    2016-10-03

    Electron-transfer reactions at ambient aqueous interfaces represent one of the most fundamental and ubiquitous chemical reactions. Here the dynamics of the charge transfer to solvent (CTTS) reaction from iodide was probed at the ambient water/air interface by phase-sensitive transient second-harmonic generation. Using the three allowed polarization combinations, distinctive dynamics assigned to the CTTS state evolution and to the subsequent solvating electron-iodine contact pair have been resolved. The CTTS state is asymmetrically solvated in the plane of the surface, while the subsequent electron solvation dynamics are very similar to those observed in the bulk, although slightly faster. Between 3 and 30 ps, a small phase shift distinguishes an electron bound in a contact pair with iodine and a free hydrated electron at the water/air interface. Our results suggest that the hydrated electron is fully solvated in a region of reduced water density at the interface.

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

    SciTech Connect

    Nakano, Hiroshi

    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.

  4. Charging of metal clusters in helium droplets exposed to intense femtosecond laser pulses.

    PubMed

    Döppner, T; Diederich, Th; Przystawik, A; Truong, N X; Fennel, Th; Tiggesbäumker, J; Meiwes-Broer, K-H

    2007-09-07

    We review the strong field (10(13)-10(16) W cm(-2)) laser excitation of metal clusters (Cd(N), Ag(N) and Pb(N)) embedded in He nanodroplets. Plasmon enhanced ionization obtained by stretching the laser pulses to several hundreds of femtoseconds or by using dual pulses with a suitable optical delay leads to a Coulomb explosion of highly charged atomic ions. The charging dynamics can be well described by corresponding semiclassical Vlasov simulations. The influence of the He environment on the ionization process and on the final charge distribution is discussed. Evidence is found that He(2+) is generated in collisions with highly charged metal ions. In contrast, singly and doubly charged ions with low recoil energies induce the formation of He snowballs with a distinct shell structure around the ion. Laser intensity thresholds for snowball formation and for the ionization of clusters are investigated by applying intensity selective scanning.

  5. Mesoscale Lattices Assembled from Charge-Tunable Block Copolymer Blends in Selective Solvents

    NASA Astrophysics Data System (ADS)

    Kim, Seyoung; Choi, Jewon; Choi, Soo-Hyung; Char, Kookheon

    Recent studies revealed that block copolymer (BCP) microdomains are capable of being organized into unusual symmetries such as the Frank-Casper phases. These unique structures result from a compromise between domain geometry and space-filling constraint; in other words, the deformability of soft matter. Our mesoscale micellar lattices co-assembled from the blends of oppositely charged BCPs demonstrate the nature of deformable soft materials in a distinctive way. The micellar structures and interactions of BCPs in selective solvents can be finely tuned by controlling the charge density such that the spherical micelles further assemble into hexagonal arrays. The micellar lattices show unconventional symmetry and sub-10 nm clean facet formation compared to hard-sphere counterparts reported so far. We attribute these novel phenomena to multi-compartment intrastructure of the micelles assembled and their strong interactions, since the crystalline symmetry disappears with a subtle control of solvency, mixing ratio of BCP blends, and micellar interactions. Analysis on the nucleation condition reveals that such deviation in the micellar lattices arises from the soft nature of BCP assemblies which can be readily deformed upon swelling.

  6. Generating electric current based on the solvent-dependent charging effects of defective boron nitride nanosheets.

    PubMed

    Que, Ronghui; Huang, Yucheng; Li, Qinling; Yao, Hong; Geng, Baoyou; Shao, Mingwang

    2014-11-26

    This work presents a method of generating electric current based on the defects of few-layer boron nitride nanosheets (BNNSs). The density functional theory calculations showed that the atomic charge of the B atom in acetone was more positive than in water. The electrostatic force microscopy measurements illustrated that the local electrical potential was 0.35 mV in acetone, while the potential signal was very difficult to capture when using water as the dispersant. This effect was further demonstrated by the performance of the acoustic energy-harvesting nanogenerator: the BNNSs were assembled into a film after being dispersed in acetone and then integrated into the generator device, generating average output current of ∼0.98 nA, which was much better than 0.2 nA, the average output current of another device with water as the dispersant. These results demonstrated that solvent effects made the as-prepared BNNSs carry net charges, which could be utilized to harvest acoustic energy and generate current.

  7. Charge-transfer dynamics and nonlocal dielectric permittivity tuned with metamaterial structures as solvent analogues

    NASA Astrophysics Data System (ADS)

    Lee, Kwang Jin; Xiao, Yiming; Woo, Jae Heun; Kim, Eunsun; Kreher, David; Attias, André-Jean; Mathevet, Fabrice; Ribierre, Jean-Charles; Wu, Jeong Weon; André, Pascal

    2017-07-01

    Charge transfer (CT) is a fundamental and ubiquitous mechanism in biology, physics and chemistry. Here, we evidence that CT dynamics can be altered by multi-layered hyperbolic metamaterial (HMM) substrates. Taking triphenylene:perylene diimide dyad supramolecular self-assemblies as a model system, we reveal longer-lived CT states in the presence of HMM structures, with both charge separation and recombination characteristic times increased by factors of 2.4 and 1.7--that is, relative variations of 140 and 73%, respectively. To rationalize these experimental results in terms of driving force, we successfully introduce image dipole interactions in Marcus theory. The non-local effect herein demonstrated is directly linked to the number of metal-dielectric pairs, can be formalized in the dielectric permittivity, and is presented as a solid analogue to local solvent polarity effects. This model and extra PH3T:PC60BM results show the generality of this non-local phenomenon and that a wide range of kinetic tailoring opportunities can arise from substrate engineering. This work paves the way toward the design of artificial substrates to control CT dynamics of interest for applications in optoelectronics and chemistry.

  8. 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.

  9. 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.

  10. Solvent effects on global reactivity properties for neutral and charged systems using the sequential Monte Carlo quantum mechanics model.

    PubMed

    Jaramillo, Paula; Pérez, Patricia; Fuentealba, Patricio; Canuto, Sylvio; Coutinho, Kaline

    2009-04-02

    The energy of the frontier molecular orbitals and reactivity indices such as chemical potential, hardness, and electrophilicity of neutral and charged molecules have been investigated in aqueous solution using explicit model for the solvent with the sequential Monte Carlo/quantum mechanics methodology. The supermolecular structures of the solute-solvent system were generated by Monte Carlo simulation. Statistically uncorrelated structures have been extracted for quantum mechanical calculations of the solute surrounded by the first solvation shell, using explicit water molecules, and the second and third shells as atomic point charges. The supermolecular calculations treating both the solute and the solvent explicitly were performed within density functional theory. The solvent dependence of the frontier molecular orbital energies was analyzed and used to calculate the reactivity indices in solution. The dependence of the results with respect to the number of explicit solvent molecules is also analyzed. It is seen that for the systems considered here, the energies of the highest occupied molecular orbital and the lowest unoccupied molecular orbital show a strong dependence with the number of solvent molecules. However, the properties derived from these are relatively stable. In particular, the results reported here for the reactivity indices obtained using the first solvation shell are similar to those obtained for the limit bulk value. For comparison, the reactivity indices were also calculated in the gas phase and using the polarizable continuum model (PCM). As frequently reported in the literature, neutral molecules do not show significant changes in the reactivity indices between gas phase and the PCM model. However, with the explicit solvent model some important changes were observed: a larger negative chemical potential, a smaller hardness, and a larger electrophilicity. The stabilization of an anion corresponding to a negative chemical potential is obtained

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

    PubMed

    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(-)) in diethyl ether (DEE) to those of sodide (Na(-)) 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 electrons 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(-) CTTS band producing a greater number of long-lived electrons than is seen following the corresponding red-edge excitation of the Na(-) CTTS band. This indicates that the CTTS excited states of K(-) 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 alkali metal anions essentially

  12. A counter-charge layer in generalized solvents framework for electrical double layers in neat and hybrid ionic liquid electrolytes

    SciTech Connect

    Huang, Jingsong; Feng, Guang; Sumpter, Bobby G; Qiao, Rui; Meunier, Vincent

    2011-01-01

    Room-temperature ionic liquids (RTILs) have received significant attention as electrolytes due to a number of attractive properties such as their wide electrochemical windows. Since electrical double layers (EDLs) are the cornerstone for the applications of RTILs in electrochemical systems such as supercapacitors, it is important to develop an understanding of the structure capacitance relationships for these systems. Here we present a theoretical framework termed counter-charge layer in generalized solvents (CGS) for describing the structure and capacitance of the EDLs in neat RTILs and in RTILs mixed with different mass fractions of organic solvents. Within this framework, an EDL is made up of a counter-charge layer exactly balancing the electrode charge, and of polarized generalized solvents (in the form of layers of ion pairs, each of which has a zero net charge but has a dipole moment the ion pairs thus can be considered as a generalized solvent) consisting of all RTILs inside the system except the counter-ions in the counter-charge layer, together with solvent molecules if present. Several key features of the EDLs that originate from the strong ion ion correlation in RTILs, e.g., overscreening of electrode charge and alternating layering of counter-ions and co-ions, are explicitly incorporated into this framework. We show that the dielectric screening in EDLs is governed predominately by the polarization of generalized solvents (or ion pairs) in the EDL, and the capacitance of an EDL can be related to its microstructure with few a priori assumptions or simplifications. We use this framework to understand two interesting phenomena observed in molecular dynamics simulations of EDLs in a neat IL of 1-butyl-3- methylimidazolium tetrafluoroborate ([BMIM][BF4]) and in a mixture of [BMIM][BF4] and acetonitrile (ACN): (1) the capacitance of the EDLs in the [BMIM][BF4]/ACN mixture increases only slightly when the mass fraction of ACN in the mixture increases from zero

  13. Ultrafast photo-induced charge transfer of 1-naphthol and 2-naphthol to halocarbon solvents

    NASA Astrophysics Data System (ADS)

    Chaudhuri, Subhajyoti; Rudshteyn, Benjamin; Prémont-Schwarz, Mirabelle; Pines, Dina; Pines, Ehud; Huppert, Dan; Nibbering, Erik T. J.; Batista, Victor S.

    2017-09-01

    We explore the fluorescence quenching of 1-naphthol and 2-naphthol in halocarbon solvents by using time-correlated single-photon-counting, femtosecond IR-spectroscopy and quantum chemistry computations. We find that halocarbon solvents facilitate a de-excitation mechanism via solute-solvent electron transfer. Decay rates are modulated by close contact interactions between the π-electronic structure of naphthols and halocarbon molecules in their first solvation shell. 1-naphthol exhibits faster decay rates than 2-naphthol due to closer interactions with the solvent.

  14. Solvation effect on conformations of 1,2:Dimethoxyethane: Charge dependent nonlinear response in implicit solvent models

    PubMed Central

    Jha, Abhishek K; Freed, Karl F

    2009-01-01

    We provide an improvement in the Langevin-Debye model currently being used in some implicit solvent models for computer simulations of solvation free energies of small organic molecules, as well as of biomolecular folding and binding. The analysis is based on the implementation of a charge-dependent Langevin-Debye (qLD) model that is modified by subsequent corrections due to Onsager and Kirkwood. The physical content of the model is elucidated by discussing the general treatment within the LD model of the self-energy of a charge submerged in a dielectric medium for three different limiting conditions and by considering the nonlinear response of the medium. The modified qLD model is used to refine an implicit solvent model (previously applied to protein dynamics). The predictions of the modified implicit solvent model are compared with those from explicit solvent molecular dynamics simulations for the equilibrium conformational populations of 1,2-dimethoxyethane (DME), which is the shortest ether molecule to reproduce the local conformational properties of PEO, a polymer with tremendous technological importance and a wide variety of applications. Because the conformational population preferences of DME change dramatically upon solvation, DME provides a good test case to validate our modified qLD model. PMID:18205504

  15. Lateral resolution of desorption nanoelectrospray: a nanospray tip without nebulizing gas as a source of primary charged droplets.

    PubMed

    Hartmanová, L; Lorencová, I; Volný, M; Fryčák, P; Havlíček, V; Chmelíčková, H; Ingr, T; Lemr, K

    2016-04-07

    Desorption nanoelectrospray (nanoDESI) was described in 2007 and it represents a miniaturized version of desorption electrospray without the assistance of the nebulizing gas. Compared to DESI, a nanoelectrospray tip (2 ± 1 μm I.D.) generates primary charged droplets of smaller sizes and lower spray liquid flow rates. This is the first report on utilization of nanoDESI for mass spectrometry imaging (MSI). Its new coupling with a Q-TOF instrument allowed faster mass spectra acquisition (4 Hz) essential for MSI of fine surface details. To evaluate nanoDESI potential for mass spectrometry imaging, etched glass substrates with Rhodamine B patterns of different dimensions were prepared. The Rhodamine B lines were analysed in 1D scanning mode and their width was determined experimentally by nanoDESI measurement. The experimental data revealed that the lateral resolution of nanoDESI is close to 30 μm along the x-axis (orthogonal to the inlet). 2D scanning mode confirmed good resolution along both axes as dye squares with dimensions about 60 μm × 60 μm were easily distinguished. The low flow rate of the spray liquid reduced undesirable analyte washing effects, which allowed repeated scanning analysis of the surface. The presented results demonstrate the applicability of nanoDESI for high surface resolution mass spectrometry imaging.

  16. Synthesis and spectrophotometric studies of charge transfer complexes of p-nitroaniline with benzoic acid in different polar solvents

    NASA Astrophysics Data System (ADS)

    Singh, Neeti; Ahmad, Afaq

    2014-09-01

    The charge transfer complexes of the donor p-nitroaniline (PNA) with the π-acceptor benzoic acid (BEA) have been studied spectrophotometrically in various solvents such as acetone, ethanol, and methanol at room temperature using an absorption spectrophotometer. The outcome suggests that the formation of the CT-complex is comparatively high in less polar solvent. The stoichiometry of the CT-complex was found to be 1:1. The physical parameters of the CT-complex were evaluated by the Benesi-Hildebrand equation. The data are discussed in terms of the formation constant (KCT), molar extinction coefficient (ɛCT), Standard Gibbs free energy (ΔG0), oscillator strength (f), transition dipole moment (μEN), resonance energy (RN) and ionization potential (ID). The formation constant (KCT) of the complex was depends upon the nature of electron acceptor, donor, and polarity of solvents used. It is also observed that a charge transfer molecular complex is stabilized by hydrogen bonding. The formation of the complex has been confirmed by UV-visible, FT-IR, 1H NMR and TGA/DTA. The structure of the CT-complex is [(PNA)+ (BEA)-]. A general mechanism for its formation of the complex has also been proposed.

  17. Photoexcitation and charge-transfer-to-solvent relaxation dynamics of the I(-)(CH3CN) complex.

    PubMed

    Mak, Chun C; Timerghazin, Qadir K; Peslherbe, Gilles H

    2013-08-15

    Photoexcitation of iodide-acetonitrile clusters, I(-)(CH3CN)n, to the charge-transfer-to-solvent (CTTS) state and subsequent cluster relaxation could result in the possible formation of cluster analogues of the bulk solvated electron. In this work, the relaxation process of the CTTS excited iodide-acetonitrile binary complex, [I(-)(CH3CN)]*, is investigated using rigorous ab initio quantum chemistry calculations and direct-dynamics simulations to gain insight into the role and motion of iodine and acetonitrile in the relaxation of CTTS excited I(-)(CH3CN)n. Computed potential energy curves and profiles of the excited electron vertical detachment energy for [I(-)(CH3CN)]* along the iodine-acetonitrile distance coordinate reveal for the first time significant dispersion effects between iodine and the excited electron, which can have a significant stabilizing effect on the latter. Results of direct-dynamics simulations demonstrate that [I(-)(CH3CN)]* undergoes dissociation to iodine and acetonitrile fragments, resulting in decreased stability of the excited electron. The present work provides strong evidence of solvent translational motion and iodine ejection as key aspects of the early time relaxation of CTTS excited I(-)(CH3CN)n that can also have a substantial impact on the subsequent electron solvation processes and further demonstrates that intricate details of the relaxation process of CTTS excited iodide-polar solvent molecule clusters make it heavily solvent-dependent.

  18. Direct Observation of Charge-Transfer-to-Solvent Reactions: Femtosecond Studies of the Photoexcited Alkali Metal Anion Sodide (Na-)

    NASA Astrophysics Data System (ADS)

    Schwartz, Benjamin

    2000-03-01

    Charge-transfer-to-solvent (CTTS) transitions have been the subject of a great deal of interest recently because they represent the simplest possible charge transfer reaction: the CTTS electron transfer from an atomic ion to a cavity in the surrounding solvent involves only electronic degrees of freedom. Most of the work in this area, both experimental and theoretical, has focused on aqueous halides. Experimentally, however, halides are a poor choice for studying the CTTS phenomenon because the relevant spectroscopic transitions are deep in the UV and because the charge transfer dynamics can be monitored only indirectly through the appearance of the solvated electron. In this talk, we show that these difficulties can be overcome by taking advantage of the CTTS transitions in solutions of alkali metal anions, in particular, the near-IR CTTS band of sodide (Na ) in tetrahydrofuran (THF). Using femtosecond pump-probe techniques, we have been able to spectroscopically separate and identify transient absorption contributions not only from the solvated electron, but also from the bleaching dynamics of the Na ground state and from the absorption of the neutral sodium atom. Perhaps most importantly, we also have been able to directly observe the decay of the Na * excited CTTS state, providing the first direct measure of the electron transfer rate for any CTTS system. Taken together, the data at a variety of pump and probe wavelengths provide a direct test for several kinetic models of the CTTS process. The model which best fits the data assumes a delayed ejection of the electron from the CTTS excited state in 700 fs. Once ejected, a fraction of the electrons recombine with the neutral sodium parent atom on a 1.3 ps time scale. The fraction of electrons that recombine depends sensitively on the choice of excitation wavelength, suggesting multiple pathways for charge transfer. All the results are compared to previous studies of both CTTS dynamics and alkali metal solutions

  19. Accelerated Chemical Reactions and Organic Synthesis in Leidenfrost Droplets.

    PubMed

    Bain, Ryan M; Pulliam, Christopher J; Thery, Fabien; Cooks, R Graham

    2016-08-22

    Leidenfrost levitated droplets can be used to accelerate chemical reactions in processes that appear similar to reaction acceleration in charged microdroplets produced by electrospray ionization. Reaction acceleration in Leidenfrost droplets is demonstrated for a base-catalyzed Claisen-Schmidt condensation, hydrazone formation from precharged and neutral ketones, and for the Katritzky pyrylium into pyridinium conversion under various reaction conditions. Comparisons with bulk reactions gave intermediate acceleration factors (2-50). By keeping the volume of the Leidenfrost droplets constant, it was shown that interfacial effects contribute to acceleration; this was confirmed by decreased reaction rates in the presence of a surfactant. The ability to multiplex Leidenfrost microreactors, to extract product into an immiscible solvent during reaction, and to use Leidenfrost droplets as reaction vessels to synthesize milligram quantities of product is also demonstrated. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. 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.

  1. Effect of partial atomic charges on the calculated free energy of solvation of poly(vinyl alcohol) in selected solvents.

    PubMed

    Noorjahan, Abolfazl; Choi, Phillip

    2015-03-01

    It is well-known that properties of poly(vinyl alcohol) (PVA) in the pure and solution states depend largely on the hydrogen bonding networks formed. In the context of molecular simulation, such networks are handled through the Coulombic interactions. Therefore, a good set of partial atom charges (PACs) for simulations involving PVA is highly desirable. In this work, we calculated the PACs for PVA using a few commonly used population analysis schemes with a hope to identify an accurate set of PACs for PVA monomers. To evaluate the quality of the calculated parameters, we have benchmarked their predictions for free energy of solvation (FES) in selected solvents by molecular dynamics simulations against the ab initio calculated values. Selected solvents were water, ethanol and benzene as they covered a range of size and polarity. Also, PVA with different tacticities were used to capture their effect on the calculated FESs. Based on our results, neither PACs nor FESs are affected by the chain tacticity. While PACs predicted by the Merz-Singh-Kollman scheme were close to original values in the OPLS-AA force field in way that no significant difference in properties of pure PVA was observed, free energy of solvation calculated using such PACs showed greater agreement with ab initio calculated values than those calculated by OPLS-AA (and all other schemes used in this work) in all three solvents considered.

  2. Equation of motion for the solvent polarization apparent charges in the polarizable continuum model: Application to time-dependent CI

    NASA Astrophysics Data System (ADS)

    Pipolo, Silvio; Corni, Stefano; Cammi, Roberto

    2017-02-01

    The dynamics of the electrons for a molecule in solution is coupled to the dynamics of its polarizable environment, i.e., the solvent. To theoretically investigate such electronic dynamics, we have recently developed equations of motion (EOM) for the apparent solvent polarization charges that generate the reaction field in the Polarizable Continuum Model (PCM) for solvation and we have coupled them to a real-time time-dependent density functional theory (RT TDDFT) description of the solute [S. Corni et al., J. Phys. Chem. A 119, 5405 (2014)]. Here we present an extension of the EOM-PCM approach to a Time-Dependent Configuration Interaction (TD CI) description of the solute dynamics, which is free from the qualitative artifacts of RT TDDFT in the adiabatic approximation. As tests of the developed approach, we investigate the solvent Debye relaxation after an electronic excitation of the solute obtained either by a π pulse of light or by assuming the idealized sudden promotion to the excited state. Moreover, we present EOM for the Onsager solvation model and we compare the results with PCM. The developed approach provides qualitatively correct real-time evolutions and is promising as a general tool to investigate the electron dynamics elicited by external electromagnetic fields for molecules in solution.

  3. Solvent accessibility, residue charge and residue volume, the three ingredients of a robust amino acid substitution matrix.

    PubMed

    Goodarzi, Hani; Katanforoush, Ali; Torabi, Noorossadat; Najafabadi, Hamed Shateri

    2007-04-21

    Cost measure matrices or different amino acid indices have been widely used for studies in many fields of biology. One major criticism of these studies might be based on the unavailability of an unbiased and yet effective amino acid substitution matrix. Throughout this study we have devised a cost measure matrix based on the solvent accessibility, residue charge, and residue volume indices. Performed analyses on this novel substitution matrix (i.e. solvent accessibility charge volume (SCV) matrix) support the uncontaminated nature of this matrix regarding the genetic code. Although highly similar to a number of previously available cost measure matrices, the SCV matrix results in a more significant optimality in the error-buffering capacity of the genetic code when compared to many other amino acid substitution matrices. Besides, a method to compare an SCV-based scoring matrix with a number of widely used matrices has been devised, the results of which highlights the robustness of this matrix in protein family discrimination.

  4. Photoinduced charge generation rates in soluble P3HT : PCBM nano-aggregates predict the solvent-dependent film morphology

    NASA Astrophysics Data System (ADS)

    Roy, Palas; Jha, Ajay; Dasgupta, Jyotishman

    2016-01-01

    The device efficiency of bulk heterojunction (BHJ) solar cells is critically dependent on the nano-morphology of the solution-processed polymer : fullerene blend. Active control on blend morphology can only emanate from a detailed understanding of solution structures during the film casting process. Here we use photoinduced charge transfer (CT) rates to probe the effective length scale of the pre-formed solution structures and their energy disorder arising from a mixture of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) in three different organic solvents. The observed solvent-dependent ultrafast biphasic rise of the transient polaron state in solution along with changes detected in the C&z.dbd;C stretching frequency of bound PCBM provides direct evidence for film-like P3HT : PCBM interfaces in solution. Using the diffusive component of the charge transfer rate, we deduce ~3-times larger functional nano-domain size in toluene than in chlorobenzene thereby correctly predicting the relative polymer nanofiber widths observed in annealed films. We thus provide first experimental evidence for the postulated polymer : fullerene : solvent ternary phase that seeds the eventual morphology in spin-cast films. Our work motivates the design of new chemical additives to tune the grain size of the evolving polymer : fullerene domains within the solution phase.The device efficiency of bulk heterojunction (BHJ) solar cells is critically dependent on the nano-morphology of the solution-processed polymer : fullerene blend. Active control on blend morphology can only emanate from a detailed understanding of solution structures during the film casting process. Here we use photoinduced charge transfer (CT) rates to probe the effective length scale of the pre-formed solution structures and their energy disorder arising from a mixture of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) in three

  5. Na(-) photolysis in THF: Charge transfer to solvent studied from the donors perspective in <10 fs detail.

    PubMed

    Shoshanim, Ofir; Ruhman, Sanford

    2008-07-28

    Two and three pulse photolysis experiments on terahydrofuran (THF) solutions of Na(-), utilizing hyperspectral probing, are described. The objective is to probe the extent and duration of energetic correlations between the primary charge transfer to solvent (CTTS) fragments which are an e(-) and Na(0). The latter is characterized by an intense visible absorption spectrum with fine structure reflecting the atom's immediate solvent environment. Pump-probe experiments with approximately 6 fs pulses show that for the majority of irradiated ions, the electron ejection and production of unperturbed Na(0) is effectively over in approximately 15 fs, with no precursors. Three pulse experiments further demonstrate this to be true for nearly all ions irradiated at 3 eV. Thus, the 400 nm data provide a detailed spectral record of the formation and subsequent solvation and polarization of neutral sodium bubbles in THF. Measures are presented for parametrizing the ensuing spectral evolution. In contrast, exciting at 1.5 eV, the red edge of the CTTS band leads to charge transfer with less than unity quantum efficiency. The complementary fraction of absorbing ions is photostable at 800 nm, presumably due to preferential solvent stabilization. Prompt secondary irradiation at 2 microm can complete ionization of that population leading to additional generation of Na(0) but exhibiting much more pronounced spectral structure. Thus, at low photon energies, a short lived correlated and bound electronic excited state is produced with significant yield. These results are discussed in terms of classical models for CTTS spectra, as well as more recent simulations and experiments concerning CTTS in this and other related systems.

  6. Solvent additive to achieve highly ordered nanostructural semicrystalline DPP copolymers: toward a high charge carrier mobility.

    PubMed

    An, Tae Kyu; Kang, Il; Yun, Hui-jun; Cha, Hyojung; Hwang, Jihun; Park, Seonuk; Kim, Jiye; Kim, Yu Jin; Chung, Dae Sung; Kwon, Soon-Ki; Kim, Yun-Hi; Park, Chan Eon

    2013-12-23

    A facile spin-coating method in which a small percentage of the solvent additive, 1-chloronaphthalene (CN), is found to increase the drying time during film deposition, is reported. The field-effect mobility of a PDPPDBTE film cast from a chloroform-CN mixed solution is 0.46 cm(2) V(-1) s(-1). The addition of CN to the chloroform solution facilitates the formation of highly crystalline polymer structures.

  7. Direct observation of charge-transfer-to-solvent (CTTS) reactions: Ultrafast dynamics of the photoexcited alkali metal anion sodide (Na-)

    NASA Astrophysics Data System (ADS)

    Barthel, Erik R.; Martini, Ignacio B.; Schwartz, Benjamin J.

    2000-06-01

    Charge-transfer-to-solvent (CTTS) transitions have been the subject of a great deal of interest recently because they represent the simplest possible charge transfer reaction: The CTTS electron transfer from an atomic ion to a cavity in the surrounding solvent involves only electronic degrees of freedom. Most of the work in this area, both experimental and theoretical, has focused on aqueous halides. Experimentally, however, halides make a challenging choice for studying the CTTS phenomenon because the relevant spectroscopic transitions are deep in the UV and because the charge-transfer dynamics can be monitored only indirectly through the appearance of the solvated electron. In this paper, we show that these difficulties can be overcome by taking advantage of the CTTS transitions in solutions of alkali metal anions, in particular, the near-IR CTTS band of sodide (Na-) in tetrahydrofuran (THF). Using femtosecond pump-probe techniques, we have been able to spectroscopically separate and identify transient absorption contributions not only from the solvated electron, but also from the bleaching dynamics of the Na- ground state and from the absorption of the neutral sodium atom. Perhaps most importantly, we also have been able to directly observe the decay of the Na-* excited CTTS state, providing the first direct measure of the electron transfer rate for any CTTS system. Taken together, the data at a variety of pump and probe wavelengths provide a direct test for several kinetic models of the CTTS process. The model which best fits the data assumes a delayed ejection of the electron from the CTTS excited state in ˜700 fs. Once ejected, a fraction of the electrons, which remain localized in the vicinity of the neutral sodium parent atom, recombine on a ˜1.5-ps time scale. The fraction of electrons that recombine depends sensitively on the choice of excitation wavelength, suggesting multiple pathways for charge transfer. The spectrum of the neutral sodium atom, which

  8. Combined application of dispersive liquid-liquid microextraction based on the solidification of floating organic droplets and charged aerosol detection for the simple and sensitive quantification of macrolide antibiotics in human urine.

    PubMed

    Jia, Shaodong; Li, Jing; Park, So-Ra; Ryu, Yeonsuk; Park, Il Ho; Park, Jeong Hill; Hong, Soon-Sun; Kwon, Sung Won; Lee, Jeongmi

    2013-12-01

    A novel analytical method combining dispersive liquid-liquid microextraction based on the solidification of floating organic droplets (DLLME-SFO) and liquid chromatography with charged aerosol detection (LC-CAD) was established. For the first time, CAD was applied for the detection of macrolide antibiotics lacking chromophores. Parameters influencing the microextraction efficiency were systematically investigated, and the optimized microextraction conditions yielded high enrichment factors in the range of 60-106. The combined application of DLLME-SFO and LC-CAD provided the sensitivity of the method, expressed as the limit of detection (LOD), as low as 10 to 40ngmL(-1) and intra-day and inter-day precisions below 8.7% and 12.6%, respectively. The measured absolute recovery values were approximately 100%, indicating that the extraction efficiency was very high. Direct comparisons of the liquid-liquid extraction and organic solvent precipitation methods demonstrated that the proposed method was more sensitive, specific, rapid, and environmentally friendly for the determination of five macrolide antibiotics in human urine. The results suggest that the combined use of DLLME-SFO and LC-CAD may be applicable to the analysis of various compounds with poor to no chromophores in complex matrices.

  9. Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent

    SciTech Connect

    Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.

    2015-06-21

    The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism.

  10. Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent

    NASA Astrophysics Data System (ADS)

    Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.

    2015-06-01

    The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism.

  11. Dynamics of electron solvation in methanol: Excited state relaxation and generation by charge-transfer-to-solvent.

    PubMed

    Elkins, Madeline H; Williams, Holly L; Neumark, Daniel M

    2015-06-21

    The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism.

  12. The ultrafast charge-transfer-to-solvent dynamics of iodide in tetrahydrofuran. 1. Exploring the roles of solvent and solute electronic structure in condensed-phase charge-transfer reactions.

    PubMed

    Bragg, Arthur E; Schwartz, Benjamin J

    2008-01-17

    Although they represent the simplest possible charge-transfer reactions, the charge-transfer-to-solvent (CTTS) dynamics of atomic anions exhibit considerable complexity. For example, the CTTS dynamics of iodide in water are very different from those of sodide (Na-) in tetrahydrofuran (THF), leading to the question of the relative importance of the solvent and solute electronic structures in controlling charge-transfer dynamics. In this work, we address this issue by investigating the CTTS spectroscopy and dynamics of I- in THF, allowing us to make detailed comparisons to the previously studied I-/H2O and Na-/THF CTTS systems. Since THF is weakly polar, ion pairing with the counterion can have a substantial impact on the CTTS spectroscopy and dynamics of I- in this solvent. In this study, we have isolated "counterion-free" I- in THF by complexing the Na+ counterion with 18-crown-6 ether. Ultrafast pump-probe experiments reveal that THF-solvated electrons (e-THF) appear 380 +/- 60 fs following the CTTS excitation of "free" I- in THF. The absorption kinetics are identical at all probe wavelengths, indicating that the ejected electrons appear with no significant dynamic solvation but rather with their equilibrium absorption spectrum. After their initial appearance, ejected electrons do not exhibit any additional dynamics on time scales up to approximately 1 ns, indicating that geminate recombination of e-THF with its iodine atom partner does not occur. Competitive electron scavenging measurements demonstrate that the CTTS excited state of I- in THF is quite large and has contact with scavengers that are several nanometers away from the iodide ion. The ejection time and lack of electron solvation observed for I- in THF are similar to what is observed following CTTS excitation of Na- in THF. However, the relatively slow ejection time, the complete lack of dynamic solvation, and the large ejection distance/lack of recombination dynamics are in marked contrast to the CTTS

  13. Effect of Crystallizable Solvent on Phase Separation and Charge Transport in Polymer-fullerene Films

    NASA Astrophysics Data System (ADS)

    Kaewprajak, A.; Lohawet, K.; Wutikhun, T.; Meemuk, B.; Kumnorkaew, P.; Sagawa, T.

    2017-09-01

    The effect of 1,3,5-trichlorobenzene (TCB) as crystallizable solvent on poly[N-9‧-heptadecanyl-2,7-carbazole-alt-5,5-(4‧,7‧-di-2-thienyl-2‧,1‧,3‧-benzothiadiazole)] (PCDTBT) and [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) bulk heterojunction (BHJ) was investigated. We found that phase separation of PCDTBT and PC71BM and formation of the condensed network of polymers were appropriately regulated by addition of TCB in the BHJ films, which were confirmed by optical microscopic, AFM, and TEM observations in addition to current-voltage analyses. Through the formation of a good continuous pathway for carrier transport by the addition of TCB, 2.5 times enhancement of the hole mobility in the BHJ film was attained from 5.82 × 10‑5 cm2 V‑1 s‑1 without TCB to 1.48 × 10‑4 cm2 V‑1 s‑1 with 20 mg ml‑1 of TCB.

  14. Charge separation in a covalently-linked phthalocyanine-oligo(p-phenylenevinylene)-C60 system. Influence of the solvent polarity.

    PubMed

    Cid, Juan-José; Kahnt, Axel; Vázquez, Purificación; Guldi, Dirk M; Torres, Tomás

    2012-03-01

    A photo- and redoxactive system ZnPc-oPPV-C(60)2, in which the photoexcited state electron donor - zinc phthalocyanine - and the ground state electron acceptor - C(60) - are connected by a oligo(p-phenylenevinylene) (oPPV) spacer, has been synthesized in a multi-step synthesis by means of two consecutive Wadsworth-Horner-Emmons and a dipolar 1,3-cycloaddition reactions as key steps. The simpler system ZnPc-C(60)1 has also been prepared as a reference model for photophysical studies. In this regards, the photophysical investigations by means of fluorescence, flash photolysis, and transient-absorption spectroscopy have manifested a clear dependence between charge transfer kinetics and spatial arrangement. In both systems, intramolecular charge separation evolves from the photoexcited ZnPc and yields the ZnPc(·+)/C(60)(·-) radical ion pairs. Interestingly, the ZnPc(·+)/C(60)(·-) radical ion pair lifetimes and quantum yields are strongly impacted by the solvent polarity and the distance. To this end, maximum radical ion pair lifetimes of 2900 and 5530 ps were found in anisol for 1 and 2, respectively.

  15. The effect of solvent polarity on the balance between charge transfer and non-charge transfer pathways in the sensitization of singlet oxygen by pipi triplet states.

    PubMed

    Schmidt, Reinhard

    2006-05-11

    A large set of literature kinetic data on triplet (T(1)) sensitization of singlet oxygen by two series of biphenyl and naphthalene sensitizers in solvents of strongly different polarity has been analyzed. The rate constants and the efficiencies of singlet oxygen formation are quantitatively reproduced by a model that assumes the competition of a non-charge transfer (nCT) and a CT deactivation channel. nCT deactivation occurs from a fully established spin-statistical equilibrium of (1)(T(1)(3)Sigma) and (3)(T(1)(3)Sigma) encounter complexes by internal conversion (IC) to lower excited complexes that dissociate to yield O(2)((1)Sigma(g)(+)), O(2)((1)Delta(g)), and O(2)((3)Sigma(g)(-)). IC of (1,3)(T(1)(3)Sigma) encounter complexes is controlled by an energy gap law that is generally valid for the transfer of electronic energy to and from O(2). (1,3)(T(1)(3)Sigma) nCT complexes form in competition to IC (1)(T(1)(3)Sigma) and (3)(T(1)(3)Sigma) exciplexes if CT interactions between T(1) and O(2) are important. The rate constants of exciplex formation depend via a Marcus type parabolic model on the corresponding free energy change DeltaG(CT), which varies with sensitizer triplet energy, oxidation potential, and solvent polarity. O(2)((1)Sigma(g)(+)), O(2)((1)Delta(g)), and O(2)((3)Sigma(g)(-)) are formed in the product ratio (1/6):(1/12):(3/4) in the CT deactivation channel. The balance between nCT and CT deactivation is described by the relative contribution p(CT) of CT induced deactivation calculated for a sensitizer of known triplet energy from its quenching rate constant. It is shown how the change of p(CT) influences the quenching rate constant and the efficiency of singlet oxygen formation in both series of sensitizers. p(CT) is sensitive to differences of solvent polarity and varies for the biphenyls and the naphthalenes as sigmoidal with DeltaG(CT). This quantitative model represents a realistic and general mechanism for the quenching of pipi triplet states by O

  16. 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

  17. 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.

  18. Effect of droplet shape on ring stains from dried liquid

    NASA Astrophysics Data System (ADS)

    Santiago, Melvin; Brown, Katherine; Mathur, Harsh

    A landmark experimental paper on coffee stains by Deegan et al included a simple theoretical analysis of circular droplets. The analysis was based on a model informally called the Maxwell House equations. It describes the evolving height profile of the droplet, the evaporation of the solvent and the outflow of solute to the rim of the droplet. Since typical droplets are not circles, here we extend the analysis to more general shapes. We find that for thin droplets the height profile may be determined by solving Poisson's equation in a domain corresponding to the footprint of the droplet. Evaporation is treated in a simple approximation via an electrostatic analogy and is dominated by the sharp edges of the droplet. Assuming zero vorticity allows us to analyze the solvent flow in droplets of arbitrary shape. We compare circular droplets to other shapes including long linear droplets, ring shaped droplets and droplets with an elliptical footprint

  19. 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.

  20. Determination of fungicides in fruit juice by ultrasound-assisted dispersive liquid-liquid microextraction based on solidification of floating organic solvent droplets followed by high performance liquid chromatography.

    PubMed

    Fan, Run-Zhen; Liu, Congyun; Jiang, Wenqing; Wang, Xiaonan; Liu, Fengmao

    2014-01-01

    Ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) based on solidification of the floating organic solvent droplets (SFO) combined with HPLC was used for determination of five fungicides in fruit juice samples. 1-Dodecanol, which has a low density and low toxicity, was used as the extraction solvent in UA-DLLME. The solidification of floating organic droplets facilitates the transfer of analytes from the aqueous phase to the organic phase. This method was easy, quick, inexpensive, precise, and linear over a wide range. Under the optimized conditions, the enrichment factors for a 5 mL fruit juice sample were 25 to 56, and the LODs for the five fungicides ranged from 5 to 50 microg/L. The average recoveries ranged from 71.8 to 118.2% with RSDs of 0.9 to 13.9%. Application of the DLLME-SFO technique allows successful separation and preconcentration of the fungicides at a low concentration level in fruit juice samples.

  1. Intramolecular charge transfer and dielectric solvent relaxation in n-propyl cyanide. N-phenylpyrrole and 4-dimethylamino-4'-cyanostilbene.

    PubMed

    Druzhinin, Sergey I; Galievsky, Victor A; Yoshihara, Toshitada; Zachariasse, Klaas A

    2006-11-30

    Fast intramolecular charge transfer (ICT) accompanied by dual fluorescence from a locally excited (LE) and an ICT state taking place with N-phenylpyrrole (PP) in the solvent n-propyl cyanide (PrCN) is investigated as a function of temperature between 25 and -112 degrees C. The LE and ICT fluorescence decays from -45 to -70 degrees C can be adequately fitted with two exponentials, in accordance with a two state (LE + ICT) reaction mechanism, similar to what has been observed with PP in the more polar and less viscous alkyl cyanides acetonitrile (MeCN) and ethyl cyanide (EtCN). At lower temperatures, triple-exponential fits are required for the LE and ICT decays. The ICT emission band maximum of the time-resolved fluorescence spectra of PP in PrCN at -100 degrees C displays a spectral shift from 29 230 cm-1 at t = 0 to 27 780 cm-1 at infinite time, which equilibration process is attributed to dielectric solvent relaxation. From the time dependence of this shift, in global analysis with that of the band integrals BI(LE) and BI(ICT) of the time-resolved LE and ICT fluorescence bands, the decay times 119 and 456 ps are obtained. Dielectric relaxation times of 20 and 138 ps are determined from the double-exponential spectral solvation response function C(t) of the probe molecule 4-dimethylamino-4'-cyanostilbene in PrCN at -100 degrees C. It is concluded from the similarity of the times 119 ps (PP) and 138 ps (DCS) that the deviation from double-exponential character for the fluorescence decays of PP in PrCN below -70 degrees C is due to the interference of dielectric solvent relaxation with the ICT reaction. This fact complicates the kinetic analysis of the LE and ICT fluorescence decays. The kinetic analysis for PP in PrCN is hence restricted to temperatures between -70 and -45 degrees C. From this analysis, the forward and backward ICT activation energies Ea (12 kJ/mol) and Ed (17 kJ/mol) are obtained, giving an ICT stabilization enthalpy -DeltaH of 5 kJ/mol. A

  2. 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

    SciTech Connect

    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 BF4- counterions to the simulation. At each SOC the packing of PTMA, the solvent, and the counterions 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.

  3. 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 BF4- counterions to the simulation. At each SOC the packing of PTMA, the solvent, and the counterions were examined.more » 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

  4. On the Field Dependence of Free Charge Carrier Generation and Recombination in Blends of PCPDTBT/PC70BM: Influence of Solvent Additives.

    PubMed

    Albrecht, Steve; Schindler, Wolfram; Kurpiers, Jona; Kniepert, Juliane; Blakesley, James C; Dumsch, Ines; Allard, Sybille; Fostiropoulos, Konstantinos; Scherf, Ullrich; Neher, Dieter

    2012-03-01

    We have applied time-delayed collection field (TDCF) and charge extraction by linearly increasing voltage (CELIV) to investigate the photogeneration, transport, and recombination of charge carriers in blends composed of PCPDTBT/PC70BM processed with and without the solvent additive diiodooctane. The results suggest that the solvent additive has severe impacts on the elementary processes involved in the photon to collected electron conversion in these blends. First, a pronounced field dependence of the free carrier generation is found for both blends, where the field dependence is stronger without the additive. Second, the fate of charge carriers in both blends can be described with a rather high bimolecular recombination coefficients, which increase with decreasing internal field. Third, the mobility is three to four times higher with the additive. Both blends show a negative field dependence of mobility, which we suggest to cause bias-dependent recombination coefficients.

  5. Solvent-drop Assisted Mechanochemical Synthesis of the Black and Green Polymorphs of the Tetrathiafulvalene-chloranil Charge Transfer Salt

    SciTech Connect

    S Benjamin; S Pagola; Z Huba; E Carpenter; T Abdel-Fattah

    2011-12-31

    This work describes the synthesis of the green and black polymorphic forms of the tetrathiafulvalene-chloranil (TTF-CA) charge transfer salt as pure phases, by solvent-assisted mechanochemistry. Both materials were characterized using laboratory and high-resolution X-ray powder diffraction (XRPD), elemental analysis and scanning electron microscopy (SEM). The high-resolution XRPD pattern of the TTF-CA black polymorph was indexed with a triclinic lattice a = 10.756(5) {angstrom}, b = 11.057(4) {angstrom}, c = 6.614(2) {angstrom}, {alpha} = 101.36(2){sup o}, {beta} = 93.69(3){sup o}, {gamma} = 89.37(3){sup o}, V = 769.6(5) {angstrom}{sup 3}. The chemical stability of these phases upon heating was investigated using thermogravimetric analysis (TGA), elemental analysis and X-ray powder diffraction (XRPD), indicating that both polymorphs undergo chemical decomposition, and ruling out the transition to an air-stable high temperature polymorph.

  6. Dynamical calculations of charge-transfer-to-solvent excited states of small I- (CH3CN)n clusters.

    PubMed

    Takayanagi, Toshiyuki

    2006-06-08

    Relaxation dynamics of photoexcited charge-transfer-to-solvent (CTTS) states for the I(-)(CH(3)CN)(n) (n = 2 and 3) clusters has been theoretically studied using electronic structure methods. First, we have calculated several lowest singlet and triplet potential energy surfaces using the multireference configuration interaction method. It was found that the character of the singlet CTTS excited-state potential surfaces is very similar to that of the triplet CTTS states. Due to a small singlet-triplet splitting, the lowest triplet potential energy surface was used as a good model to understand the dynamics of the photoexcited singlet CTTS states. We have carried out direct molecular dynamics simulations on the lowest triplet surface at the B3LYP level. When an I(-) anion is exteriorly solvated by CH(3)CN molecules, we found that the (CH(3)CN)(n)(-) anion cluster is effectively produced. In addition, when the I(-) anion is placed in the interior in I(-)(CH(3)CN)(n) clusters, photoexcitation gives an acetonitrile monomer anion plus neutral monomers. However, if the initial geometric configuration is distorted from the minimum structure, we also found that the (CH(3)CN)(2)(-) anion cluster, where an excess electron is internally trapped, is formed via I(-)(CH(3)CN)(2) + hnu --> I + (CH(3)CN)(2)(-) process.

  7. Intramolecular charge transfer with crystal violet lactone in acetonitrile as a function of temperature: reaction is not solvent-controlled.

    PubMed

    Druzhinin, Sergey I; Demeter, Attila; Zachariasse, Klaas A

    2013-08-22

    Intramolecular charge transfer (ICT) with crystal violet lactone (CVL) in the excited singlet state takes place in solvents more polar than n-hexane, such as ethyl acetate, tetrahydrofuran, and acetonitrile (MeCN). In these solvents, the fluorescence spectrum of CVL consists of two emission bands, from a locally excited (LE) and an ICT state. The dominant deactivation channel of the lowest excited singlet state is internal conversion, as the quantum yields of fluorescence (0.007) and intersystem crossing (0.015) in MeCN at 25 °C are very small. CVL is a weakly coupled electron donor/acceptor (D/A) molecule, similar to an exciplex (1)(A(-)D(+)). A solvatochromic treatment of the LE and ICT emission maxima results in the dipole moments μe(LE) = 17 D and μe(ICT) = 33 D, much larger than those previously reported. This discrepancy is attributed to different Onsager radii and spectral fluorimeter calibration. The LE and ICT fluorescence decays of CVL in MeCN are double exponential. As determined by global analysis, the LE and ICT decays at 25 °C have the times τ2 = 9.2 ps and τ1 = 1180 ps, with an amplitude ratio of 35.3 for LE. From these parameters, the rate constants ka = 106 × 10(9) s(-1) and kd = 3.0 × 10(9) s(-1) of the forward and backward reaction in the LE ⇄ ICT equilibrium are calculated, resulting in a free enthalpy difference ΔG of -8.9 kJ/mol. The amplitude ratio of the ICT fluorescence decay equals -1.0, which signifies that the ICT state is not prepared by light absorption in the S0 ground state, but originates exclusively from the directly excited LE precursor. From the temperature dependence of the fluorescence decays of CVL in MeCN (-45 to 75 °C), activation energies E(a) = 3.9 kJ/mol (LE → ICT) and E(d) = 23.6 kJ/mol (ICT → LE) are obtained, giving an enthalpy difference ΔH (= E(a) - E(d)) of -19.7 kJ/mol, and an entropy difference ΔS = -35.5 J mol(-1) K(-1). These data show that the ICT reaction of CVL in MeCN is not barrierless

  8. Ultrafast charge-transfer-to-solvent dynamics of iodide in tetrahydrofuran. 2. Photoinduced electron transfer to counterions in solution.

    PubMed

    Bragg, Arthur E; Schwartz, Benjamin J

    2008-04-24

    The excited states of atomic anions in liquids are bound only by the polarization of the surrounding solvent. Thus, the electron-detachment process following excitation to one of these solvent-bound states, known as charge-transfer-to-solvent (CTTS) states, provides a useful probe of solvent structure and dynamics. These transitions and subsequent relaxation dynamics also are influenced by other factors that alter the solution environment local to the CTTS anion, including the presence of cosolutes, cosolvents, and other ions. In this paper, we examine the ultrafast CTTS dynamics of iodide in liquid tetrahydrofuran (THF) with a particular focus on how the solvent dynamics and the CTTS electron-ejection process are altered in the presence of various counterions. In weakly polar solvents such as THF, iodide salts can be strongly ion-paired in solution; the steady-state UV-visible absorption spectroscopy of various iodide salts in liquid THF indicates that the degree of ion-pairing changes from strong to weak to none as the counterion is switched from Na+ to tetrabutylammonium (t-BA+) to crown-ether-complexed Na+, respectively. In our ultrafast experiments, we have excited the I- CTTS transition of these various iodide salts at 263 nm and probed the dynamics of the CTTS-detached electrons throughout the visible and near-IR. In the previous paper of this series (Bragg, A. E.; Schwartz, B. J. J. Phys. Chem. B 2008, 112, 483-494), we found that for "counterion-free" I- (obtained by complexing Na+ with a crown ether) the CTTS electrons were ejected approximately 6 nm from their partner iodine atoms, the result of significant nonadiabatic coupling between the CTTS excited state and extended electronic states supported by the naturally existing solvent cavities in liquid THF, which also serve as pre-existing electron traps. In contrast, for the highly ion-paired NaI/THF system, we find that approximately 90% of the CTTS electrons are "captured" by a nearby Na+ to form (Na

  9. An experimental and theoretical study of solvent hydrogen-bond-donating capacity effects on ultrafast intramolecular charge transfer of LD 490

    NASA Astrophysics Data System (ADS)

    Li, Hui; Yin, Hang; Liu, Xiaochun; Shi, Ying; Jin, Mingxing; Ding, Dajun

    2017-09-01

    The excited-state intramolecular charge transfer (ICT) of LD 490 were investigated in different hydrogen-bond-donating solvents (α scale) on the basis of the Kamlet-Taft solvatochromic parameters (π*, α, β). The femtosecond transient absorption spectra and the kinetics decay rate reveal that with an increase of solvent's α capacity, the long-lived picosecond process, which is attributed to the ICT, becomes much faster. Combining with time-dependent density functional theory (TDDFT) calculations, we demonstrate that the enhancement of α acidity substantially increases the electronegativity of the carbonyl oxygen in LD 490, which strengthen excited-state intermolecular hydrogen bonding interactions and consequently facilitate the ICT process.

  10. A perspective on MALDI alternatives-total solvent-free analysis and electron transfer dissociation of highly charged ions by laserspray ionization.

    PubMed

    Trimpin, Sarah

    2010-05-01

    Progress in research is hindered by analytical limitations, especially in biological areas in which sensitivity and dynamic range are critical to success. Inherent difficulties of characterization associated with complexity arising from heterogeneity of various materials including topologies (isomeric composition) and insolubility also limit progress. For this reason, we are developing methods for total solvent-free analysis by mass spectrometry consisting of solvent-free ionization followed by solvent-free gas-phase separation. We also recently constructed a novel matrix-assisted laser desorption ionization (MALDI) source that provides a simple, practical and sensitive way of producing highly charged ions by laserspray ionization (LSI) or singly charged ions commonly observed with MALDI by choice of matrix or matrix preparation. This is the first ionization source with such freedom-an extremely powerful analytical 'switch'. Multiply charged LSI ions allow molecules exceeding the mass-to-charge range of the instrument to be observed and permit for the first time electron transfer dissociation fragment ion analysis.

  11. Solvent-dependent intramolecular charge transfer dual fluorescence of p-dimethylaminobenzanilide bearing steric ortho,ortho-dimethyl substituents at amido aniline.

    PubMed

    Zhang, Xuan; Jiang, Yun-Bao

    2011-11-01

    Intramolecular charge transfer (ICT) dual fluorescence was observed in various organic solvents with p-dimethylaminobenzanilide (DMBA) derivatives bearing ortho-methyl (DMOMBA) and ortho,ortho-dimethyl (DMDMBA) substituents at amido aniline moiety. Ab initio calculation and absorption spectral data indicated that high steric hindrance was introduced by the ortho,ortho-dimethyl substitutions. It was found that, with DMDMBA, the CT emission initially shifted to the red with increasing solvent polarity from cyclohexane (CHX, 480 nm) to diethyl ether (DEE, 520 nm), similar to those of DMBA derivatives with the ortho-, meta- or para-methyl substitutions at amido aniline moiety. However, there is a characteristic blue-shift of the long wavelength emission between DEE and tetrahydrofuran (THF, 424 nm) then a bathochromic shift again in highly polar solvent acetonitrile (ACN, 484 nm). The unusual solvent-dependent CT emission was ascribed to two competitive CT channels. One is benzanilide (BA)-like CT, whose CT reaction occurs from amido aniline to benzoyl moiety in nonpolar solvent CHX and DEE; the other one is p-dimethylaminobenzamide (DMABA)-like, whose CT reaction occurs from dimethylamino to benzanilide moiety in highly polar solvent THF and ACN. These findings revealed the steric effect plays an important role in the ICT process, which may alter the properties of the electron donor and/or acceptor, but also change the reaction potential.

  12. Solvent bandwidth dependence and band asymmetry features of charge-transfer transitions in N-pyridinium phenolates

    SciTech Connect

    Kjaer, A.M.; Ulstrup, J.

    1987-04-01

    They have investigated the shape of the solvatochromic absorption band for Betaine-26 2,4,6-triphenyl-N-(di-tert-butyl-4-hydroxyphenyl)pyridinium ion in a range of polar, apolar, protic, and aprotic solvents. Multiphonon band theory, including both molecular modes and a vibrationally dispersive solvent, indicates that the solvents fall in three categories: (1) The bandshape for polar, aprotic solvents is well reproduced by that for a structureless continuous dielectric and a single high-frequency molecular mode. Solvent broadening correlates with epsilon/sub o//sup -1/ - epsilon/sub s//sup -1/, epsilon/sub o/ being the optical and epsilon/sub s/ the static dielectric constant. The molecular frequency, Omega/sub c/, and displacement, ..delta../sub c/, are not very solvent dependent, emphasizing their molecular character, and the value Omega/sub c/ approx. = 1600 cm/sup -1/ suggests that C-O, C-N, and C-C stretching is involved. (2) Bands for apolar, aprotic solvents correspond to the same model. Omega/sub c/ and ..delta../sub c/ are again not very solvent dependent and coincide with the values for polar aprotic solvents. The solvent broadening is solvent independent, and wider than that for a structureless dielectric. This points to multipolar, dispersive, pressure, or pseudopotential forces as coupling mechanisms. (3) The bandshape for normal alcohols can only be produced by a model resting on two molecular modes and a vibrational high-frequency solvent tail. Broadening, asymmetry, molecular frequencies, and deuterium isotope effects trace the protic solvent spectral entanglement to coupling between betaine-26 and a local mode group with features of both O-H stretching and bending and of librational solvent motion.

  13. High-Voltage Droplet Dispenser

    NASA Technical Reports Server (NTRS)

    Eichenberg, Dennis J.

    2003-01-01

    An apparatus that is extremely effective in dispensing a wide range of droplets has been developed. This droplet dispenser is unique in that it utilizes a droplet bias voltage, as well as an ionization pulse, to release a droplet. Apparatuses that deploy individual droplets have been used in many applications, including, notably, study of combustion of liquid fuels. Experiments on isolated droplets are useful in that they enable the study of droplet phenomena under well-controlled and simplified conditions. In this apparatus, a syringe dispenses a known value of liquid, which emerges from, and hangs onto, the outer end of a flat-tipped, stainless steel needle. Somewhat below the needle tip and droplet is a ring electrode. A bias high voltage, followed by a high-voltage pulse, is applied so as to attract the droplet sufficiently to pull it off the needle. The voltages are such that the droplet and needle are negatively charged and the ring electrode is positively charged.

  14. 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.

  15. Spectrophotometric studies on the charge-transfer interaction between p-nitroaniline with chloranilic acid as π-acceptor in different polar solvents

    NASA Astrophysics Data System (ADS)

    Singh, Neeti; Ahmad, Afaq

    2017-01-01

    The charge transfer interaction between the donor p-nitroaniline with the acceptor chloranilic acid has been studied spectrophotometrically in various solvents such as chloroform, ethanol, and methanol at room temperature. The results indicate that formation of CTC in non-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 (KCT), molar extinction coefficient (εCT), standard free energy (ΔG), oscillator strength (f), transition dipole moment (μN), resonance energy (RN) and ionization potential (ID). The results indicate that the formation constant (KCT) for the complex was shown to be dependent upon the nature of electron acceptor, donor and polarity of solvents that were used. The formation of the complex has been confirmed by UV-visible, FT-IR, and 1H NMR techniques.

  16. Two-Dimensional Self-Assembly and Chemical Synthesis of Charged Gold Nanoparticles in Non-Polar Solvents

    NASA Astrophysics Data System (ADS)

    Martin, Matthew Nichols

    Gold nanoparticles between 1 and 10 nm in diameter exhibit size-dependent electronic and optical properties that cannot be explained by molecular science and which deviate significantly from their bulk counterparts. For example, the melting temperature of gold nanoparticles less than 5 nm in diameter is around 300 °C [1], whereas bulk gold melts at over 1000 °C [2]. Gold nanoparticles require precise control over particle diameter in order to exploit and tailor their unique properties; however, tuning the size reproducibly and predictably has proved to be a challenge. One of the most difficult obstacles to overcome is nanoparticle aggregation, since nanoparticles flocculate at room temperature quite readily. In 1994, Brust et al. solved the aggregation problem by introducing monolayer protection coatings on gold nanoparticles, in which organic ligand molecules are attached to the nanoparticle surface and create a physical barrier between the gold core and solvent. This was a definitive solution to size stability, since nanoparticles never aggregate, however the synthesis method does not generate monodisperse nanoparticles and has poor size-tuning capabilities. We developed a synthesis method for gold nanoparticles that improves greatly upon the Brust method. Starting from scratch, we discovered a "sweet zone" for aqueous gold nanoparticles, revealing how to make "naked" (stabilizer-free) gold nanoparticles which are continuously and precisely controlled between 3.2 and 5.2 nm in diameter, both reproducibly and predictably. Naked nanoparticles are then coated with organic 1-dodecanethiol ligand molecules, and transferred to hexane. Since all reaction byproducts remain in the water-phase, no postsynthesis cleaning or size-filtering is necessary, reducing the total synthesis time from ~24 hours in the Brust method, to less than 10 minutes. Surprisingly, our nanoparticles are highly negatively charged in nonpolar solvents. This unexpectedly caused nanoparticles to be

  17. A Study of the Crystallizations Possible on the Surface of a Spherical Droplet Using Coulomb Interactions Between Point Charges

    DTIC Science & Technology

    1990-01-01

    of any commercial products. This report may not be cited for purposes of advertisement. Reproduction of this document in whole or in part is...symer.Fo the~ ~ ~ ~ left N 2 2 2 ’All Fiur 4 Euiibiu Fgue wthfie-ol rtaioa planes. N -67(n h lf) n -77. - S.12 at least part of a hemisphere. Examples of...subtracted is then U2 - 2Tr* Integrall 0 (Phi*Sigma d&) where Phi is the potential due to the point charge at the center of the bare area and is

  18. Raman and theoretical study of the solvent effects on the sizable intramolecular charge transfer in the push-pull 5-(dimethylamino)-5'-nitro-2,2'-bithiophene.

    PubMed

    Ortí, Enrique; Viruela, Pedro M; Viruela, Rafael; Effenberger, Franz; Hernandez, Víctor; López Navarrete, Juan T

    2005-10-06

    In this paper, we analyze the degree of intramolecular charge transfer in a push-pull pi-conjugated system, 5-(dimethylamino)-5'-nitro-2,2'-bithiophene, from changes in frequencies and relative intensities of its strongest Raman scatterings in a bunch of solvents with different polarities. Density functional theory (DFT) was used as a support of the experimental study. Solvent effects on the molecular and electronic structures and on the vibrational properties were estimated by performing B3LYP/6-31G calculations within the framework of the polarized continuum model (PCM) developed by Tomasi. Calculations reveal that the molecule is highly polarized in the ground state and behaves as a very efficient photoinduced push-pull system. The polarization of the molecule strongly increases with solvent polarity and determines that the profile of the Raman spectra greatly changes from one solvent to another and in going to the solid. The strongest Raman scattering associated with the nu(sym)(NO(2)) stretching undergoes a downshift of 48 cm(-1) in passing from CCl(4) to the solid. DFT calculations provide a comprehensive interpretation of the evolution of the Raman spectra with solvent polarity.

  19. 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.

  20. Mechanism of the intramolecular charge transfer state formation in all-trans-β-apo-8'-carotenal: influence of solvent polarity and polarizability.

    PubMed

    Ragnoni, Elena; Di Donato, Mariangela; Iagatti, Alessandro; Lapini, Andrea; Righini, Roberto

    2015-01-15

    In this work we analyzed the infrared and visible transient absorption spectra of all-trans-β-apo-8'-carotenal in several solvents, differing in both polarity and polarizability at different excitation wavelengths. We correlate the solvent dependence of the kinetics and the band shape changes in the infrared with that of the excited state absorption bands in the visible, and we show that the information obtained in the two spectral regions is complementary. All the collected time-resolved data can be interpreted in the frame of a recently proposed relaxation scheme, according to which the major contributor to the intramolecular charge transfer (ICT) state is the bright 1Bu(+) state, which, in polar solvents, is dynamically stabilized through molecular distortions and solvent relaxation. A careful investigation of the solvent effects on the visible and infrared excited state bands demonstrates that both solvent polarity and polarizability have to be considered in order to rationalize the excited state relaxation of trans-8'-apo-β-carotenal and clarify the role and the nature of the ICT state in this molecule. The experimental observations reported in this work can be interpreted by considering that at the Franck-Condon geometry the wave functions of the S1 and S2 excited states have a mixed ionic/covalent character. The degree of mixing depends on solvent polarity, but it can be dynamically modified by the effect of polarizability. Finally, the effect of different excitation wavelengths on the kinetics and spectral dynamics can be interpreted in terms of photoselection of a subpopulation of partially distorted molecules.

  1. Solvent dependence on bond length alternation and charge distribution in phenol blue: a Car-Parrinello molecular dynamics investigation.

    PubMed

    Murugan, N Arul; Rinkevicius, Zilvinas; Agren, Hans

    2009-04-30

    Car-Parrinello mixed quantum mechanics/classical mechanics (CP-QM/MM) calculations are performed for phenol blue (PB) in chloroform and water solvents along with Car-Parrinello molecular dynamics (CPMD) calculations on PB in the gas phase. The solvent effect on molecular geometry, particularly of bond length alternation (BLA), has been studied. As reported for similar donor-acceptor polyenic systems, a remarkable solvent effect is seen on the BLA. The calculated BLA parameter suggests that PB is in the neutral form in the gas phase and in chloroform solvent, while in water, it is cyanine-like, which is a mixture of neutral and zwitterionic resonant forms, something that clarifies the controversial reports on the structure of PB in chloroform. We have also verified that the structures obtained from CPMD and CP-QM/MM calculations are correct by calculating absorption spectra for PB in the gas phase and in chloroform solvent and compared with experimental results. To understand the structure for PB in the gas phase and in water solvent, we have carried out Mayer bond order analysis, supporting that the structure of PB in water is cyanine-like. Moreover, PB in water is found to be much more polarized than that in chloroform solvent. Overall, the present work demonstrates that CP-QM/MM calculations can be used to understand the solvent effects on polyenic and merocyanine-like systems, which are usually difficult to model.

  2. A novel extraction method for β-carotene and other carotenoids in fruit juices using air-assisted, low-density solvent-based liquid-liquid microextraction and solidified floating organic droplets.

    PubMed

    Sricharoen, Phitchan; Limchoowong, Nunticha; Techawongstien, Suchila; Chanthai, Saksit

    2016-07-15

    Green extraction using air-assisted, low-density solvent-based liquid-liquid microextraction and solidified floating organic droplets (AA-LDS-LLME-SFOD) prior to spectrophotometry was successfully applied for quantitation of carotenoids in fruit juices. Under optimal conditions, β-carotene could be quantified with a linear response up to a concentration of 60 μg mL(-1). The procedure was performed in a microcentrifuge tube with 40 μL of 1-dodecanol as the extraction solvent and a 1.0 mL juice sample containing 8% NaCl under seven extraction cycles of air pumping by syringe. This method was validated based on linearity (0.2-30 μg mL(-1), R(2) 0.998), limit of detection (0.04 μg mL(-1)) and limit of quantification (0.13 μg mL(-1)). The precision, expressed as the relative standard deviation (RSD) of the calibration curve slope (n=12), for inter-day and intra-day analysis was 4.85% and 7.92%, respectively. Recovery of β-carotene was in the range of 93.6-101.5%. The newly proposed method is simple, rapid and environmentally friendly, particularly as a useful screening test for food analysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Dancing Droplets

    NASA Astrophysics Data System (ADS)

    Cira, Nate; Prakash, Manu

    2013-11-01

    Inspired by the observation of intricate and beautifully dynamic patterns generated by food coloring on corona treated glass slides, we have investigated the behavior of propylene glycol and water droplets on clean glass surfaces. These droplets exhibit a range of interesting behaviors including long distance attraction or repulsion, and chasing/fleeing upon contact. We present explanations for each of these behaviors, and propose a detailed model for the long distance interactions based on vapor facilitated coupling. Finally we use our understanding to create several novel devices which: passively sort droplets by surface tension, spontaneously align droplets, drive droplets in circles, and cause droplets to bounce on a vertical surface. The simplicity of this system lends it particularly well to application as a toy model for physical systems with force fields and biological systems such as chemotaxis and motility.

  4. Solvent effects on the metal-to-ligand charge transfer transition of the complex [Ru(NH3)5(Pyrazine)]2+

    NASA Astrophysics Data System (ADS)

    Chagas, Marcelo A.; Rocha, Willian R.

    2014-09-01

    In this work the solvent effects on the structure and metal-to-ligand charge transfer (MLCT) transition of the complex [Ru(NH3)5(Pyrazine)]2+ was investigated in aqueous solution, using the hybrid Density Functional Theory/Effective Fragment Potential Hamiltonian (DFT/EFP/MD) approach. The MLCT transition causes a large charge separation in the complex and produces a dipole moment variation of 8.3 ± 1.1 Debye upon excitation in solution and causes a large red-shift of 0.55 ± 0.15 eV. The solvatochromic shift can be attributed to the large charge separation accompanying the MLCT transition in solution.

  5. Short-range and long-range solvent effects on charge-transfer-to-solvent transitions of I- and K+I- contact ion pair dissolved in supercritical ammonia.

    PubMed

    Sciaini, G; Fernández-Prini, R; Estrin, D A; Marceca, E

    2007-05-07

    Vertical excitation and electron detachment energies associated with the optical absorption of iodide ions dissolved in supercritical ammonia at 420 K have been calculated in two limiting scenarios: as a solvated free I- ion and forming a K+I- contact ion pair (CIP). The evolution of the transition energies as a result of the gradual building up of the solvation structure was studied for each absorbing species as the solvent's density increased, i.e., changing the NH3 supercritical thermodynamic state. In both cases, if the solvent density is sufficiently high, photon absorption produces a spatially extended electron charge beyond the volume occupied by the solvated solute core; this excited state resembles a typical charge-transfer-to-solvent (CTTS) state. A combination of classical molecular dynamics simulations followed by quantum mechanical calculations for the ground, first-excited, and electron-detached electronic states have been carried out for the system consisting of one donor species (free I- ion or K+I- CIP) surrounded by ammonia molecules. Vertical excitation and electron detachment energies were obtained by averaging 100 randomly chosen microconfigurations along the molecular dynamics trajectory computed for each thermodynamic condition (fluid density). Short- and long-range contributions of the solvent-donor interaction upon the CTTS states of I- and K+I- were identified by performing additional electronic structure calculations where only the solvent interaction due to the first neighbor molecules was taken into account. These computations, together with previous experimental evidence that we collected for the system, have been used to analyze the solvent effects on the CTTS transition. In this paper we have established the following: (i) the CTTS electron of free I- ion or K+I- CIP presents similar features, and it gradually localizes in close proximity of the iodine parent atom when the ammonia density is increased; (ii) for the free I- ion, the

  6. Photoinduced charge generation rates in soluble P3HT : PCBM nano-aggregates predict the solvent-dependent film morphology.

    PubMed

    Roy, Palas; Jha, Ajay; Dasgupta, Jyotishman

    2016-02-07

    The device efficiency of bulk heterojunction (BHJ) solar cells is critically dependent on the nano-morphology of the solution-processed polymer : fullerene blend. Active control on blend morphology can only emanate from a detailed understanding of solution structures during the film casting process. Here we use photoinduced charge transfer (CT) rates to probe the effective length scale of the pre-formed solution structures and their energy disorder arising from a mixture of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) in three different organic solvents. The observed solvent-dependent ultrafast biphasic rise of the transient polaron state in solution along with changes detected in the C=C stretching frequency of bound PCBM provides direct evidence for film-like P3HT : PCBM interfaces in solution. Using the diffusive component of the charge transfer rate, we deduce ∼3-times larger functional nano-domain size in toluene than in chlorobenzene thereby correctly predicting the relative polymer nanofiber widths observed in annealed films. We thus provide first experimental evidence for the postulated polymer : fullerene : solvent ternary phase that seeds the eventual morphology in spin-cast films. Our work motivates the design of new chemical additives to tune the grain size of the evolving polymer : fullerene domains within the solution phase.

  7. First principles multielectron mixed quantum/classical simulations in the condensed phase. II. The charge-transfer-to-solvent states of sodium anions in liquid tetrahydrofuran.

    PubMed

    Glover, William J; Larsen, Ross E; Schwartz, Benjamin J

    2010-04-14

    Gas-phase atomic anions lack bound electronic excited states, yet in solution many of these anions exhibit intense absorption bands due to the presence of excited states, referred to as charge-transfer-to-solvent (CTTS) states that are bound only by the presence of the solvent. CTTS spectra thus serve as delicate probes of solute-solvent interactions, but the fact that they are created by the interactions of a solute with many solvent molecules makes them a challenge to describe theoretically. In this paper, we use mixed quantum/classical molecular dynamics with the two-electron Fourier-grid (2EFG) electronic structure method presented in the previous paper [W. J. Glover, R. E. Larsen, and B. J. Schwartz, J. Chem. Phys. 132, 144101 (2010)] to simulate the CTTS states of a sodium anion in liquid tetrahydrofuran, Na(-)/THF. Since our 2EFG method is based on configuration interaction with single and double excitations in a grid basis, it allows for an exact treatment of the two valence electrons of the sodium anion. To simulate Na(-)/THF, we first develop a new electron-THF pseudopotential, and we verify the accuracy of this potential by reproducing the experimental absorption spectrum of an excess electron in liquid THF with near quantitative accuracy. We also are able to reproduce the CTTS spectrum of Na(-)/THF and find that the CTTS states of Na(-) exhibit a Rydberg-like progression due to the pre-existing long-range solvent polarization around the anion. We also find that the CTTS states are highly mixed with the disjoint electronic states supported by naturally occurring solvent cavities that exist in liquid THF. This mixing explains why the solvated electrons that are ejected following CTTS excitation appear with their equilibrium absorption spectrum. The mixing of the CTTS and solvent-cavity states also explains why the recombination of the electron and its geminate Na(0) partner occurs on slower time scales when photoexciting in the blue compared to in the red

  8. Morphological transition of the host-structure influences solvent-relaxation: a wavelength-selective fluorescence exploration through environment-sensitive intramolecular charge transfer photophysics.

    PubMed

    Paul, Bijan Kumar; Guchhait, Nikhil

    2011-10-15

    Here, we report the modulation of photo-induced intramolecular charge transfer (ICT) photophysics of N,N-dimethylaminonaphthyl-acrylo-nitrile (DMANAN) associated with sphere-to-rod structural transition of SDS micelles induced by increasing ionic strength of the medium. Emphasis is rendered on the exploration of solvent-relaxation associated with this transition on the basis of wavelength-selective fluorescence technique which includes monitoring of red-edge excitation shift (REES) and excitation/emission anisotropy profiles. Based on micropolarity determination and organization of solvent water around the probe microenvironment we argue that the present results advocate for rod-shaped micelles to be a better mimic for membrane bilayers than spherical micelles. Copyright © 2011 Elsevier B.V. All rights reserved.

  9. Morphological transition of the host-structure influences solvent-relaxation: A wavelength-selective fluorescence exploration through environment-sensitive intramolecular charge transfer photophysics

    NASA Astrophysics Data System (ADS)

    Paul, Bijan Kumar; Guchhait, Nikhil

    2011-10-01

    Here, we report the modulation of photo-induced intramolecular charge transfer (ICT) photophysics of N,N-dimethylaminonaphthyl-acrylo-nitrile (DMANAN) associated with sphere-to-rod structural transition of SDS micelles induced by increasing ionic strength of the medium. Emphasis is rendered on the exploration of solvent-relaxation associated with this transition on the basis of wavelength-selective fluorescence technique which includes monitoring of red-edge excitation shift (REES) and excitation/emission anisotropy profiles. Based on micropolarity determination and organization of solvent water around the probe microenvironment we argue that the present results advocate for rod-shaped micelles to be a better mimic for membrane bilayers than spherical micelles.

  10. Charge-induced conformational changes of PEG-(Na(+))(n) in a vacuum and aqueous nanodroplets.

    PubMed

    Consta, Styliani; Chung, Jun Kyung

    2011-09-08

    Charged-induced conformational changes of sodiated poly(ethylene glycol) (PEG-(Na(+))(n)) in a vacuum and water droplets were studied using molecular simulations. In a vacuum, compact and partially unwound conformations were identified by analyzing occupation probabilities on reaction surfaces defined by the accessible surface area of the macroion, the distance between the centers of mass of the PEG molecule and of the cations and radius of gyration of the macromolecule. The critical charge of the macromolecule for which there is coexistence of various conformations was estimated using the Rayleigh criterion for the breakdown of highly charged droplets and compared with that observed in the simulations. The simulation findings agreed well with the Rayleigh prediction. The properties of sodiated PEG macromolecules in the presence of solvent and ions were also investigated. It was found that the macroion becomes saturated with charge. The highly charged state leads to an extended conformation that is partially expelled by the droplet. However, a portion of the chain is still in contact with the solvent. Drying-out of the solvent leaves the macroion in a stretched necklace-like conformation. The mechanism of release of sodiated PEG from an aqueous droplet was shown to be distinctly different from that of a protonated polyhistidine in a water nanodroplet, demonstrating sensitivity of the disintegration mechanism of the nanodroplet to the degree of hydrophilicity of the macroion.

  11. Manipulating the production and recombination of electrons during electron transfer: Femtosecond control of the charge-transfer-to-solvent (CTTS) dynamics of the sodium anion.

    PubMed

    Martini, Ignacio B; Barthel, Erik R; Schwartz, Benjamin J

    2002-06-26

    The scavenging of a solvated electron represents the simplest possible electron-transfer (ET) reaction. In this work, we show how a sequence of femtosecond laser pulses can be used to manipulate an ET reaction that has only electronic degrees of freedom: the scavenging of a solvated electron by a single atom in solution. Solvated electrons in tetrahydrofuran are created via photodetachment using the charge-transfer-to-solvent (CTTS) transition of sodide (Na(-)). The CTTS process ejects electrons to well-defined distances, leading to three possible initial geometries for the back ET reaction between the solvated electrons and their geminate sodium atom partners (Na(0)). Electrons that are ejected within the same solvent cavity as the sodium atom (immediate contact pairs) undergo back ET in approximately 1 ps. Electrons ejected one solvent shell away from the Na(0) (solvent-separated contact pairs) take hundreds of picoseconds to undergo back ET. Electrons ejected more than one solvent shell from the sodium atom (free solvated electrons) do not recombine on subnanosecond time scales. We manipulate the back ET reaction for each of these geometries by applying a "re-excitation" pulse to promote the localized solvated electron ground state into a highly delocalized excited-state wave function in the fluid's conduction band. We find that re-excitation of electrons in immediate contact pairs suppresses the back ET reaction. The kinetics at different probe wavelengths and in different solvents suggest that the recombination is suppressed because the excited electrons can relocalize into different solvent cavities upon relaxation to the ground state. Roughly one-third of the re-excited electrons do not collapse back into their original solvent cavities, and of these, the majority relocalize into a cavity one solvent shell away. In contrast to the behavior of the immediate pair electrons, re-excitation of electrons in solvent-separated contact pairs leads to an early time

  12. Charging free energy calculations using the Generalized Solvent Boundary Potential (GSBP) and periodic boundary condition: a comparative analysis using ion solvation and oxidation free energy in proteins.

    PubMed

    Lu, Xiya; Cui, Qiang

    2013-02-21

    Free energy simulations using a finite sphere boundary condition rather than a periodic boundary condition (PBC) are attractive in the study of very large biomolecular systems. To understand the quantitative impact of various approximations in such simulations, we compare charging free energies in both solution and protein systems calculated in a linear response framework with the Generalized Solvent Boundary Potential (GSBP) and PBC simulations. For simple ions in solution, we find good agreements between GSBP and PBC charging free energies, once the relevant correction terms are taken into consideration. For PBC simulations with the particle-mesh-Ewald for long-range electrostatics, the contribution (ΔG(P-M)) due to the use of a particle rather than molecule based summation scheme in real space is found to be significant, as pointed out by Hünenberger and co-workers. For GSBP, when the inner region is close to be charge neutral, the key correction is the overpolarization of water molecules at the inner/outer dielectric boundary; the magnitude of the correction (ΔG(s-pol)), however, is relatively small. For charging (oxidation) free energy in proteins, the situation is more complex, although good agreement between GSBP and PBC can still be obtained when care is exercised. The smooth dielectric boundary approximation inherent to GSBP tends to make significant errors when the inner region is featured with a high net charge. However, the error can be corrected with Poisson-Boltzmann calculations using snapshots from GSBP simulations in a straightforward and robust manner. Because of the more complex charge and solvent distributions, the magnitudes of ΔG(P-M) and ΔG(s-pol) in protein simulations appear to be different from those derived for solution simulations, leading to uncertainty in directly comparing absolute charging free energies from PBC and GSBP simulations for protein systems. The relative charging/oxidation free energies, however, are robust. With the

  13. Altering the self-organization of dyes on titania with dyeing solvents to tune the charge-transfer dynamics of sensitized solar cells.

    PubMed

    Wang, Yinglin; Yang, Lin; Zhang, Jing; Li, Renzhi; Zhang, Min; Wang, Peng

    2014-04-14

    Herein we selected the model organic donor-acceptor dye C218 and modulated the self-organization of dye molecules on the surface of titania by changing the dyeing solvent from chlorobenzene to a mixture of acetonitrile and tert-butanol. We further unveiled the relationship between the microstructure of a dye layer and the multichannel charge-transfer dynamics that underlie the photovoltaic performance of dye-sensitized solar cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Microscopic solvation and femtochemistry of charge-transfer reactions: the problem of benzene(s)-iodine binary complexes and their solvent structures

    NASA Astrophysics Data System (ADS)

    Cheng, P. Y.; Zhong, D.; Zewail, A. H.

    1995-08-01

    Charge-transfer reactions are studied on the femtosecond and picosecond time scales and under controlled composition in a molecular beam. The system of interest is iodine in aromatic and non-aromatic solvents, which goes back to Hildebrand and Mulliken almost 50 years ago. For the first time, the isolated binary complex and its solvated structural dynamics are studied. The product iodine atoms are positively identified and the concept of harpoon mechanism introduced. The dynamics are related to the impact geometry of the transition state and the electronic structure. A global potential energy surface is described with molecular dynamics detailing the motion in the reaction coordinates.

  15. Persisting Water Droplets on Water Surfaces†

    PubMed Central

    Klyuzhin, Ivan S.; Ienna, Federico; Roeder, Brandon; Wexler, Adam; Pollack, Gerald H.

    2011-01-01

    Droplets of various liquids may float on the respective surfaces for extended periods of time prior to coalescence. We explored the features of delayed coalescence in highly purified water. Droplets several millimeters in diameter were released from a nozzle onto a water surface. Results showed that droplets had float times up to hundreds of milliseconds. When the droplets did coalesce, they did so in stepwise fashion, with periods of quiescence interspersed between periods of coalescence. Up to six steps were noted before the droplet finally vanished. Droplets were released in a series, which allowed the detection of unexpected abrupt float-time changes throughout the duration of the series. Factors such as electrostatic charge, droplet size, and sideways motion had considerable effect on droplet lifetime, as did reduction of pressure, which also diminished the number of steps needed for coalescence. On the basis of present observations and recent reports, a possible mechanism for noncoalescence is considered. PMID:20961076

  16. Droplet Handling

    NASA Astrophysics Data System (ADS)

    Torii, Toru

    When quantitative analysis or quantitative chemical synthesis is performed using a micrototal analysis system (microTAS), the technologies for precise metering, transporting, and mixing of droplets are required. In this chapter, several technologies for the handling of droplets are described. For metering, dispensing and transporting of droplets, pneumatic and electrokinetic forces are used. Separation of cells and particles is also performed by electrical operation. Other handling technique, such as ultrasonic or centrifugal force applications, are also reviewed. Robotic synthesis devices or high throughput screening devices are promising applications for these technologies.

  17. Droplet handling.

    PubMed

    Torii, Toru

    2010-01-01

    When quantitative analysis or quantitative chemical synthesis is performed using a micrototal analysis system (microTAS), the technologies for precise metering, transporting, and mixing of droplets are required. In this chapter, several technologies for the handling of droplets are described. For metering, dispensing and transporting of droplets, pneumatic and electrokinetic forces are used. Separation of cells and particles is also performed by electrical operation. Other handling technique, such as ultrasonic or centrifugal force applications, are also reviewed. Robotic synthesis devices or high throughput screening devices are promising applications for these technologies.

  18. Dynamics of charge recombination processes in the singlet electron-transfer state of pyrene-pyromellitic dianhydride systems in various solvents. Picosecond laser photolysis studies

    SciTech Connect

    Mataga, N.; Shioyama, H.; Kanda, Y.

    1987-01-15

    In order to elucidate the underlying mechanisms showing that no dissociated ion radicals are produced even in acetonitrile solution when some complexes of the strong electron donors and acceptors with CT absorption bands in the visible region are photoexcited, the authors have made detailed time-resolved transient absorption spectral measurements and time-resolved fluorescence measurements upon the pyrene-pyromellitic dianhydride (PMDA) system in various solvents with picosecond laser spectroscopy. A weakly fluorescent electron-transfer (ET) state with 400-ps lifetime is formed by photoexcitation in benzene solution, while nonfluorescent geminate ion pairs with much shorter lifetimes due to the charge recombination (CR) deactivation are formed in more polar solvents. In all solutions examined, dissociation into free ions from the geminate pair cannot compete with the CR deactivation which becomes faster in more polar solvents due to the decrease of the energy gap between the ion pair and neutral ground state. Moreover, it has been demonstrated that ion pairs produced by encounter between excited pyrene and unexcited PMDA in acetonitrile have more loose structure and show a smaller CR rate constant than those produced by exciting the ground-state complex.

  19. Intramolecular charge transfer and trans-cis isomerization of the DCM styrene dye in polar solvents. A CS INDO MRCI study

    NASA Astrophysics Data System (ADS)

    Marguet, S.; Mialocq, J. C.; Millie, P.; Berthier, G.; Momicchioli, F.

    1992-03-01

    The solvent-induced changes of trans-cis isomerization efficiency and electronic structure of the excited state of the DCM dye have been considered by means of CS INDO MRCI calculations. The potential energy curves, dipole moments and atomic charge densities as a function of two internal coordinates, namely the rotation angle about the central "double" bond and the twisting of the dimethylamino group, have been obtained for the ground state and the lowest excited states. The structural requirements for the existence of ICT (intramolecular charge transfer) excited states have been investigated by considering internal rotations about three single bonds. The reliability of the potential surfaces and of the solvation models has been discussed with reference to test-calculations on the DMABN molecule. In the first excited singlet state of DCM, the low-energy barrier for the trans-cis isomerization has been found unaffected by the solvent polarity. The only singlet excited state presenting a large ICT character has been found to be the S 2 state for a perpendicularly twisted conformation of the dimethylamino group (TICT state). The assumption of a deactivation of the trans-isomer in the locally excited state through the TICT funnel has been largely discussed with reference to the simplifications of the present theoretical approach.

  20. Splashing Droplets

    NASA Technical Reports Server (NTRS)

    VanderWal, Randall L.; Kizito, John Patrick; Berger, Gordon M.; Iwan, J.; Alexander, D.; Tryggvason, Gretar

    2002-01-01

    Current data on droplet breakup is scarce for the sizes and velocities typical of practical applications such as in spray combustion processes and coating processes. While much more representative of practical applications, the small spatial scales and rapid time-scales prevent detailed measurement of the internal fluid dynamics and liquid property gradients produced by impinging upon surfaces. Realized through the extended spatial and temporal scales afforded by a microgravity environment, an improved understanding of drop breakup dynamics is sought to understand and ultimately control the impingement dynamics of droplets upon surfaces in practical situations. The primary objective of this research will be to mark the onset of different 'splashing modes' and to determine their temperature, pressure and angle dependence for impinging droplets representative of practical fluids. In addition, we are modeling the evolution of droplets that do not initially splash but rather undergo a 'fingering' evolution observed on the spreading fluid front and the transformation of these fingers into splashed products. An example of our experimental data is presented below. These images are of Isopar V impacting a mirror-polished surface. They were acquired using a high-speed camera at 1000 frames per second. They show the spreading of a single droplet after impact and ensuing finger instabilities. Normal gravity experimental data such as this will guide low gravity measurements in the 2.2 second drop tower and KC-135 aircraft as available. Presently we are in the process of comparing the experimental data of droplet shape evolution to numerical models, which can also capture the internal fluid dynamics and liquid property gradients such as produced by impingement upon a heated surface. To-date isothermal numerical data has been modeled using direct numerical simulations of representative splashing droplets. The data obtained so far indicates that the present model describes well

  1. Charge-transfer-to-solvent reactions from I- to water, methanol, and ethanol studied by time-resolved photoelectron spectroscopy of liquids

    NASA Astrophysics Data System (ADS)

    Okuyama, Haruki; Suzuki, Yoshi-Ichi; Karashima, Shutaro; Suzuki, Toshinori

    2016-08-01

    The charge-transfer-to-solvent (CTTS) reactions from iodide (I-) to H2O, D2O, methanol, and ethanol were studied by time-resolved photoelectron spectroscopy of liquid microjets using a magnetic bottle time-of-flight spectrometer with variable pass energy. Photoexcited iodide dissociates into a weak complex (a contact pair) of a solvated electron and an iodine atom in similar reaction times, 0.3 ps in H2O and D2O and 0.5 ps in methanol and ethanol, which are much shorter than their dielectric relaxation times. The results indicate that solvated electrons are formed with minimal solvent reorganization in the long-range solvent polarization field created for I-. The photoelectron spectra for CTTS in H2O and D2O—measured with higher accuracy than in our previous study [Y. I. Suzuki et al., Chem. Sci. 2, 1094 (2011)]—indicate that internal conversion yields from the photoexcited I-* (CTTS) state are less than 10%, while alcohols provide 2-3 times greater yields of internal conversion from I-*. The overall geminate recombination yields are found to be in the order of H2O > D2O > methanol > ethanol, which is opposite to the order of the mutual diffusion rates of an iodine atom and a solvated electron. This result is consistent with the transition state theory for an adiabatic outer-sphere electron transfer process, which predicts that the recombination reaction rate has a pre-exponential factor inversely proportional to a longitudinal solvent relaxation time.

  2. Charge-transfer-to-solvent reactions from I(-) to water, methanol, and ethanol studied by time-resolved photoelectron spectroscopy of liquids.

    PubMed

    Okuyama, Haruki; Suzuki, Yoshi-Ichi; Karashima, Shutaro; Suzuki, Toshinori

    2016-08-21

    The charge-transfer-to-solvent (CTTS) reactions from iodide (I(-)) to H2O, D2O, methanol, and ethanol were studied by time-resolved photoelectron spectroscopy of liquid microjets using a magnetic bottle time-of-flight spectrometer with variable pass energy. Photoexcited iodide dissociates into a weak complex (a contact pair) of a solvated electron and an iodine atom in similar reaction times, 0.3 ps in H2O and D2O and 0.5 ps in methanol and ethanol, which are much shorter than their dielectric relaxation times. The results indicate that solvated electrons are formed with minimal solvent reorganization in the long-range solvent polarization field created for I(-). The photoelectron spectra for CTTS in H2O and D2O-measured with higher accuracy than in our previous study [Y. I. Suzuki et al., Chem. Sci. 2, 1094 (2011)]-indicate that internal conversion yields from the photoexcited I(-*) (CTTS) state are less than 10%, while alcohols provide 2-3 times greater yields of internal conversion from I(-*). The overall geminate recombination yields are found to be in the order of H2O > D2O > methanol > ethanol, which is opposite to the order of the mutual diffusion rates of an iodine atom and a solvated electron. This result is consistent with the transition state theory for an adiabatic outer-sphere electron transfer process, which predicts that the recombination reaction rate has a pre-exponential factor inversely proportional to a longitudinal solvent relaxation time.

  3. Coarse-grained simulations of charge, current and flow in heterogeneous media.

    PubMed

    Rotenberg, Benjamin; Pagonabarraga, Ignacio; Frenkel, Daan

    2010-01-01

    We present a coarse-grained simulation method for complex charged systems. This mesoscopic model couples a hydrodynamic description to a free energy functional accounting for the interactions between solvent(s) and charged solutes. It is implemented in a hybrid lattice-based algorithm, whereby the evolution of the overall mass and momentum is taken care of via a Lattice Boltzmann scheme, whereas the composition and ionic concentrations are updated using the link-flux method. Several applications illustrate the power of this coarse-grained model for charged heterogeneous media: the transport of charged tracers in charged porous media, the deformation of an oil droplet in water under the effect of an applied electric field, and the distribution of ions at an oil-water interface as a function of their affinity for both solvents.

  4. High-Voltage Droplet Dispenser Developed

    NASA Technical Reports Server (NTRS)

    Eichenberg, Dennis J.; VanderWal, Randy L.

    2001-01-01

    Various techniques have been applied to deploying individual droplets for many applications, such as the study of the combustion of liquid fuels. Isolated droplet studies are useful in that they allow phenomena to be studied under well-controlled and simplified conditions. A high-voltage droplet dispenser has been developed that is extremely effective in dispensing a wide range of droplets. The dispenser is quite unique in that it utilizes a droplet bias voltage, as well as an ionization pulse, to release the droplet. The droplet is deployed from the end of a needle. A flat-tipped, stainless steel needle attached to a syringe dispenses a known value of liquid that hangs on the needle tip. Somewhat below the droplet is an annular ring electrode. A bias voltage, followed by a voltage pulse, is applied to attract the droplet sufficiently to pull it off the needle. The droplet and needle are oppositely charged relative to the annular electrode. The needle is negatively charged, and the annular ring is positively charged.

  5. 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.

  6. Droplet microactuator system

    NASA Technical Reports Server (NTRS)

    Pamula, Vamsee K. (Inventor); Srinivasan, Vijay (Inventor); Pollack, Michael G. (Inventor); Eckhardt, Allen E. (Inventor); Paik, Philip Y. (Inventor)

    2010-01-01

    The present invention relates to a droplet microactuator system. According to one embodiment, the droplet microactuator system includes: (a) a droplet microactuator configured to conduct droplet operations; (b) a magnetic field source arranged to immobilize magnetically responsive beads in a droplet during droplet operations; (c) a sensor configured in a sensing relationship with the droplet microactuator, such that the sensor is capable of sensing a signal from and/or a property of one or more droplets on the droplet microactuator; and (d) one or more processors electronically coupled to the droplet microactuator and programmed to control electrowetting-mediated droplet operations on the droplet actuator and process electronic signals from the sensor.

  7. A novel actuation technique for the on-demand injection of charge-free conducting droplets in a viscous dielectric liquid

    NASA Astrophysics Data System (ADS)

    Raisin, Jonathan; Atten, Pierre; Reboud, Jean-Luc

    2013-03-01

    The paper presents recent improvements and results on the on-demand injection of small electrically neutral water drops in oil by high electric field pulses. The technique consists in applying a voltage pulse promoting the deformation of a water meniscus at the end of a capillary tube through the action of electric forces. For pulses of calibrated energy, the transient deformation can lead to the inertia-based ejection of a small uncharged droplet. Application of in-house developed multi-stage electric pulses offers, in contrast to usual single pulses, wider ranges of droplet size, improved reproducibility and stable ejection trajectories. Influence of the main parameters on the extracted droplet diameter is presented: it is shown that, by using capillary tubes of outer tip diameter close to 0.5 mm, it is possible to obtain, in a reproducible way, drops of diameter ranging from less than 15 μm up to more than 250 μm.

  8. 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.

  9. Kinetics of complex plasma with liquid droplets

    NASA Astrophysics Data System (ADS)

    Misra, Shikha; Mishra, S. K.; Sodha, M. S.

    2013-12-01

    This paper provides a theoretical basis for the reduction of electron density by spray of water (or other liquids) in hot plasma. This phenomenon has been observed in a hypersonic flight experiment for relief of radio black out, caused by high ionization in the plasma sheath of a hypersonic vehicle, re-entering the atmosphere. The analysis incorporates a rather little known phenomenon for de-charging of the droplets, viz., evaporation of ions from the surface and includes the charge balance on the droplets and number cum energy balance of electrons, ions, and neutral molecules; the energy balance of the evaporating droplets has also been taken into account. The analysis has been applied to a realistic situation and the transient variations of the charge and radius of water droplets, and other plasma parameters have been obtained and discussed. The analysis through made in the context of water droplets is applicable to all liquids.

  10. Kinetics of complex plasma with liquid droplets

    SciTech Connect

    Misra, Shikha; Sodha, M. S.; Mishra, S. K.

    2013-12-15

    This paper provides a theoretical basis for the reduction of electron density by spray of water (or other liquids) in hot plasma. This phenomenon has been observed in a hypersonic flight experiment for relief of radio black out, caused by high ionization in the plasma sheath of a hypersonic vehicle, re-entering the atmosphere. The analysis incorporates a rather little known phenomenon for de-charging of the droplets, viz., evaporation of ions from the surface and includes the charge balance on the droplets and number cum energy balance of electrons, ions, and neutral molecules; the energy balance of the evaporating droplets has also been taken into account. The analysis has been applied to a realistic situation and the transient variations of the charge and radius of water droplets, and other plasma parameters have been obtained and discussed. The analysis through made in the context of water droplets is applicable to all liquids.

  11. Modular droplet actuator drive

    NASA Technical Reports Server (NTRS)

    Pollack, Michael G. (Inventor); Paik, Philip (Inventor)

    2011-01-01

    A droplet actuator drive including a detection apparatus for sensing a property of a droplet on a droplet actuator; circuitry for controlling the detection apparatus electronically coupled to the detection apparatus; a droplet actuator cartridge connector arranged so that when a droplet actuator cartridge electronically is coupled thereto: the droplet actuator cartridge is aligned with the detection apparatus; and the detection apparatus can sense the property of the droplet on a droplet actuator; circuitry for controlling a droplet actuator coupled to the droplet actuator connector; and the droplet actuator circuitry may be coupled to a processor.

  12. Determination of nicotine in tobacco with second-order spectra data of charge-transfer complex in ethanol-water binary solvents processed by parallel factor analysis.

    PubMed

    Gao, Shuqin; Liao, Lifu; Xiao, Xilin; Zhao, Zhiyuan; Du, Nan; Du, Jiangfeng

    2010-05-01

    A new spectrophotometric method for the determination of nicotine in mixtures without pre-separation has been proposed. Nicotine could react with 2,4-dinitrophenol through a charge-transfer reaction to form a colored complex. The second-order data from the visible absorption spectra of the complex in a series of ethanol-water binary solvents with various water volume fractions could be expressed as the combination of two bilinear data matrices. With the bilinear model, the second-order spectra data of mixtures containing nicotine and other interferents could be analysed by using second-order calibration algorithms, and the determination of nicotine in the mixtures could be achieved. The algorithm used here was parallel factor analysis. The method has been successfully used to determine nicotine in tobacco samples with satisfactory results.

  13. Determination of nicotine in tobacco with second-order spectra data of charge-transfer complex in ethanol-water binary solvents processed by parallel factor analysis

    NASA Astrophysics Data System (ADS)

    Gao, Shuqin; Liao, Lifu; Xiao, Xilin; Zhao, Zhiyuan; Du, Nan; Du, Jiangfeng

    2010-05-01

    A new spectrophotometric method for the determination of nicotine in mixtures without pre-separation has been proposed. Nicotine could react with 2,4-dinitrophenol through a charge-transfer reaction to form a colored complex. The second-order data from the visible absorption spectra of the complex in a series of ethanol-water binary solvents with various water volume fractions could be expressed as the combination of two bilinear data matrices. With the bilinear model, the second-order spectra data of mixtures containing nicotine and other interferents could be analysed by using second-order calibration algorithms, and the determination of nicotine in the mixtures could be achieved. The algorithm used here was parallel factor analysis. The method has been successfully used to determine nicotine in tobacco samples with satisfactory results.

  14. Charge-transfer-to-solvent-driven dissolution dynamics of I- (H2O)2-5 upon excitation: excited-state ab initio molecular dynamics simulations.

    PubMed

    Kołaski, Maciej; Lee, Han Myoung; Pak, Chaeho; Kim, Kwang S

    2008-01-09

    In contrast to the extensive theoretical investigation of the solvation phenomena, the dissolution phenomena have hardly been investigated theoretically. Upon the excitation of hydrated halides, which are important substances in atmospheric chemistry, an excess electron transfers from the anionic precursor (halide anion) to the solvent and is stabilized by the water cluster. This results in the dissociation of hydrated halides into halide radicals and electron-water clusters. Here we demonstrate the charge-transfer-to-solvent (CTTS)-driven femtosecond-scale dissolution dynamics for I-(H2O)n=2-5 clusters using excited state (ES) ab initio molecular dynamics (AIMD) simulations employing the complete-active-space self-consistent-field (CASSCF) method. This study shows that after the iodine radical is released from I-(H2O)n=2-5, a simple population decay is observed for small clusters (2 solvent molecules rearrange themselves to a lower free energy structure. The CTTS-driven dissolution dynamics could be useful in designing the receptors which are able to bind and release ions in host-guest chemistry.

  15. Solvent and temperature effects on diastereodifferentiating Paternó-Büchi reaction of chiral alkyl cyanobenzoates with diphenylethene upon direct versus charge-transfer excitation.

    PubMed

    Matsumura, Kazuyuki; Mori, Tadashi; Inoue, Yoshihisa

    2010-08-20

    In the Paternó-Büchi reaction of chiral p-cyanobenzoates (1) with 1,1-diphenylethene (2), we revealed that the excited charge-transfer (CT) complex formed upon selective excitation at the CT band is distinctly different in structure and reactivity from the conventional exciplex generated through the direct excitation of acceptor 1 which subsequently associates with donor 2. Thus, the favored diastereoface upon photocycloaddition, as well as the temperature- and solvent-dependent behavior of the product's diastereoselectivity, were highly contrasting, often opposite, to each other upon direct versus CT excitation. From the activation parameters obtained by the Eyring analyses of the diastereoselectivity, we are able to infer that the conventional exciplex is relatively flexible and susceptible to the environmental variants, whereas the CT complex is better pi-pi stacked and more rigid in the ground state and also in the excited state, leading to the significantly smaller differential activation enthalpies and entropies. More interestingly, the signs of the differential activation parameters determined for direct and CT excitation are consistently opposite to each other and the isokinetic temperatures calculated therefrom differ significantly, unambiguously revealing the distinctly different nature in structure and reactivity of these two excited-state complex species. Thus, the combined use of irradiation wavelength, temperature, and solvent provides us with a convenient, powerful tool not only for elucidating the mechanistic details of photoreaction but also for critically controlling the stereochemical outcomes of photochirogenic reaction.

  16. Detection of heavy-metal ions using liquid crystal droplet patterns modulated by interaction between negatively charged carboxylate and heavy-metal cations.

    PubMed

    Han, Gyeo-Re; Jang, Chang-Hyun

    2014-10-01

    Herein, we demonstrated a simple, sensitive, and rapid label-free detection method for heavy-metal (HM) ions using liquid crystal (LC) droplet patterns on a solid surface. Stearic-acid-doped LC droplet patterns were spontaneously generated on an n-octyltrichlorosilane (OTS)-treated glass substrate by evaporating a solution of the nematic LC, 4-cyano-4'-pentylbiphenyl (5CB), dissolved in heptane. The optical appearance of the droplet patterns was a dark crossed texture when in contact with air, which represents the homeotropic orientation of the LC. This was caused by the steric interaction between the LC molecules and the alkyl chains of the OTS-treated surface. The dark crossed appearance of the acid-doped LC patterns was maintained after the addition of phosphate buffered saline (PBS) solution (pH 8.1 at 25°C). The deprotonated stearic-acid molecules self-assembled through the LC/aqueous interface, thereby supporting the homeotropic anchoring of 5CB. However, the optical image of the acid-doped LC droplet patterns incubated with PBS containing HM ions appeared bright, indicating a planar orientation of 5CB at the aqueous/LC droplet interface. This dark to bright transition of the LC patterns was caused by HM ions attached to the deprotonated carboxylate moiety, followed by the sequential interruption of the self-assembly of the stearic acid at the LC/aqueous interface. The results showed that the acid-doped LC pattern system not only enabled the highly sensitive detection of HM ions at a sub-nanomolar concentration but it also facilitated rapid detection (<10 min) with simple procedures.

  17. 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.

  18. Nanospiral Formation by Droplet Drying: One Molecule at a Time.

    PubMed

    Wan, Lei; Li, Li; Mao, Guangzhao

    2011-12-01

    We have created nanospirals by self-assembly during droplet evaporation. The nanospirals, 60-70 nm in diameter, formed when solvent mixtures of methanol and m-cresol were used. In contrast, spin coating using only methanol as the solvent produced epitaxial films of stripe nanopatterns and using only m-cresol disordered structure. Due to the disparity in vapor pressure between the two solvents, droplets of m-cresol solution remaining on the substrate serve as templates for the self-assembly of carboxylic acid molecules, which in turn allows the visualization of solution droplet evaporation one molecule at a time.

  19. 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.

  20. Structural and thermodynamical properties of charged hard spheres in a mixture with core-softened model solvent.

    PubMed

    Lukšič, Miha; Hribar-Lee, Barbara; Vlachy, Vojko; Pizio, O

    2012-12-28

    The canonical Monte Carlo computer simulations and integral equation theory were applied to examine the structural and thermodynamic properties of a mixture of ions and a core-softened fluid molecules. The positive and negative ions forming a +1:-1 salt were modeled as charged hard spheres, immersed in the dielectric medium. It was shown previously that the core-softened fluid under study is characterized by a set of structural, thermodynamic, and dynamic anomalies. The principal objective of this work was to elucidate how the presence of ions alters this behavior. The structural properties of the mixtures are discussed in terms of the pair distribution functions; in addition, the pair contribution to the excess entropy was calculated. Thermodynamic properties are investigated by using the dependencies of energy and compressibility factor on density, composition of the mixture, and reduced temperature. The heat capacity was also evaluated. Our principal findings concern the description of structural anomalies in the mixture, the dependence of the temperature of maximum density on the ionic concentration, and establishing the regions delimiting the structural and thermodynamic anomalies of the model mixture.

  1. Foam droplet separation for nanoparticle synthesis

    NASA Astrophysics Data System (ADS)

    Tyree, Corey A.; Allen, Jonathan O.

    2008-03-01

    A novel approach to nanoparticle synthesis was developed whereby foam bubble bursting produced aerosol droplets, an approach patterned after the marine foam aerosol cycle. The droplets were dried to remove solvent, leaving nanometer-sized particles composed of precursor material. Nanoparticles composed of sodium chloride (mean diameter, bar{D}_p≈ 100 nm), phosphotungstic acid (bar{D}_p≈ 55 nm), and bovine insulin ({D}_p≈ 5-30 nm) were synthesized. Foam droplet separation can be carried out at ambient temperature and pressure. The `soft' nature of the process makes it compatible with a wide range of materials.

  2. 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.

  3. Electric-Field-Enhanced Jumping-Droplet Condensation

    NASA Astrophysics Data System (ADS)

    Miljkovic, Nenad; Preston, Daniel; Enright, Ryan; Limia, Alexander; Wang, Evelyn

    2013-11-01

    When condensed droplets coalesce on a superhydrophobic surface, the resulting droplet can jump due to the conversion of surface energy into kinetic energy. This frequent out-of-plane droplet jumping has the potential to enhance condensation heat and mass transfer. In this work, we demonstrated that these jumping droplets accumulate positive charge that can be used to further increase condensation heat transfer via electric fields. We studied droplet jumping dynamics on silanized nanostructured copper oxide surfaces. By characterizing the droplet trajectories under various applied external electric fields (0 - 50 V/cm), we show that condensation on superhydrophobic surfaces results in a buildup of negative surface charge (OH-) due to dissociated water ion adsorption on the superhydrophobic coating. Consequently, the opposite charge (H3O +) accumulates on the coalesced jumping droplet. Using this knowledge, we demonstrate electric-field-enhanced jumping droplet condensation whereby an external electric field opposes the droplet vapor flow entrainment towards the condensing surface to increase the droplet removal rate and overall surface heat transfer by 100% when compared to state-of-the-art dropwise condensing surfaces. This work not only shows significant condensation heat transfer enhancement through the passive charging of condensed droplets, but promises a low cost approach to increase efficiency for applications such as atmospheric water harvesting and dehumidification.

  4. Photofragment Coincidence Imaging of Small I- (H2O)n Clusters Excited to the Charge-transfer-to-solvent State

    SciTech Connect

    Neumark, D. E. Szpunar, K. E. Kautzman, A. E. Faulhaber, and D. M.; Kautzman, K.E.; Faulhaber, A.E.; Faulhaber, A.E.

    2005-11-09

    The photodissociation dynamics of small I{sup -}(H{sub 2}O){sub n} (n = 2-5) clusters excited to their charge-transfer-to-solvent (CTTS) states have been studied using photofragment coincidence imaging. Upon excitation to the CTTS state, two photodissociation channels were observed. The major channel ({approx}90%) is a 2-body process forming neutral I + (H{sub 2}O){sub n} photofragments, and the minor channel is a 3-body process forming I + (H{sub 2}O){sub n-1} + H{sub 2}O fragments. Both process display translational energy (P(E{sub T})) distributions peaking at E{sub T} = 0 with little available energy partitioned into translation. Clusters excited to the detachment continuum rather than to the CTTS state display the same two channels with similar P(E{sub T}) distributions. The observation of similar P(E{sub T}) distributions from the two sets of experiments suggests that in the CTTS experiments, I atom loss occurs after autodetachment of the excited (I(H{sub 2}O){sub n}{sup -})* cluster, or, less probably, that the presence of the excess electron has little effect on the departing I atom.

  5. Electron dynamics in charge-transfer-to-solvent states of aqueous chloride revealed by Cl- 2p resonant Auger-electron spectroscopy.

    PubMed

    Winter, Bernd; Aziz, Emad F; Ottosson, Niklas; Faubel, Manfred; Kosugi, Nobuhiro; Hertel, Ingolf V

    2008-06-04

    Charge-transfer-to-solvent (CTTS) excited states of aqueous chloride are studied by a novel experimental approach based on resonant inner-shell photoexcitation, Cl(-)aq 2p --> e(i), i = 1-4, which denotes a series of excitations to lowest and higher CTTS states. These states are clearly identified through the occurrence of characteristic spectator Auger decays to double Cl 3p valence-hole states, where the CTTS states can be more stabilized as compared to single Cl(-)aq 2p core excitations and optical valence excitations. Furthermore, we have found for the first time that the CTTS electron e(i) bound by a single Cl 2p hole not only behaves as a spectator e(i) --> e'(i), bound by a double valence-hole state before relaxation of the excited electron (i) itself, but also shows electron dynamics to the relaxed lowest state, e(i) --> e'(1*). This interpretation is supported by ab initio calculations. The key to performing photoelectron and Auger-electron spectroscopy studies from aqueous solutions is the use of a liquid microjet in ultrahigh vacuum in conjunction with synchrotron radiation.

  6. A Correction Method for Attenuated Total Reflection-Far Ultraviolet Spectra Via the Use of Charge Transfer to Solvent Band Intensities of Iodide in the Ultraviolet Region.

    PubMed

    Ikehata, Akifumi; Goto, Takeyoshi; Morisawa, Yusuke

    2017-07-01

    Attenuated total reflection (ATR) spectra, which are often used in IR analysis, can be transformed into extinction and refraction spectra by Kramers-Kronig transformation (KKT) with Fresnel equations. However, it is often difficult to obtain correct optical indices due to the inherent instrumental functions. This paper proposes a simple practical method for correction of KKT with two parameters, which include all the effects of the instrumental function. In order to obtain the parameters of the instrumental function, absorption ratios of charge transfer to solvent (CTTS) transitions of aqueous iodide ions observed at 195 nm and 230 nm were used as a standard. The absorption indices calculated from the ATR spectra with the parameters correspond reasonably well to those given by the transmittance spectra not only in the UV region but also in the far-ultraviolet (FUV, 120-200 nm) region. By applying the corrected KKT to the ATR-FUV spectra of aqueous potassium halide solutions in the range of 0-2 M, correct features of the absorption spectra of KCl and KBr, whose CTTS bands are thought to be observed in FUV region, were confirmed. It is possible to use the parameters representing the instrument function as long as the instrument is not changed.

  7. Emergence of charge-transfer-to-solvent band in the absorption spectra of hydrogen halides on ice nanoparticles: spectroscopic evidence for acidic dissociation.

    PubMed

    Oncák, Milan; Slavícek, Petr; Poterya, Viktoriya; Fárník, Michal; Buck, Udo

    2008-06-19

    Extensive ab initio calculations complemented by a photodissociation experiment at 193 nm elucidate the nature of hydrogen halide molecules bound on free ice nanoparticles. Electronic absorption spectra of small water clusters (up to 5 water molecules) and water clusters doped with hydrogen fluoride, hydrogen chloride and hydrogen bromide were calculated. The spectra were modeled at the time-dependent density functional (TDDFT) level of theory with the BHandHLYP functional using the reflection principle. We observe the emergence of a charge-transfer-to-solvent (CTTS) band in the absorption spectra upon the acidic dissociation of the hydrogen halides. The CTTS band provides a spectroscopically observable feature for the acidic dissociation. The calculated spectra were compared with our new experimental photodissociation data for larger water clusters doped with HCl and HBr. We conclude that HCl and HBr dissociate to a large extent on the surface of ice nanoparticles at temperatures near 120 K and photoactive products are formed. The acidic dissociation of HX leads to an enhancement by about 4 orders of magnitude of the HCl photolysis rate in the 200-300 nm region, which is potentially relevant for the halogen budget in the atmosphere.

  8. Photofragment coincidence imaging of small I-(H2O)n clusters excited to the charge-transfer-to-solvent state.

    PubMed

    Szpunar, David E; Kautzman, Kathryn E; Faulhaber, Ann Elise; Neumark, Daniel M

    2006-02-07

    The photodissociation dynamics of small I-(H2O)n(n=2-5) clusters excited to their charge-transfer-to-solvent (CTTS) states have been studied using photofragment coincidence imaging. Upon excitation to the CTTS state, two photodissociation channels were observed. The major channel (approximately 90%) is a two-body process forming neutral I+(H2O)n photofragments, and the minor channel is a three-body process forming I+(H2O)n-1+H2O fragments. Both processes display translational energy [P(ET)] distributions peaking at ET=0 with little available energy partitioned into translation. Clusters excited to the detachment continuum rather than to the CTTS state display the same two channels with similar P(ET) distributions. The observation of similar P(ET) distributions from the two sets of experiments suggests that in the CTTS experiments, I atom loss occurs after autodetachment of the excited [I(H2O)n-]* cluster or, less probably, that the presence of the excess electron has little effect on the departing I atom.

  9. Watching Na atoms solvate into (Na+,e-) contact pairs: untangling the ultrafast charge-transfer-to-solvent dynamics of Na- in tetrahydrofuran (THF).

    PubMed

    Cavanagh, Molly C; Larsen, Ross E; Schwartz, Benjamin J

    2007-06-21

    With the large dye molecules employed in typical studies of solvation dynamics, it is often difficult to separate the intramolecular relaxation of the dye from the relaxation associated with dynamic solvation. One way to avoid this difficulty is to study solvation dynamics using an atom as the solvation probe; because atoms have only electronic degrees of freedom, all of the observed spectroscopic dynamics must result from motions of the solvent. In this paper, we use ultrafast transient absorption spectroscopy to investigate the solvation dynamics of newly created sodium atoms that are formed following the charge transfer to solvent (CTTS) ejection of an electron from sodium anions (sodide) in liquid tetrahydrofuran (THF). Because the absorption spectra of the sodide reactant, the sodium atom, and the solvated electron products overlap, we first examined the dynamics of the ejected CTTS electron in the infrared to build a detailed model of the CTTS process that allowed us to subtract the spectroscopic contributions of the sodide bleach and the solvated electron and cleanly reveal the spectroscopy of the solvated atom. We find that the neutral sodium species created following CTTS excitation of sodide initially absorbs near 590 nm, the position of the gas-phase sodium D-line, suggesting that it only weakly interacts with the surrounding solvent. We then see a fast solvation process that causes a red-shift of the sodium atom's spectrum in approximately 230 fs, a time scale that matches well with the results of MD simulations of solvation dynamics in liquid THF. After the fast solvation is complete, the neutral sodium atoms undergo a chemical reaction that takes place in approximately 740 fs, as indicated by the observation of an isosbestic point and the creation of a species with a new spectrum. The spectrum of the species created after the reaction then red-shifts on a approximately 10-ps time scale to become the equilibrium spectrum of the THF-solvated sodium atom

  10. Mechanism of Charging and Supercharging Molecules in Electrospray Ionization

    PubMed Central

    Iavarone, Anthony T.; Williams*, Evan R.

    2005-01-01

    The origin of the extent of charging and the mechanism by which multiply charged ions are formed in electrospray ionization have been hotly debated for over a decade. Many factors can affect the number of charges on an analyte ion. Here, we investigate the extent of charging of poly(propyleneimine) dendrimers (generations 3.0 and 5.0), cytochrome c, poly(ethylene glycol)s, and 1,n-diaminoalkanes formed from solutions of different composition. We demonstrate that in the absence of other factors, the surface tension of the electrospray droplet late in the desolvation process is a significant factor in determining the overall analyte charge. For poly(ethylene glycol)s, 1,n-diaminoalkanes, and poly(propyleneimine) dendrimers electrosprayed from single-component solutions, there is a clear relationship between the analyte charge and the solvent surface tension. Addition of m-nitrobenzyl alcohol (m-NBA) into electrospray solutions increases the charging when the original solution has a lower surface tension than m-NBA, but the degree of charging decreases when this compound is added to water, which has a higher surface tension. Similarly, the charging of cytochrome c ions formed from acidified denaturing solutions generally increases with increasing surface tension of the least volatile solvent. For the dendrimers investigated, there is a strong correlation between the average charge state of the dendrimer and the Rayleigh limiting charge calculated for a droplet of the same size as the analyte molecule and with the surface tension of the electrospray solvent. A bimodal charge distribution is observed for larger dendrimers formed from water/m-NBA solutions, suggesting the presence of more than one conformation in solution. A similar correlation is found between the extent of charging for 1,n-diaminoalkanes and the calculated Rayleigh limiting charge. These results provide strong evidence that multiply charged organic ions are formed by the charged residue mechanism. A

  11. 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

  12. Correlating droplet size with temperature changes in electrospray source by optical methods.

    PubMed

    Soleilhac, Antonin; Dagany, Xavier; Dugourd, Philippe; Girod, Marion; Antoine, Rodolphe

    2015-08-18

    We investigated how the temperature and size of charged droplets are affected by the electrospray ionization (ESI) process, using in situ measurements involving laser-induced fluorescence and Mie scattering on a thermal gradient focusing ESI source. Rhodamine dyes were employed as temperature indicators using ratiometric intensity-based fluorescence techniques. The results were compared to lifetime-based techniques using tris(2,2'-bipyridyl)dichlororuthenium(II) hexahydrate, [Ru(bpy)3](2+). Both methods gave similar profiles. Nevertheless, the precision and sensitivity were higher for lifetime-based techniques in comparison to intensity-based techniques. Global warming (with ΔT ∼10 K) of the ESI plume is reported while the size of the droplet decreases along the plume. The global warming indicates that the conductive thermal transfer (between the superheated sheath gas and the solvent) is predominant and stronger than the cooling effect due to the evaporation of the droplets, and this outcome is effectively reproduced by a diffusion-controlled evaporation model. Thermal gradient focusing ESI sources therefore appear to be efficient sources for evaporating large amounts of solvent, along with an increase in temperature.

  13. 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.

  14. Effects of solvent, pH and β-cyclodextrin on the photophysical properties of 4-hydroxy-3,5-dimethoxybenzaldehyde: intramolecular charge transfer associated with hydrogen bonding effect

    NASA Astrophysics Data System (ADS)

    Stalin, T.; Rajendiran, N.

    2005-10-01

    The photophysical properties of 4-hydroxy-3,5-dimethoxybenzaldehyde (HDMB) in various solvents, pH and in aqueous β-cyclodextrin (CD) have been investigated. In non-polar solvents, HDMB gives only one emission maxima; whereas, in polar solvents it shows a dual luminescence. The increase in Stokes shift with increase in polarity is much more for longer wavelength (LW) than for a shorter wavelength (SW) band. This behaviour indicates the formation of an intramolecular charge transfer (ICT) state through relaxation from the normal excited state. Especially in water, the ICT emission is further red shifted to 430 nm with the normal emission band at 330 nm and the relative fluorescence intensities between 330 nm and 430 nm emission bands are affected by the excitation wavelength. However, this excitation wavelength dependence is not large in aqueous β-CD solutions. These results suggest that the ICT state in polar solvents/water is stabilized through exciplex formation by the hydrogen-bonding interaction between the carbonyl group and polar solvents/water. The ground and excited state p Ka values for the neutral-monoanion equilibrium have been measured and discussed. HDMB forms a 1:1 inclusion complex with β-CD. A mechanism is proposed to explain the inclusion process.

  15. Effects of solvent, pH and beta-cyclodextrin on the photophysical properties of 4-hydroxy-3,5-dimethoxybenzaldehyde: intramolecular charge transfer associated with hydrogen bonding effect.

    PubMed

    Stalin, T; Rajendiran, N

    2005-10-01

    The photophysical properties of 4-hydroxy-3,5-dimethoxybenzaldehyde (HDMB) in various solvents, pH and in aqueous beta-cyclodextrin (CD) have been investigated. In non-polar solvents, HDMB gives only one emission maxima; whereas, in polar solvents it shows a dual luminescence. The increase in Stokes shift with increase in polarity is much more for longer wavelength (LW) than for a shorter wavelength (SW) band. This behaviour indicates the formation of an intramolecular charge transfer (ICT) state through relaxation from the normal excited state. Especially in water, the ICT emission is further red shifted to 430 nm with the normal emission band at 330 nm and the relative fluorescence intensities between 330 nm and 430 nm emission bands are affected by the excitation wavelength. However, this excitation wavelength dependence is not large in aqueous beta-CD solutions. These results suggest that the ICT state in polar solvents/water is stabilized through exciplex formation by the hydrogen-bonding interaction between the carbonyl group and polar solvents/water. The ground and excited state pK(a) values for the neutral-monoanion equilibrium have been measured and discussed. HDMB forms a 1:1 inclusion complex with beta-CD. A mechanism is proposed to explain the inclusion process.

  16. Solvent alternatives guide

    SciTech Connect

    Elion, J.M.; Monroe, K.R.; Hill, E.A.

    1996-06-01

    It is no longer legal to manufacture or import chlorofluorocarbon 113 or methyl chloroform solvents, and companies that currently clean their parts with either material are now required to implement environmentally safe substitutes. To help find alternative methods, Research Triangle Institute`s Surface Cleaning Technology Program has designed a Solvent Alternatives Guide (SAGE), an online tool that enables access to practical information and recommendations for acceptable solvents. Developed in partnership with the US Environmental Protection Agency, SAGE is available free of charge on the Internet`s World Wide Web.

  17. A new droplet generator

    NASA Technical Reports Server (NTRS)

    Slack, W. E.

    1982-01-01

    A new droplet generator is described. A loud speaker driven extractor needle was immersed in a pendant drop. Pulsing the speaker extracted the needle forming a fluid ligament which will decay into a droplet. The droplets were sized by stroboscopic photographs. The droplet's size was changed by varying the amplitude of the speaker pulses and the extractor needle diameter. The mechanism of droplet formation is discussed and photographs of ligament decay are presented. The droplet generator worked well on both oil and water based pesticide formulations. Current applications and results are discussed.

  18. UV-Vis spectroscopy and density functional study of solvent effect on the charge transfer band of the n → σ* complexes of 2-Methylpyridine and 2-Chloropyridine with molecular iodine

    NASA Astrophysics Data System (ADS)

    Gogoi, Pallavi; Mohan, Uttam; Borpuzari, Manash Protim; Boruah, Abhijit; Baruah, Surjya Kumar

    2017-03-01

    UV-Vis spectroscopy has established that Pyridine substitutes form n→σ* charge transfer (CT) complexes with molecular Iodine. This study is a combined approach of purely experimental UV-Vis spectroscopy, Multiple linear regression theory and Computational chemistry to analyze the effect of solvent upon the charge transfer band of 2-Methylpyridine-I2 and 2-Chloropyridine-I2 complexes. Regression analysis verifies the dependence of the CT band upon different solvent parameters. Dielectric constant and refractive index are considered among the bulk solvent parameters and Hansen, Kamlet and Catalan parameters are taken into consideration at the molecular level. Density Functional Theory results explain well the blue shift of the CT bands in polar medium as an outcome of stronger donor acceptor interaction. A logarithmic relation between the bond length of the bridging atoms of the donor and the acceptor with the dielectric constant of the medium is established. Tauc plot and TDDFT study indicates a non-vertical electronic transition in the complexes. Buckingham and Lippert Mataga equations are applied to check the Polarizability effect on the CT band.

  19. Droplet fusion by alternating current (AC) field electrocoalescence in microchannels.

    PubMed

    Chabert, Max; Dorfman, Kevin D; Viovy, Jean-Louis

    2005-10-01

    We present a system for the electrocoalescence of microfluidic droplets immersed in an immiscible solvent, where the undeformed droplet diameters are comparable to the channel diameter. The electrodes are not in direct contact with the carrier liquid or the droplets, thereby minimizing the risk of cross-contamination between different coalescence events. Results are presented for the coalescence of buffered aqueous droplets in both quiescent and flowing fluorocarbon streams, and on-flight coalescence is demonstrated. The capillary-based system presented here is readily amenable to further miniaturization to any lab-on-a-chip application where the conductivity of the droplets is much greater than the conductivity of the stream containing them, and should aid in the further application of droplet microreactors to biological analyses.

  20. Directional electrostatic accretion process employing acoustic droplet formation

    NASA Technical Reports Server (NTRS)

    Oeftering, Richard C. (Inventor)

    1996-01-01

    The present invention is directed to an apparatus for manufacturing a free standing solid metal part. In the present invention metal droplets are produced from a free surface pool of molten metal is when an acoustic wave impacts an acoustic lens that is contiguous with the free standing pool of molten metal. The metal droplets are then charged and deflected toward a target. The build up of the metal droplets combine to form the free standing solid metal part.

  1. Electric field mediated spraying of miniaturized droplets inside microchannel.

    PubMed

    Timung, Seim; Chaudhuri, Joydip; Borthakur, Manash Pratim; Mandal, Tapas Kumar; Biswas, Gautam; Bandyopadhyay, Dipankar

    2017-06-01

    We report a facile and noninvasive way to disintegrate a microdroplet into a string of further miniaturized ones under the influence of an external electrohydrodynamic field inside a microchannel. The deformation and breakup of the droplet was engendered by the Maxwell's stress originating from the accumulation of induced and free charges at the oil-water interface. While at smaller field intensities, for example less than 1 MV/m, the droplet deformed into a plug, at relatively higher field intensities, e.g. ∼1.16 MV/m, a pair of droplets having opposite surface charge was formed. The charged droplets showed an interesting periodic bridging and breakup during their translation motion across the channel. For even higher field intensities, for example more than 1.2 MV/m, the entire droplet underwent dielectrophoresis toward one of the electrodes before experiencing a strong attractive force from the other electrode to deform into a shape of a Taylor cone. With progress in time, mimicking the electrospraying phenomenon, the cone tip periodically ejected a string of miniaturized water droplets to form a microemulsion inside the channel. The frequency and size of the droplet ejection could be tuned by varying the applied field intensity. A water droplet of ∼214 μm diameter could continuously eject droplets of size ∼10 μm or even smaller to form a microemulsion inside the channel. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. 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.

  3. Mechanisms of droplet combustion

    NASA Technical Reports Server (NTRS)

    Law, C. K.

    1982-01-01

    The fundamental physico-chemical mechanisms governing droplet vaporization and combustion are discussed. Specific topics include governing equations and simplifications, the classical d(2)-Law solution and its subsequent modification, finite-rate kinetics and the flame structure, droplet dynamics, near- and super-critical combustion, combustion of multicomponent fuel blends/emulsions/suspensions, and droplet interaction. Potential research topics are suggested.

  4. Salt stains from evaporating droplets

    PubMed Central

    Shahidzadeh, Noushine; Schut, Marthe F. L.; Desarnaud, Julie; Prat, Marc; Bonn, Daniel

    2015-01-01

    The study of the behavior of sessile droplets on solid substrates is not only associated with common everyday phenomena, such as the coffee stain effect, limescale deposits on our bathroom walls , but also very important in many applications such as purification of pharmaceuticals, de-icing of airplanes, inkjet printing and coating applications. In many of these processes, a phase change happens within the drop because of solvent evaporation, temperature changes or chemical reactions, which consequently lead to liquid to solid transitions in the droplets. Here we show that crystallization patterns of evaporating of water drops containing dissolved salts are different from the stains reported for evaporating colloidal suspensions. This happens because during the solvent evaporation, the salts crystallize and grow during the drying. Our results show that the patterns of the resulting salt crystal stains are mainly governed by wetting properties of the emerging crystal as well as the pathway of nucleation and growth, and are independent of the evaporation rate and thermal conductivity of the substrates. PMID:26012481

  5. Jumping-droplet electrostatic energy harvesting

    NASA Astrophysics Data System (ADS)

    Miljkovic, Nenad; Preston, Daniel J.; Enright, Ryan; Wang, Evelyn N.

    2014-07-01

    Micro- and nanoscale wetting phenomena have been an active area of research due to its potential for improving engineered system performance involving phase change. With the recent advancements in micro/nanofabrication techniques, structured surfaces can now be designed to allow condensing coalesced droplets to spontaneously jump off the surface due to the conversion of excess surface energy into kinetic energy. In addition to being removed at micrometric length scales (˜10 μm), jumping water droplets also attain a positive electrostatic charge (˜10-100 fC) from the hydrophobic coating/condensate interaction. In this work, we take advantage of this droplet charging to demonstrate jumping-droplet electrostatic energy harvesting. The charged droplets jump between superhydrophobic copper oxide and hydrophilic copper surfaces to create an electrostatic potential and generate power during formation of atmospheric dew. We demonstrated power densities of ˜15 pW/cm2, which, in the near term, can be improved to ˜1 μW/cm2. This work demonstrates a surface engineered platform that promises to be low cost and scalable for atmospheric energy harvesting and electric power generation.

  6. Single droplet separations and surface partition coefficient measurements using laser ablation mass spectrometry

    PubMed Central

    Jorabchi, Kaveh; Smith, Lloyd M.

    2010-01-01

    Surface activity of analytes plays a significant role in many chemical and physical phenomena. We present here a mass spectrometric method to characterize surface activity and solute partitioning between bulk liquid and the gas-liquid interface in droplets. The approach employs ablation by an IR laser from the surface of a microliter droplet deposited on a stainless steel post. The ablated material is ionized for mass spectrometric analysis by either droplet charging or by post-ionization in an electrospray plume. Three areas of application have been explored using this method; 1) separations in a single droplet: continuous ablation by a series of many successive laser pulses results in faster depletion of more surface active analytes, effectively comprising a surface activity-based separation. 2) Partition coefficient measurements: droplet volume is held constant during ablation by continually replenishing lost solvent. This leads to analyte-specific ion signal decay curves that may be fitted to a model based on Langmuir adsorption isotherms and simple analytical expressions, yielding quantitative values for the analyte surface partition coefficients. 3) Studies of the relationship between surface partitioning and HPLC phase partitioning: comparisons of surface activities measured by laser desorption with retention times in reversed phase HPLC reveal that the relationship between the two partitioning processes is very sensitive to chemical structure. Poor correlation between the retention time and surface activity is also observed within a subcategory of analytes (peptides). This effect is attributed to multi-modal solute-stationary phase interactions. The laser desorption approach presented here provides direct information on analyte surface activities free from the complications encountered in chromatographic methods due to chemical structure variations. PMID:19886638

  7. Patterning droplets with durotaxis

    PubMed Central

    Style, Robert W.; Che, Yonglu; Park, Su Ji; Weon, Byung Mook; Je, Jung Ho; Hyland, Callen; German, Guy K.; Power, Michael P.; Wilen, Larry A.; Wettlaufer, John S.; Dufresne, Eric R.

    2013-01-01

    Numerous cell types have shown a remarkable ability to detect and move along gradients in stiffness of an underlying substrate—a process known as durotaxis. The mechanisms underlying durotaxis are still unresolved, but generally believed to involve active sensing and locomotion. Here, we show that simple liquid droplets also undergo durotaxis. By modulating substrate stiffness, we obtain fine control of droplet position on soft, flat substrates. Unlike other control mechanisms, droplet durotaxis works without imposing chemical, thermal, electrical, or topographical gradients. We show that droplet durotaxis can be used to create large-scale droplet patterns and is potentially useful for many applications, such as microfluidics, thermal control, and microfabrication. PMID:23798415

  8. Ternary water-in-oil microemulsions made of cationic surfactants, water, and aromatic solvents. 3. Self-diffusion studies in relation to exchange of material between droplets and percolation

    SciTech Connect

    Zana, R.; Lang, J. ); Canet, D. )

    1991-04-18

    Ternary water-in-oil microemulsions using alkylbenzyldimethylammonium chloride (alkyl = dodecyl (N12), tetradecyl (N14), and hexadecyl (N16)) surfactants and benzene or chlorobenzene as oils have been investigated by means of electrical conductivity and NMR self-diffusion. The variations of the water self-diffusion coefficient with the (water)/(surfactant) molar concentration ratio {omega} and with the volume fraction of benzene in the oil mixture in water/(benzene + chlorobenzene)/N16 microemulsions are well correlated with the changes of electrical conductivity, as expected from a model of microemulsions where the water cores of the droplets become increasingly connected above the percolation threshold. These connections, however, have a strongly dynamic character. This model permits the authors to explain the widely differing magnitudes of the changes of electrical conductivity, water self-diffusion coefficient, and rate of exchange reactants between droplets upon increasing {omega}. The self-diffusion coefficient of the oil has been found to be about half that of the bulk oil, as in studies reported by others.

  9. Charge effects and nanoparticle pattern formation in electrohydrodynamic NanoDrip printing of colloids.

    PubMed

    Richner, Patrizia; Kress, Stephan J P; Norris, David J; Poulikakos, Dimos

    2016-03-21

    Advancing open atmosphere printing technologies to produce features in the nanoscale range has important and broad applications ranging from electronics to photonics, plasmonics and biology. Recently an electrohydrodynamic printing regime has been demonstrated in a rapid dripping mode (termed NanoDrip), where the ejected colloidal droplets from nozzles of diameters of O (1 μm) can controllably reach sizes an order of magnitude smaller than the nozzle and can generate planar and out-of-plane structures of similar sizes. Despite the demonstrated capabilities, our fundamental understanding of important aspects of the physics of NanoDrip printing needs further improvement. Here we address the topics of charge content and transport in NanoDrip printing. We employ quantum dot and gold nanoparticle dispersions in combination with a specially designed, auxiliary, asymmetric electric field, targeting the understanding of charge locality (particles vs. solvent) and particle distribution in the deposits as indicated by the dried nanoparticle patterns (footprints) on the substrate. We show that droplets of alternating charge can be spatially separated when applying an ac field to the nozzle. The nanoparticles within a droplet are distributed asymmetrically under the influence of the auxiliary lateral electric field, indicating that they are the main carriers. We also show that the ligand length of the nanoparticles in the colloid affects their mobility after deposition (in the sessile droplet state).

  10. Calculating the binding free energies of charged species based on explicit-solvent simulations employing lattice-sum methods: An accurate correction scheme for electrostatic finite-size effects

    PubMed Central

    Rocklin, Gabriel J.; Mobley, David L.; Dill, Ken A.; Hünenberger, Philippe H.

    2013-01-01

    calculations for a given system, its dependence on the box size being analytical. The latter scheme also provides insight into the physical origin of the finite-size effects. These two schemes also encompass a correction for discrete solvent effects that persists even in the limit of infinite box sizes. Application of either scheme essentially eliminates the size dependence of the corrected charging free energies (maximal deviation of 1.5 kJ mol−1). Because it is simple to apply, the analytical correction scheme offers a general solution to the problem of finite-size effects in free-energy calculations involving charged solutes, as encountered in calculations concerning, e.g., protein-ligand binding, biomolecular association, residue mutation, pKa and redox potential estimation, substrate transformation, solvation, and solvent-solvent partitioning. PMID:24320250

  11. Calculating the binding free energies of charged species based on explicit-solvent simulations employing lattice-sum methods: An accurate correction scheme for electrostatic finite-size effects

    NASA Astrophysics Data System (ADS)

    Rocklin, Gabriel J.; Mobley, David L.; Dill, Ken A.; Hünenberger, Philippe H.

    2013-11-01

    calculations for a given system, its dependence on the box size being analytical. The latter scheme also provides insight into the physical origin of the finite-size effects. These two schemes also encompass a correction for discrete solvent effects that persists even in the limit of infinite box sizes. Application of either scheme essentially eliminates the size dependence of the corrected charging free energies (maximal deviation of 1.5 kJ mol-1). Because it is simple to apply, the analytical correction scheme offers a general solution to the problem of finite-size effects in free-energy calculations involving charged solutes, as encountered in calculations concerning, e.g., protein-ligand binding, biomolecular association, residue mutation, pKa and redox potential estimation, substrate transformation, solvation, and solvent-solvent partitioning.

  12. Calculating the binding free energies of charged species based on explicit-solvent simulations employing lattice-sum methods: an accurate correction scheme for electrostatic finite-size effects.

    PubMed

    Rocklin, Gabriel J; Mobley, David L; Dill, Ken A; Hünenberger, Philippe H

    2013-11-14

    calculations for a given system, its dependence on the box size being analytical. The latter scheme also provides insight into the physical origin of the finite-size effects. These two schemes also encompass a correction for discrete solvent effects that persists even in the limit of infinite box sizes. Application of either scheme essentially eliminates the size dependence of the corrected charging free energies (maximal deviation of 1.5 kJ mol(-1)). Because it is simple to apply, the analytical correction scheme offers a general solution to the problem of finite-size effects in free-energy calculations involving charged solutes, as encountered in calculations concerning, e.g., protein-ligand binding, biomolecular association, residue mutation, pKa and redox potential estimation, substrate transformation, solvation, and solvent-solvent partitioning.

  13. Calculating the binding free energies of charged species based on explicit-solvent simulations employing lattice-sum methods: An accurate correction scheme for electrostatic finite-size effects

    SciTech Connect

    Rocklin, Gabriel J.; Mobley, David L.; Dill, Ken A.; Hünenberger, Philippe H.

    2013-11-14

    -periodic PB calculations for a given system, its dependence on the box size being analytical. The latter scheme also provides insight into the physical origin of the finite-size effects. These two schemes also encompass a correction for discrete solvent effects that persists even in the limit of infinite box sizes. Application of either scheme essentially eliminates the size dependence of the corrected charging free energies (maximal deviation of 1.5 kJ mol{sup −1}). Because it is simple to apply, the analytical correction scheme offers a general solution to the problem of finite-size effects in free-energy calculations involving charged solutes, as encountered in calculations concerning, e.g., protein-ligand binding, biomolecular association, residue mutation, pK{sub a} and redox potential estimation, substrate transformation, solvation, and solvent-solvent partitioning.

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

    DOEpatents

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

    2017-08-01

    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.

  15. 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.

  16. 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.

  17. Electric-field-induced response of a droplet embedded in a polyelectrolyte gel

    NASA Astrophysics Data System (ADS)

    Mohammadi, Aliasghar

    2013-08-01

    The electric-field induced response of a droplet embedded in a quenched polyelectrolyte gel is calculated theoretically. The response comprises the droplet translation and the electric-field induced flow fields within the droplet. The gel is modeled as a soft, and electrically charged porous solid saturated with a salted Newtonian fluid. The droplet is considered an incompressible Newtonian fluid with no free charge. An analytical solution, using the perturbation methodology and linear superposition, is obtained for the leading-order steady response to a DC electric-field. The fluid within the droplet is driven due to hydrodynamic coupling with the electroosmotic flow. The fluid velocity within the droplet is linearly proportional to the electroosmotic flow. Moreover, the microrheological response function of a droplet within a polyelectrolyte gel is also provided, highlighting the importance of boundary conditions at the droplet-gel interface on microrheological measurements.

  18. Electric-Field-Assisted Droplet Dispensing on Immiscible Fluids

    NASA Astrophysics Data System (ADS)

    Uhm, Taewoong; Hong, Jiwoo; Lee, Sang Joon; Kang, In Seok

    2014-11-01

    Dispensing tiny droplets is a basic and crucial process in numerous practical applications, such as printed electronics, DNA microarray, and digital microfluidics. The precise positioning with demanded size of droplets is the main issue of dispensing tiny droplets. Furthermore, capability of dispensing charged droplets on the immiscible fluids could bring out more utilities. In this work, we demonstrate the droplet dispensing on immiscible fluids by means of electrical charge concentration (ECC). This results from the fact that the droplet is generated by electric force caused by electric induction between the surface of droplet and the immiscible fluid. The temporal evolution of the droplet-dispensing process was observed consecutively with a high-speed camera. In addition, the relationship between the size of dispensed droplet and the parameters, such as physical properties of fluids and electrical field strength, is established. This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (Grant Number: 2013R1A1A2011956).

  19. The roles of electronic exchange and correlation in charge-transfer- to-solvent dynamics: Many-electron nonadiabatic mixed quantum/classical simulations of photoexcited sodium anions in the condensed phase.

    PubMed

    Glover, William J; Larsen, Ross E; Schwartz, Benjamin J

    2008-10-28

    The charge-transfer-to-solvent (CTTS) reactions of solvated atomic anions serve as ideal models for studying the dynamics of electron transfer: The fact that atomic anions have no internal degrees of freedom provides one of the most direct routes to understanding how the motions of solvent molecules influence charge transfer, and the relative simplicity of atomic electronic structure allows for direct contact between theory and experiment. To date, molecular dynamics simulations of the CTTS process have relied on a single-electron description of the atomic anion-only the electron involved in the charge transfer has been treated quantum mechanically, and the electronic structure of the atomic solute has been treated via pseudopotentials. In this paper, we examine the severity of approximating the electronic structure of CTTS anions with a one-electron model and address the role of electronic exchange and correlation in both CTTS electronic structure and dynamics. To do this, we perform many-electron mixed quantum/classical molecular dynamics simulations of the ground- and excited-state properties of the aqueous sodium anion (sodide). We treat both of the sodide valence electrons quantum mechanically and solve the Schrodinger equation using configuration interaction with singles and doubles (CISD), which provides an exact solution for two electrons. We find that our multielectron simulations give excellent general agreement with experimental results on the CTTS spectroscopy and dynamics of sodide in related solvents. We also compare the results of our multielectron simulations to those from one-electron simulations on the same system [C. J. Smallwood et al., J. Chem. Phys. 119, 11263 (2003)] and find substantial differences in the equilibrium CTTS properties and the nonadiabatic relaxation dynamics of one- and two-electron aqueous sodide. For example, the one-electron model substantially underpredicts the size of sodide, which in turn results in a dramatically

  20. Wetting of polymers by their solvents.

    PubMed

    Lequeux, François; Talini, Laurence; Verneuil, Emilie; Delannoy, Guillaume; Valois, Pauline

    2016-02-01

    We review the studies on the wetting of soluble polymeric substrates by their solvents, both in the literature and conducted in our group in the past decade. When a droplet of solvent spreads on a soluble polymer layer, its wetting angle can strongly vary with the contact line velocity even at capillary numbers smaller than unity, in contrast to non-soluble substrates. The solvent content in the polymer is a key parameter for the spreading dynamics; that content is set by the initial conditions, but also by the transfers occurring from the droplet to the polymer layer during spreading. We focus on hydrophilic amorphous polymers that are glassy at room temperature, and we discuss the consequences on wetting of the very large changes in the polymer physical properties induced by solvent sorption. We finally present new results on polymers of varying molar masses, and show how they open new perspectives for a better understanding of powder dissolution.

  1. Controlling the Growth Modes of Femtoliter Sessile Droplets Nucleating on Chemically Patterned Surfaces

    NASA Astrophysics Data System (ADS)

    Zhang, Xuehua; Bao, Lei; Werbiuk, Zenon; Lohse, Detlef

    2016-11-01

    Femtoliter droplet arrays on immersed substrates are essential elements in a broad range of advanced droplet-based technologies, such as light manipulation, sensing, and high throughput diagnosis. Solvent exchange is a bottom-up approach for producing those droplets from a pulse of oil oversaturation when a good solvent of the droplet liquid is displaced by a poor solvent. The position and arrangement of the droplets are regulated by chemical micropatterns on the substrate. Here we show experimentally and theoretically that the growth modes of droplets confined in planar micropatterns on the surface can be manipulated through the laminar flow of the solvent exchange. The control parameters are the area size of the micropatterns and the flow rate, and the observables are the contact angle and the final droplet volume. For a given pattern size, the Peclet number of the flow determines whether the growing droplets switch from an initial constant contact angle mode to a subsequent constant contact radius mode. Good agreement is achieved between the experimental results and our theoretical model that describes the dependence of the final droplet size on Pe.

  2. Japan's research on droplet and droplet array combustion

    NASA Technical Reports Server (NTRS)

    Kono, Michikata

    1995-01-01

    In Japan, the ignition and combustion of the droplet and droplet array have been investigated by using microgravity condition. This is the short introduction of those studies; interactive combustion of two droplets, ignition experiment on droplet array, and microexplosion behavior of an emulsified fuel droplet.

  3. 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.

  4. 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.

  5. Droplets on liquids and their journey into equilibrium.

    PubMed

    Bommer, Stefan; Cartellier, Florian; Jachalski, Sebastian; Peschka, Dirk; Seemann, Ralf; Wagner, Barbara

    2013-08-01

    The morphological path of droplets on a liquid substrate towards equilibrium is investigated experimentally and theoretically. The droplets emerge in the late stage of a dewetting process of short chained polystyrene (PS) dewetting from liquid polymethyl-methacrylate (PMMA). The three-dimensional droplet profiles are obtained experimentally by combining the in situ imaged PS/air interface during equilibration and the ex situ imaged PS/PMMA interface after removal of the PS by a selective solvent. Numerically the transient drop shapes are calculated by solving the thin-film equation in lubrication approximation using the experimentally determined input parameter like viscosity, film thickness and surface tensions. The numerically obtained droplet morphologies and time scales agree very well with the experimental drop shapes. An unexpected observation is that droplets with identical volumes synchronise their motion and become independent of the initial geometry long time before equilibrium is reached.

  6. Flow invariant droplet formation for stable parallel microreactors

    NASA Astrophysics Data System (ADS)

    Riche, Carson T.; Roberts, Emily J.; Gupta, Malancha; Brutchey, Richard L.; Malmstadt, Noah

    2016-02-01

    The translation of batch chemistries onto continuous flow platforms requires addressing the issues of consistent fluidic behaviour, channel fouling and high-throughput processing. Droplet microfluidic technologies reduce channel fouling and provide an improved level of control over heat and mass transfer to control reaction kinetics. However, in conventional geometries, the droplet size is sensitive to changes in flow rates. Here we report a three-dimensional droplet generating device that exhibits flow invariant behaviour and is robust to fluctuations in flow rate. In addition, the droplet generator is capable of producing droplet volumes spanning four orders of magnitude. We apply this device in a parallel network to synthesize platinum nanoparticles using an ionic liquid solvent, demonstrate reproducible synthesis after recycling the ionic liquid, and double the reaction yield compared with an analogous batch synthesis.

  7. Flow invariant droplet formation for stable parallel microreactors

    PubMed Central

    Riche, Carson T.; Roberts, Emily J.; Gupta, Malancha; Brutchey, Richard L.; Malmstadt, Noah

    2016-01-01

    The translation of batch chemistries onto continuous flow platforms requires addressing the issues of consistent fluidic behaviour, channel fouling and high-throughput processing. Droplet microfluidic technologies reduce channel fouling and provide an improved level of control over heat and mass transfer to control reaction kinetics. However, in conventional geometries, the droplet size is sensitive to changes in flow rates. Here we report a three-dimensional droplet generating device that exhibits flow invariant behaviour and is robust to fluctuations in flow rate. In addition, the droplet generator is capable of producing droplet volumes spanning four orders of magnitude. We apply this device in a parallel network to synthesize platinum nanoparticles using an ionic liquid solvent, demonstrate reproducible synthesis after recycling the ionic liquid, and double the reaction yield compared with an analogous batch synthesis. PMID:26902825

  8. The direct injection of liquid droplets into low pressure plasmas

    SciTech Connect

    Ogawa, D.; Saraf, I.; Sra, A.; Timmons, R.; Goeckner, M.; Overzet, L.

    2009-03-15

    A much greater number of useful precursors for plasma-enhanced chemical vapor deposition (PECVD) can be dispersed in high vapor pressure solvents than can be put into the vapor phase directly. In order to enable the use of such precursors, the authors investigated a method by which one can directly inject these liquids as microdroplets into low pressure PECVD environments. The solvent evaporates first leaving behind the desired precursor in the gas/plasma. The plasma dissociates the vapor and causes the deposition of a composite film (from precursor, solvent, and plasma gas). The authors made preliminary tests using Fe nanoparticles in hexane and were able to incorporate over 4% Fe in the resulting thin films. In addition, the authors simulated the process. The time required for a droplet to fully evaporate is a function of the background pressure, initial liquid temperature, droplet-vapor interactions, and initial droplet size. A typical evaporation time for a 50 {mu}m diameter droplet of hexane is {approx}3 s without plasma at 100 mTorr. The presence of plasma can decrease the evaporation time by more than an order of magnitude. In addition, the model predicts that the temperature of the injected droplet first decreases by evaporative cooling (to {approx}180 K for hexane); however, once the solvent has fully evaporated/sublimated, the plasma heats any remaining solute. As a result the solute temperature can first fall to 180 K, then rise to nearly 750 K in less than 1 s.

  9. Structural morphology of acoustically levitated and heated nanosilica droplet

    SciTech Connect

    Kumar, Ranganathan; Tijerino, Erick; Saha, Abhishek; Basu, Saptarshi

    2010-09-20

    We study the vaporization and precipitation dynamics of a nanosilica encapsulated water droplet by levitating it acoustically and heating it with a CO{sub 2} laser. For all concentrations, we observe three phases: solvent evaporation, surface agglomeration, and precipitation leading to bowl or ring shaped structures. At higher concentrations, ring reorientation and rotation are seen consistently. The surface temperature from an infrared camera is seen to be dependent on the final geometrical shape of the droplet and its rotation induced by the acoustic field of the levitator. With nonuniform particle distribution, these structures can experience rupture which modifies the droplet rotational speed.

  10. 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.

  11. Droplet transport system and methods

    NASA Technical Reports Server (NTRS)

    Neitzel, G. Paul (Inventor)

    2010-01-01

    Embodiments of droplet transport systems and methods are disclosed for levitating and transporting single or encapsulated droplets using thermocapillary convection. One method embodiment, among others comprises providing a droplet of a first liquid; and applying thermocapillary convection to the droplet to levitate and move the droplet.

  12. Wettability effects on droplet coalescence

    NASA Astrophysics Data System (ADS)

    Graham, Percival; de Pauw, Dennis; Dolatabadi, Ali

    2012-11-01

    Droplet impingement has been studied since 1895, with the works of A.M. Worthington. Throughout the past century, a variety of interesting phenomena have been uncovered. These include the bouncing of droplets off of each other or liquid pools, intricate droplet splashing mechanics, and droplets bouncing off of superhydrophobic surfaces; to name a few. In addition to intricate phenomena, droplet dynamics are relevant to many engineering applications, such as painting, spray coating ink-jet printing, and ice accumulation. These fields all involve interactions between droplets; therefore, studying droplet coalescence would benefit them greatly. The works presented include the coalescence of droplets with different impact conditions, various offsets, and at different wettabilities. Surface wettabilities studied are hydrophilic, hydrophobic and superhydrophobic. Fascinating phenomena observed include, bouncing of the impinging droplet off of the sessile droplet, sliding of the impinging droplet along the sessile droplet, and induced detachment on the sessile droplet on superhydrophobic surfaces. In order to capture the maximum spreading of the merged droplets, models related to coalescence of droplets in air and maximum spreading of a single droplet are combined to yield a new model to predict the maximum spreading of head-on droplet impact. Based on the free surface, and accuracy of the analytical model, droplet impact could be viewed as a mix of droplet coalescence in a gaseous media and droplet impact on a dry surface. Funding from NSERC.

  13. Solvent substitution

    SciTech Connect

    Not Available

    1990-01-01

    The DOE Environmental Restoration and Waste Management Office of Technology Development and the Air Force Engineering and Services Center convened the First Annual International Workshop on Solvent Substitution on December 4--7, 1990. The primary objectives of this joint effort were to share information and ideas among attendees in order to enhance the development and implementation of required new technologies for the elimination of pollutants associated with industrial use of hazardous and toxic solvents; and to aid in accelerating collaborative efforts and technology transfer between government and industry for solvent substitution. There were workshop sessions focusing on Alternative Technologies, Alternative Solvents, Recovery/Recycling, Low VOC Materials and Treatment for Environmentally Safe Disposal. The 35 invited papers presented covered a wide range of solvent substitution activities including: hardware and weapons production and maintenance, paint stripping, coating applications, printed circuit boards, metal cleaning, metal finishing, manufacturing, compliance monitoring and process control monitoring. This publication includes the majority of these presentations. In addition, in order to further facilitate information exchange and technology transfer, the US Air Force and DOE solicited additional papers under a general Call for Papers.'' These papers, which underwent review and final selection by a peer review committee, are also included in this combined Proceedings/Compendium. For those involved in handling, using or managing hazardous and toxic solvents, this document should prove to be a valuable resource, providing the most up-to-date information on current technologies and practices in solvent substitution. Individual papers are abstracted separated.

  14. Droplet Combustion Experiment (DCE)

    NASA Technical Reports Server (NTRS)

    Haggard, John B., Jr.; Nayagan, Vedha; Dryer, Frederick L.; Williams, Forman A.

    1998-01-01

    The first space-based experiments were performed on the combustion of free, individual liquid fuel droplets in oxidizing atmospheres. The fuel was heptane, with initial droplet diameters ranging about from 1 mm to 4 mm. The atmospheres were mixtures of helium and oxygen, at pressures of 1.00, 0.50 and 0.25 bar, with oxygen mole fractions between 20% and 40%, as well as normal Spacelab cabin air. The temperatures of the atmospheres and of the initial liquid fuel were nominally 300 K. A total of 44 droplets were burned successfully on the two flights, 8 on the shortened STS-83 mission and 36 on STS-94. The results spanned the full range of heptane droplet combustion behavior, from radiative flame extinction at larger droplet diameters in the more dilute atmospheres to diffusive extinction in the less dilute atmospheres, with the droplet disappearing prior to flame extinction at the highest oxygen concentrations. Quasisteady histories of droplet diameters were observed along with unsteady histories of flame diameters. New and detailed information was obtained on burning rates, flame characteristics and soot behavior. The results have motivated new computational and theoretical investigations of droplet combustion, improving knowledge of the chemical kinetics, fluid mechanics and heat and mass transfer processes involved in burning liquid fuels.

  15. Electrophoretic mobility of oil droplets in electrolyte and surfactant solutions.

    PubMed

    Wuzhang, Jiachen; Song, Yongxin; Sun, Runzhe; Pan, Xinxiang; Li, Dongqing

    2015-10-01

    Electrophoretic mobility of oil droplets of micron sizes in PBS and ionic surfactant solutions was measured in this paper. The experimental results show that, in addition to the applied electric field, the speed and the direction of electrophoretic motion of oil droplets depend on the surfactant concentration and on if the droplet is in negatively charged SDS solutions or in positively charged hexadecyltrimethylammonium bromide (CTAB) solutions. The absolute value of the electrophoretic mobility increases with increased surfactant concentration before the surfactant concentration reaches to the CMC. It was also found that there are two vortices around the oil droplet under the applied electric field. The size of the vortices changes with the surfactant and with the electric field. The vortices around the droplet directly affect the drag of the flow field to the droplet motion and should be considered in the studies of electrophoretic mobility of oil droplets. The existence of the vortices will also influence the determination and the interpretation of the zeta potential of the oil droplets based on the measured mobility data. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Drying of DNA droplets.

    PubMed

    Fang, Xiaohua; Li, Bingquan; Petersen, Eric; Seo, Young-Soo; Samuilov, Vladimir A; Chen, Yong; Sokolov, Jonathan C; Shew, Chwen-Yang; Rafailovich, Miriam H

    2006-07-04

    The evaporation kinetics of droplets containing DNA was studied, as a function of DNA concentration. Drops containing very low DNA concentrations dried by maintaining a constant base, whereas those with high concentration dried with a constant contact angle. To understand this phenomenon, the distribution of the DNA inside the droplet was measured using confocal microscopy. The results indicated that the DNA was condensed mostly on the surface of the droplets. In the case of high concentration droplets, it formed a shell, whereas isolated islands were found for droplets of low DNA concentrations. Rheologic results indicate the formation of a hydro gel in the low concentration drops, whereas phase separation between the self-assembled DNA structures and the water phase occurred at higher concentration.

  17. Liquid droplet generation

    NASA Technical Reports Server (NTRS)

    Muntz, E. P.; Orme, Melissa; Farnham, Tony; Vandiep, G. Pham; Huerre, P.

    1989-01-01

    A pre-prototype segment of a droplet sheet generator for a liquid droplet radiator was designed, constructed and tested. The ability to achieve a uniform, non-diverging droplet sheet is limited by manufacturing tolerances on nozzle parallelism. For an array of 100, 100 micrometer diameters nozzles spaced 5 stream diameters apart, typical standard deviations in stream alignment were plus or minus 10 mrad. The drop to drop fractional speed variations of the drops in typical streams were similar and independent of position in the array. The absolute value of the speed dispersion depended on the amplitude of the disturbance applied to the stream. A second generation preliminary design of a 5200 stream segment of a droplet sheet generator was completed. The design is based on information developed during testing of the pre-prototype segment, along with the results of an acoustical analysis for the stagnation cavity pressure fluctuations used to break-up the streams into droplets.

  18. Self-propelled droplets

    NASA Astrophysics Data System (ADS)

    Seemann, Ralf; Fleury, Jean-Baptiste; Maass, Corinna C.

    2016-11-01

    Self-propelled droplets are a special kind of self-propelled matter that are easily fabricated by standard microfluidic tools and locomote for a certain time without external sources of energy. The typical driving mechanism is a Marangoni flow due to gradients in the interfacial energy on the droplet interface. In this article we review the hydrodynamic prerequisites for self-sustained locomotion and present two examples to realize those conditions for emulsion droplets, i.e. droplets stabilized by a surfactant layer in a surrounding immiscible liquid. One possibility to achieve self-propelled motion relies on chemical reactions affecting the surface active properties of the surfactant molecules. The other relies on micellar solubilization of the droplet phase into the surrounding liquid phase. Remarkable cruising ranges can be achieved in both cases and the relative insensitivity to their own `exhausts' allows to additionally study collective phenomena.

  19. Solvent effects on charge transport through solid deposits of [Os(4,4'-diphenyl-2,2'-dipyridyl)2Cl2].

    PubMed

    Forster, Robert J; Iqbal, Javed; Hjelm, Johan; Keyes, Tia E

    2004-12-01

    Mechanically attached, solid-state films of [Os(4,4'-diphenyl-2,2'-dipyridyl)2Cl2] have been formed on gold macro- and microelectrodes and their voltammetric properties investigated. The voltammetric response of these films associated with the Os(2+/3+) redox reaction is reminiscent of that observed for an ideal reversible, solution phase redox couple only when the contacting electrolyte contains of the order of 40% v/v of acetonitrile (ACN). The origin of this effect appears to involve preferential solvation of the redox centres by acetonitrile which facilitates the incorporation of charge compensating counterions. Scanning electron microscopy reveals that voltammetric cycling in 40:60 ACN-H2O containing 1.0 M LiClO4 as the electrolyte induces the formation of microcrystals. Voltammetry conducted under semi-infinite linear diffusion conditions has been used to determine the apparent diffusion coefficient, Dapp, for homogeneous charge transport through the deposit. The dynamics of charge transport decrease with increasing film thickness but appear to increase with increasing electrolyte concentration. These observations suggest that ion transport rather than the rate of electron self-exchange limit the overall rate of charge transport through these solids. When in contact with 40:60 ACN-H2O containing 1.0 M LiClO4 as electrolyte, Dapp values for oxidation and reduction are identical at 1.7 +/- 0.4 x 10(-12) cm2 s(-1). In the same electrolyte, the standard heterogeneous electron transfer rate constant, k(o), determined by fitting the full voltammogram using the Butler-Volmer formalism, is 8.3 +/- 0.5 x 10(-7) cm s(-1). The importance of these results for the rational design of solid state redox active materials for battery, display and sensor applications is considered.

  20. TDDFT study of twisted intramolecular charge transfer and intermolecular double proton transfer in the excited state of 4‧-dimethylaminoflavonol in ethanol solvent

    NASA Astrophysics Data System (ADS)

    Wang, Ye; Shi, Ying; Cong, Lin; Li, Hui

    2015-02-01

    Time-dependent density functional theory method at the def-TZVP/B3LYP level was employed to investigate the intramolecular and intermolecular hydrogen bonding dynamics in the first excited (S1) state of 4‧-dimethylaminoflavonol (DMAF) monomer and in ethanol solution. In the DMAF monomer, we demonstrated that the intramolecular charge transfer (ICT) takes place in the S1 state. This excited state ICT process was followed by intramolecular proton transfer. Our calculated results are in good agreement with the mechanism proposed in experimental work. For the hydrogen-bonded DMAF-EtOH complex, it was demonstrated that the intermolecular hydrogen bonds can induce the formation of the twisted intramolecular charge transfer (TICT) state and the conformational twisting is along the C3-C4 bond. Moreover, the intermolecular hydrogen bonds can also facilitate the intermolecular double proton transfer in the TICT state. A stepwise intermolecular double proton transfer process was revealed. Therefore, the intermolecular hydrogen bonds can alter the mechanism of intramolecular charge transfer and proton transfer in the excited state for the DMAF molecule.

  1. Coulomb crystals of oil droplets in a Paul trap

    NASA Astrophysics Data System (ADS)

    Triplett, Matt; Younger, Richard; Robertson, Scott

    1998-10-01

    Coulomb crystals of charged liquid droplets have been created in a Paul trap in air. The technique improves upon similar experiments with solid dust by having particles with a controlled and reproducible charge-to-mass ratio. The spatial configurations of crystals of a few particles have been determined.

  2. Precision stacking of nanoparticle laden sessile droplets to control solute deposit morphology

    NASA Astrophysics Data System (ADS)

    Kabi, Prasenjit; Basu, Saptarshi; Sanyal, Apratim; Chaudhuri, Swetaprovo

    2015-02-01

    Stacking pure solvent droplets on a solid substrate is apparently impossible in the absence of an external force as the second droplet will invariably spill over the first leading to a large wetted area. However, the unique feature that emerges during the drying of a nanoparticle laden droplet is the progressively enlarging thin solid film along the evaporating sessile droplet liquid periphery. This solid interface: the edge of which we shall refer to as the agglomeration front comprises of a thin layer of nanoparticle assembly and can support a carefully dispensed second droplet thereby allowing droplet stacking. It will be shown that the growth of this agglomeration front can also be effectively controlled by the dispensing time difference and the nanoparticle concentration in the two droplets. So far, we are commonly aware of material stacking in solid phase. This letter demonstrates stacking in the liquid phase and control over the thin solid interface growth.

  3. Ultrafast imaging method to measure surface tension and viscosity of inkjet-printed droplets in flight

    NASA Astrophysics Data System (ADS)

    Staat, Hendrik J. J.; van der Bos, Arjan; van den Berg, Marc; Reinten, Hans; Wijshoff, Herman; Versluis, Michel; Lohse, Detlef

    2017-01-01

    In modern drop-on-demand inkjet printing, the jetted droplets contain a mixture of solvents, pigments and surfactants. In order to accurately control the droplet formation process, its in-flight dynamics, and deposition characteristics upon impact at the underlying substrate, it is key to quantify the instantaneous liquid properties of the droplets during the entire inkjet-printing process. An analysis of shape oscillation dynamics is known to give direct information of the local liquid properties of millimeter-sized droplets and bubbles. Here, we apply this technique to measure the surface tension and viscosity of micrometer-sized inkjet droplets in flight by recording the droplet shape oscillations microseconds after pinch-off from the nozzle. From the damped oscillation amplitude and frequency we deduce the viscosity and surface tension, respectively. With this ultrafast imaging method, we study the role of surfactants in freshly made inkjet droplets in flight and compare to complementary techniques for dynamic surface tension measurements.

  4. Supercritical microgravity droplet vaporization

    NASA Technical Reports Server (NTRS)

    Hartfield, J.; Curtis, E.; Farrell, P.

    1990-01-01

    Supercritical droplet vaporization is an important issue in many combustion systems, such as liquid fueled rockets and compression-ignition (diesel) engines. In order to study the details of droplet behavior at these conditions, an experiment was designed to provide a gas phase environment which is above the critical pressure and critical temperature of a single liquid droplet. In general, the droplet begins as a cold droplet in the hot, high pressure environment. In order to eliminate disruptions to the droplet by convective motion in the gas, forced and natural convection gas motion are required to be small. Implementation of this requirement for forced convection is straightforward, while reduction of natural convection is achieved by reduction in the g-level for the experiment. The resulting experiment consists of a rig which can stably position a droplet without restraint in a high-pressure, high temperature gas field in microgravity. The microgravity field is currently achieved by dropping the device in the NASA Lewis 2.2 second drop tower. The performance of the experimental device and results to date are presented.

  5. Autonomous droplet architectures.

    PubMed

    Jones, Gareth; King, Philip H; Morgan, Hywel; de Planque, Maurits R R; Zauner, Klaus-Peter

    2015-01-01

    The quintessential living element of all organisms is the cell-a fluid-filled compartment enclosed, but not isolated, by a layer of amphiphilic molecules that self-assemble at its boundary. Cells of different composition can aggregate and communicate through the exchange of molecules across their boundaries. The astounding success of this architecture is readily apparent throughout the biological world. Inspired by the versatility of nature's architecture, we investigate aggregates of membrane-enclosed droplets as a design concept for robotics. This will require droplets capable of sensing, information processing, and actuation. It will also require the integration of functionally specialized droplets into an interconnected functional unit. Based on results from the literature and from our own laboratory, we argue the viability of this approach. Sensing and information processing in droplets have been the subject of several recent studies, on which we draw. Integrating droplets into coherently acting units and the aspect of controlled actuation for locomotion have received less attention. This article describes experiments that address both of these challenges. Using lipid-coated droplets of Belousov-Zhabotinsky reaction medium in oil, we show here that such droplets can be integrated and that chemically driven mechanical motion can be achieved.

  6. Reactive Leidenfrost droplets

    NASA Astrophysics Data System (ADS)

    Raufaste, C.; Bouret, Y.; Celestini, F.

    2016-05-01

    We experimentally investigate the reactivity of Leidenfrost droplets with their supporting substrates. Several organic liquids are put into contact with a copper substrate heated above their Leidenfrost temperature. As the liquid evaporates, the gaseous flow cleans the superficial copper oxide formed at the substrate surface and the reaction maintains a native copper spot below the evaporating droplet. The copper spot can reach several times the droplet size for the most reactive organic compounds. This study shows an interesting coupling between the physics of the Leidenfrost effect and the mechanics of reactive flows. Different applications are proposed such as drop motion tracking and vapor flow monitoring.

  7. 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.

  8. 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.

  9. Charge-transfer complexes of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone with amino molecules in polar solvents

    NASA Astrophysics Data System (ADS)

    Berto, Silvia; Chiavazza, Enrico; Ribotta, Valentina; Daniele, Pier Giuseppe; Barolo, Claudia; Giacomino, Agnese; Vione, Davide; Malandrino, Mery

    2015-10-01

    The charge-transfer complexes have scientific relevance because this type of molecular interaction is at the basis of the activity of pharmacological compounds and because the absorption bands of the complexes can be used for the quantification of electron donor molecules. This work aims to assess the stability of the charge-transfer complexes between the electron acceptor 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and two drugs, procaine and atenolol, in acetonitrile and ethanol. The stability of DDQ in solution and the time required to obtain the maximum complex formation were evaluated. The stoichiometry and the stability of the complexes were determined, respectively, by Job's plot method and by the elaboration of UV-vis titrations data. The latter task was carried out by using the non-linear global analysis approach to determine the equilibrium constants. This approach to data elaboration allowed us to overcome the disadvantages of the classical linear-regression method, to obtain reliable values of the association constants and to calculate the entire spectra of the complexes. NMR spectra were recorded to identify the portion of the donor molecule that was involved in the interaction. The data support the participation of the aliphatic amino groups in complex formation and exclude the involvement of the aromatic amine present in the procaine molecule.

  10. Hydrophobic polymers in nano-sized water droplets

    NASA Astrophysics Data System (ADS)

    Tilakaratne, Buddhi; Masood, Samina; Cheung, Margaret

    2008-03-01

    As simulations of biopolymers take place in confined and tight spaces, such as protein folding in the interior of bacteria chaperones or the exit tunnels of ribosomes, quantitative analyses of the confinement effects on both biopolymers and solvent molecules become the center of attention as the solvent-mediated interactions are too profound to solve analytically. We are in the progress to investigate the solvation of hexane molecules in various nano-sized water droplets. Free energy profiles for a single hexane molecule in droplets show that the droplet surfaces are favored. Averaged configurations of hexane molecules at the interior and the surface are computed using the umbrella sampling methods. The implications of our results for protein stability in confined spaces will be discussed.

  11. Solvent primitive model for electrolyte solutions in disordered porous matrices of charged species. Replica Ornstein-Zernike theory and grand canonical Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Lukšič, Miha; Hribar-Lee, Barbara; Baleón Tochimani, Sergio; Pizio, Orest

    2012-01-01

    We present a theoretical study of a quenched-annealed system in which an annealed component is the restricted primitive model electrolyte in a mixture with an uncharged hard sphere species, i.e. the solvent primitive model (SPM), whereas a disordered quenched medium is modelled as the restricted primitive model (RPM) electrolyte. The annealed mixture is in thermal and chemical equilibrium with an external reservoir containing the same SPM. The system is studied by using the replica Ornstein-Zernike (ROZ) integral equation theory complemented with the hypernetted chain (HNC) approximation and via the grand canonical Monte Carlo simulations. We are primarily interested in collecting computer simulation data and comparing them with theoretical predictions at room temperature (298.15 K). In terms of physical observables, our focus is in the selectivity effects of adsorption of the mixture described by the adsorption isotherms as well as by the composition isotherms. The influence of the ionic matrix density and of the bulk state of the SPM mixture on adsorption and selectivity are examined in detail. Besides, we analyse the dependence of the internal energy and the constant volume heat capacity on the conditions of adsorption. Finally, we explore briefly the effects of quenching conditions of the RPM matrix on the pair distribution functions of fluid ions in the mixture. In general, the theory is in a very good agreement with computer simulations.

  12. Water droplets interaction with super-hydrophobic surfaces

    NASA Astrophysics Data System (ADS)

    Wu, Yunying; Saito, Nagahiro; Nae, Florin Andrei; Inoue, Yasushi; Takai, Osamu

    2006-09-01

    Static and dynamic behavior of water droplets on various super-hydrophobic (SH) surfaces were investigated. First, SH plant leaves were used as samples and we found out that surface nanostructure has a great influence on the droplets dynamic behavior. Then, we made biomimetic structures by depositing SH films through microwave-plasma enhanced chemical vapor deposition (MPECVD). Next, SH surfaces were fabricated by covering previously roughened SiO x films with self-assembled monolayers (SAMs). The substrates were then charged with static electricity, and water droplets falling on tilted charged surfaces leaped up or run uphill at high speeds, proving that not only the surface nanostructure but also its chemical endgroups have a great effect on the water droplets motion on SH surfaces.

  13. Active droplet generation in microfluidics.

    PubMed

    Chong, Zhuang Zhi; Tan, Say Hwa; Gañán-Calvo, Alfonso M; Tor, Shu Beng; Loh, Ngiap Hiang; Nguyen, Nam-Trung

    2016-01-07

    The reliable generation of micron-sized droplets is an important process for various applications in droplet-based microfluidics. The generated droplets work as a self-contained reaction platform in droplet-based lab-on-a-chip systems. With the maturity of this platform technology, sophisticated and delicate control of the droplet generation process is needed to address increasingly complex applications. This review presents the state of the art of active droplet generation concepts, which are categorized according to the nature of the induced energy. At the liquid/liquid interface, an energy imbalance leads to instability and droplet breakup.

  14. 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.

  15. Aerodynamic Droplet Breakup.

    DTIC Science & Technology

    1982-05-24

    3 I SURFACE TENSION VARIATIONS ... ........ 9 I VISCOUS EFFECTS ..................... 11 WEBER NUMBER EFFECT .i. . . . . ...... 11 SU MlARY...AVMA X = 100 m/s) ...................... .8 4 SURFACE TENSION EFFECTS ON DROPLET BREAKUP .... ........ 10 5 VISCOSITY EFFECTS ON DROPLET BREAKUP...studied. The primary goal of this initial phase was to examine the effect of liquid properties (viscosity and surface tension ) on the breakup mechanism

  16. Microscopic Rayleigh Droplet Beams

    NASA Astrophysics Data System (ADS)

    Doak, R. B.

    2005-11-01

    A periodically triggered Rayleigh Droplet Beam (RDB) delivers a perfectly linear and periodic stream of identical, monoenergetic droplets that are phase-locked to the trigger signal. The droplet diameter and spacing are easily adjusted of choice of nozzle diameter and trigger frequency. Any liquid of low viscosity may be emloyed as the beam fluid. Although the field of nanofluidics is expanding rapidly, little effort has yet been devoted to ``external flows'' such as RDB's. At ASU we have generated RDB's of water and methanol down to 2 microns in droplet diameter. Nozzle clogging is the sole impediment to smaller droplets. Microscopic Rayleigh droplet beams offer tremendous potential for fundamental physical measurements, fluid dynamics research, and nanofabrication. This talk will describe the apparatus and techniques used at ASU to generate RDB's (surprisingly simple and inexpensive), discuss the triboelectric phenomena that play a role (surprisingly significant), present some initial experimental fluid dynamics measurements, and briefly survey RDB applications. Our particular interest in RDB's is as microscopic transport systems to deliver hydrated, undenatured proteins into vacuum for structure determination via serial diffraction of x-rays or electrons. This may offer the first general method for structure determination of non-crystallizable proteins.

  17. Droplet based microfluidics.

    PubMed

    Seemann, Ralf; Brinkmann, Martin; Pfohl, Thomas; Herminghaus, Stephan

    2012-01-01

    Droplet based microfluidics is a rapidly growing interdisciplinary field of research combining soft matter physics, biochemistry and microsystems engineering. Its applications range from fast analytical systems or the synthesis of advanced materials to protein crystallization and biological assays for living cells. Precise control of droplet volumes and reliable manipulation of individual droplets such as coalescence, mixing of their contents, and sorting in combination with fast analysis tools allow us to perform chemical reactions inside the droplets under defined conditions. In this paper, we will review available drop generation and manipulation techniques. The main focus of this review is not to be comprehensive and explain all techniques in great detail but to identify and shed light on similarities and underlying physical principles. Since geometry and wetting properties of the microfluidic channels are crucial factors for droplet generation, we also briefly describe typical device fabrication methods in droplet based microfluidics. Examples of applications and reaction schemes which rely on the discussed manipulation techniques are also presented, such as the fabrication of special materials and biophysical experiments.

  18. Fuel Droplet Burning During Droplet Combustion Experiment

    NASA Technical Reports Server (NTRS)

    2003-01-01

    Fuel ignites and burns in the Droplet Combustion Experiment (DCE) on STS-94 on July 4 1997, MET:2/05:40 (approximate). The DCE was designed to investigate the fundamental combustion aspects of single, isolated droplets under different pressures and ambient oxygen concentrations for a range of droplet sizes varying between 2 and 5 mm. DCE used various fuels -- in drops ranging from 1 mm (0.04 inches) to 5 mm (0.2 inches) -- and mixtures of oxidizers and inert gases to learn more about the physics of combustion in the simplest burning configuration, a sphere. The experiment elapsed time is shown at the bottom of the composite image. The DCE principal investigator was Forman Williams, University of California, San Diego. The experiment was part of the space research investigations conducted during the Microgravity Science Laboratory-1R mission (STS-94, July 1-17 1997). Advanced combustion experiments will be a part of investigations plarned for the International Space Station. (1.4MB, 13-second MPEG, screen 320 x 240 pixels; downlinked video, higher quality not available)A still JPG composite of this movie is available at http://mix.msfc.nasa.gov/ABSTRACTS/MSFC-0300168.html.

  19. Fuel Droplet Burning During Droplet Combustion Experiment

    NASA Technical Reports Server (NTRS)

    2003-01-01

    Fuel ignites and burns in the Droplet Combustion Experiment (DCE) on STS-94 on July 4 1997, MET:2/05:40 (approximate). The DCE was designed to investigate the fundamental combustion aspects of single, isolated droplets under different pressures and ambient oxygen concentrations for a range of droplet sizes varying between 2 and 5 mm. DCE used various fuels -- in drops ranging from 1 mm (0.04 inches) to 5 mm (0.2 inches) -- and mixtures of oxidizers and inert gases to learn more about the physics of combustion in the simplest burning configuration, a sphere. The experiment elapsed time is shown at the bottom of the composite image. The DCE principal investigator was Forman Williams, University of California, San Diego. The experiment was part of the space research investigations conducted during the Microgravity Science Laboratory-1R mission (STS-94, July 1-17 1997). Advanced combustion experiments will be a part of investigations plarned for the International Space Station. (1.4MB, 13-second MPEG, screen 320 x 240 pixels; downlinked video, higher quality not available)A still JPG composite of this movie is available at http://mix.msfc.nasa.gov/ABSTRACTS/MSFC-0300168.html.

  20. On the structure of an electrostatic spray of monodisperse droplets

    NASA Astrophysics Data System (ADS)

    Tang, Keqi; Gomez, Alessandro

    1994-07-01

    An experimental study has been performed on the structure of an electrostatic spray of monodisperse droplets. Such a spray is established when a liquid with sufficient electric conductivity and moderate surface tension, in the present case heptane doped with an antistatic additive, is fed through a small metal tube maintained at several kilovolts relative to a ground electrode a few centimeters away. The liquid meniscus at the outlet of the capillary takes a conical shape under the action of the electric field, with a thin jet emerging from the cone tip. This jet breaks up into charged droplets that disperse into a fine spray. Flash shadowgraph of the breakup region showed that the jet initially breaks into droplets of bimodal size distribution by varicose wave instabilities. The spray monodispersity is established farther downstream by a segregation process of electrostatic and inertial nature that confines the bulk of the mass flow rate (97%) and 85% of the total current in a core of nearly monodisperse primary droplets, with the remainder in a shroud of satellites. Droplet size, axial velocity, and concentration were measured throughout the spray by phase Doppler anemometry (PDA). The complementary use of these measurements permitted the determination of the electric field via the spray momentum equation. It was found that droplets are ejected from the jet at a relatively high velocity in a region characterized by a very intense electric field. They maintain this velocity farther downstream because of inertia, even though the field is precipitously decreasing, and ultimately decelerate under the action of the drag force and a progressively weaker electrostatic force. Velocity and concentration fields were shown to be self-similar. Comparison between the external field, due to the potential difference applied between the electrodes, and the space charge field shows that the droplet axial motion is driven primarily by the external field, whereas the droplet radial

  1. Numerical simulation of the drying of inkjet-printed droplets.

    PubMed

    Siregar, D P; Kuerten, J G M; van der Geld, C W M

    2013-02-15

    In this paper we study the behavior of an inkjet-printed droplet of a solute dissolved in a solvent on a solid horizontal surface by numerical simulation. An extended model for drying of a droplet and the final distribution of the solute on an impermeable substrate is proposed. The model extends the work by Deegan, Fischer and Kuerten by taking into account convection, diffusion and adsorption of the solute in order to describe more accurately the surface coverage on the substrate. A spherically shaped droplet is considered such that the model can be formulated as an axially symmetric problem. The droplet dynamics is driven by the combined action of surface tension and evaporation. The fluid flow in the droplet is modeled by the Navier-Stokes equation and the continuity equation, where the lubrication approximation is applied. The rate of evaporation is determined by the distribution of vapor pressure in the air surrounding the droplet. Numerical results are compared with experimental results for droplets of various sizes.

  2. 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.

  3. Spatially resolved measurements of size and velocity distributions of aerosol droplets from a direct injection nebulizer

    SciTech Connect

    Shum, S.C.K.; Johnson, S.K.; Pang, H.M.; Houk, R.S. )

    1993-05-01

    Aerosol droplet sizes and velocities from a direct injection nebulizer (DIN) are measured with radial and axial spatial resolution by phase Doppler particle analysis (PDPA). The droplets on the central axis of the spray become finer and their size becomes more uniform when [approx]20% methanol is added to the usual aqueous solvent. This could explain why the analyte signal is a maximum at this solvent composition when the DIN is used for inductively coupled plasma-mass spectrometry (ICP-MS). Mean droplet velocities are 12 to 22 m s[sup [minus]1] with standard deviations of [plus minus]4 to [plus minus]7 m s[sup [minus]1]. The outer fringes of the aerosol plume tend to be enriched in large droplets. The Sauter mean diameter (D[sub 3,2]) and velocity of the droplets also vary substantially with axial position in the aerosol plume. 35 refs., 10 figs., 1 tab.

  4. Trace Material Capture by Controlled Liquid Droplets on a Superhydrophobic/Hydrophilic Surface.

    PubMed

    Fukada, Kenta; Kawamura, Naoya; Shiratori, Seimei

    2017-09-15

    A liquid droplet in contact with a superhydrophobic surface can be used to collect dissolved trace materials after evaporating the solvent. This process effect enhances detection limits, but a liquid droplet easily rolls off a superhydrophobic surface. Keeping it at a specific collecting spot area is challenging. Here the means for controlling and capturing a liquid droplet on a superhydrophobic surface is demonstrated. To induce a liquid droplet to a collecting spot, its rolling direction was controlled by two superhydrophobic fabric guides. The liquid droplet was then captured by hydrophilic polymer and hydrophilic nanoparticles at the measuring spot. After removing the solvent, the trace compounds were evaluated with a colorimetric analysis visible to the naked eye.

  5. Dynamics of a Water Droplet over a Sessile Oil Droplet: Compound Droplets Satisfying a Neumann Condition.

    PubMed

    Iqbal, R; Dhiman, S; Sen, A K; Shen, Amy Q

    2017-06-13

    We report the dynamics of compound droplets with a denser liquid (water) droplet over a less dense sessile droplet (mineral oil) that satisfies the Neumann condition. For a fixed size of an oil droplet, depending on the size of the water droplet, either it attains the axisymmetric position or tends to migrate toward the edge of the oil droplet. For a water droplet-to-oil droplet at volume ratio Vw/Vo ≥ 0.05, stable axisymmetric configuration is achieved; for Vw/Vo < 0.05, migration of water droplet is observed. The stability and migration of water droplets of size above and below critical size, respectively, are explained using the force balance at the three-phase contact line and film tension. The larger and smaller droplets that initially attain the axisymmetric position or some radial position, respectively, evaporate continuously and thus migrate toward the edge of the oil droplet. The radial location and migration of the water droplets of different initial sizes with respect to time are studied. Experiments with water droplets on a flat oil-air interface did not show migration, which signified the role of the curved oil-air interface for droplet migration. Finally, coalescence of water droplets of size above the critical size at the axisymmetric position is demonstrated. Our compound droplet studies could be beneficial for applications involving droplet transport where contamination due to direct contact and pinning of droplets on solid surfaces is of concern. Migration and coalescence of water droplets on curved oil-air interfaces could open new frontiers in chemical and biological applications including multiphase processing and biological interaction of cells and atmospheric chemistry.

  6. Interfacial phenomena in droplet evaporation and nanoparticle-cell systems

    NASA Astrophysics Data System (ADS)

    Fang, Xiaohua

    2005-11-01

    The factors affecting droplet evaporation are discussed. It is found that the droplet morphology at a specific temperature is controlled by the physical properties of the liquid itself, such as the molecular weight, density, diffusion coefficient in air, and heat of vaporization. Two processes are included in droplet evaporation: (1) diffusion of liquid molecules into the air (diffusion part) and (2) flow of the liquid molecules from inside the droplet to the free outer shell liquid layer within the liquid-vapor interface (energy part). The diffusion part remains steady during drying and was not sensitive to the variation of temperature. The energy part, however, was an active factor and determined the differences in drop evaporation behaviors. A model is developed to measure the solubility parameters of the solvents via droplet evaporation. Droplets were deposited on Octadecyltrichlorosilane (OTS) covered silicon surfaces and the contact angle and overall drop morphology are observed using a KSV contact angle goniometer as a function of time. OTS is considered a non-absorbing surface for the solvents examined and does not affect the accuracy of the measured results. This method allows determination of the attraction forces between solvent molecules in the condensed phases. The solubility parameter values of droplets containing pure water, methanol, ethanol and butanol are measured. The test results are independent of the droplet size. The evaporation kinetics of droplets containing DNA is studied. Simultaneously, the DNA re-distribution and adsorption kinetics are measured by confocal microscopy. The DNA droplets are stained with ethidium bromide solution and deposited on OTS covered silicon surfaces. The results showed that the drying behavior depended on the DNA concentration. During drying, DNA relocation inside of the drop affects the internal forces of the liquid. A ring is formed at the air/solid/liquid interface. The absorbed amount of DNA was obtained by

  7. Generation of multicomponent polymer blend microparticles using droplet evaporation technique and modeling evaporation of binary droplet containing nonvolatile solute

    NASA Astrophysics Data System (ADS)

    Rajagopalan, Venkat Narayan

    Recently, considerable attention has been focused on the generation of nano- and micrometer scale multicomponent polymer particles with specifically tailored mechanical, electrical and optical properties. As only a few polymer-polymer pairs are miscible, the set of multicomponent polymer systems achievable by conventional methods, such as melt blending, is severely limited in property ranges. Therefore, researchers have been evaluating synthesis methods that can arbitrarily blend immiscible solvent pairs, thus expanding the range of properties that are practical. The generation of blended microparticles by evaporating a co-solvent from aerosol droplets containing two dissolved immiscible polymers in solution seems likely to exhibit a high degree of phase uniformity. A second important advantage of this technique is the formation of nano- and microscale particulates with very low impurities, which are not attainable through conventional solution techniques. When the timescale of solvent evaporation is lower than that of polymer diffusion and self-organization, phase separation is inhibited within the atto- to femto-liter volume of the droplet, and homogeneous blends of immiscible polymers can be produced. We have studied multicomponent polymer particles generated from highly monodisperse micrordroplets that were produced using a Vibrating Orifice Aerosol Generator (VOAG). The particles are characterized for both external and internal morphology along with homogeneity of the blends. Ultra-thin slices of polymer particles were characterized by a Scanning Electron Microscope (SEM), and the degree of uniformity was examined using an Electron Dispersive X-ray Analysis (EDAX). To further establish the homogeneity of the polymer blend microparticles, differential scanning calorimeter was used to measure the glass transition temperature of the microparticles obtained. These results have its significance in the field of particulate encapsulation. Also, better control of the

  8. Nematic droplets on fibers

    NASA Astrophysics Data System (ADS)

    Batista, V. M. O.; Silvestre, N. M.; Telo da Gama, M. M.

    2015-12-01

    The emergence of new techniques for the fabrication of nematic droplets with nontrivial topology provides new routes for the assembly of responsive devices. Here we explore some of the properties of nematic droplets on fibers, which constitute the basic units of a type of device that is able to respond to external stimuli, including the detection of gases. We perform a numerical study of spherical nematic droplets on fibers. We analyze the equilibrium textures for homogeneous and hybrid boundary conditions and find that in some cases the nematic avoids the nucleation of topological defects, which would provide a different optical response. We consider in detail a homeotropic nematic droplet wrapped around a fiber with planar anchoring. We investigate the effect of an electric field on the texture of this droplet. In the presence of a dc field, the system undergoes an orientational transition above a given threshold Ec, for which a ring defect is transformed into a figure-eight defect. We also consider ac fields, at high and low frequencies, and find that the textures are similar to those observed for static fields, in contrast with recently reported experiments.

  9. Microfluidic devices for droplet injection

    NASA Astrophysics Data System (ADS)

    Aubrecht, Donald; Akartuna, Ilke; Weitz, David

    2012-02-01

    As picoliter-scale reaction vessels, microfluidic water-in-oil emulsions have found application for high-throughput, large-sample number analyses. Often, the biological or chemical system under investigation needs to be encapsulated into droplets to prevent cross contamination prior to the introduction of reaction reagents. Previous techniques of picoinjection or droplet synchronization and merging enable the addition of reagents to individual droplets, but present limitations on what can be added to each droplet. We present microfluidic devices that couple the strengths of picoinjection and droplet merging, allowing us to selectively add precise volume to our droplet reactions.

  10. Sagging of evaporating droplets of colloidal suspensions on inclined substrates.

    PubMed

    Espín, Leonardo; Kumar, Satish

    2014-10-14

    A droplet of a colloidal suspension placed on an inclined substrate may sag under the action of gravity. Solvent evaporation raises the concentration of the colloidal particles, and the resulting viscosity changes may influence the sag of the droplet. To investigate this phenomenon, we have developed a mathematical model for perfectly wetting droplets based on lubrication theory and the rapid-vertical-diffusion approximation. Precursor films are assumed to be present, the colloidal particles are taken to be hard spheres, and particle and liquid dynamics are coupled through a concentration-dependent viscosity and diffusivity. Evaporation is assumed to be limited by how rapidly solvent molecules can transfer from the liquid to the vapor phase. The resulting one-dimensional system of nonlinear partial differential equations describing the evolution of the droplet height and particle concentration is solved numerically for a range of initial particle concentrations and substrate temperatures. The solutions reveal that the interaction between evaporation and non-Newtonian suspension rheology gives rise to several distinct regimes of droplet shapes and particle concentration distributions. The results provide insight into how evaporation and suspension rheology can be tuned to minimize sagging as well as the well-known coffee-ring effect, an outcome which is important for industrial coating processes.

  11. Insight into the Evaporation Dynamics of a Pair of Sessile Droplets on a Hydrophobic Substrate.

    PubMed

    Shaikeea, Angkur Jyoti Dipanka; Basu, Saptarshi

    2016-02-09

    In this work, we have demonstrated three unique regimes in the evaporation lifecycle of a pair of sessile droplets placed in variable proximity on a hydrophobic substrate. For small separation distance, the droplets undergo asymmetric spatiotemporal evaporation leading to contact angle hysteresis and suppressed vaporization. The reduced evaporation has been attributed quantitatively to the existence of a constrained vapor-rich dome between the two droplets. However, a dynamic decrease in the droplet radius due to solvent removal marks a return to symmetry in terms of evaporation and contact angle. We have described the variation in evaporation flux using a universal correction factor. We have also demonstrated the existence of a critical separation distance beyond which the droplets in the droplet pair do not affect each other. The results are crucial to a plethora of applications ranging from surface patterning to lab-on-a-chip devices.

  12. Explosion of Leidenfrost Droplets

    NASA Astrophysics Data System (ADS)

    Moreau, Florian; Colinet, Pierre; Dorbolo, Stephane

    2012-11-01

    When a drop is released on a plate heated above a given temperature, a thin layer of vapour can isolate the droplet so that it levitates over the plate. This effect was first reported by Leidenfrost in 1756. However, this fascinating subject remains an active field of research in both fundamental and applied researches. In this work, we focus on what happens when surfactant is added to the drop. The aim is to study the influence of a decrease of the surface tension. Surprisingly, as the droplet evaporates, suddenly it explodes. The evolution of the droplet and the resulting explosion are followed using a high speed camera. We show that when a critical concentration of surfactant is reached inside the drop, a shell of surfactant is formed leading to the explosion. The authors would like to thank FNRS for financial support. This work is financially supported by ODILE project (Contract No. FRFC 2.4623.11).

  13. Droplet Combustion Experiment movie

    NASA Technical Reports Server (NTRS)

    2003-01-01

    The Droplet Combustion Experiment (DCE) was designed to investigate the fundamental combustion aspects of single, isolated droplets under different pressures and ambient oxygen concentrations for a range of droplet sizes varying between 2 and 5 mm. The DCE principal investigator was Forman Williams, University of California, San Diego. The experiment was part of the space research investigations conducted during the Microgravity Science Laboratory-1 mission (STS-83, April 4-8 1997; the shortened mission was reflown as MSL-1R on STS-94). Advanced combustion experiments will be a part of investigations plarned for the International Space Station. (1.1 MB, 12-second MPEG, screen 320 x 240 pixels; downlinked video, higher quality not available)A still JPG composite of this movie is available at http://mix.msfc.nasa.gov/ABSTRACTS/MSFC-0300164.html.

  14. Droplet Combustion Experiment

    NASA Technical Reports Server (NTRS)

    2003-01-01

    The Droplet Combustion Experiment (DCE) was designed to investigate the fundamental combustion aspects of single, isolated droplets under different pressures and ambient oxygen concentrations for a range of droplet sizes varying between 2 and 5 mm. The DCE principal investigator was Forman Williams, University of California, San Diego. The experiment was part of the space research investigations conducted during the Microgravity Science Laboratory-1 mission (STS-83, April 4-8 1997; the shortened mission was reflown as MSL-1R on STS-94). Advanced combustion experiments will be a part of investigations plarned for the International Space Station. (199KB JPEG, 1311 x 1477 pixels; downlinked video, higher quality not available) The MPG from which this composite was made is available at http://mix.msfc.nasa.gov/ABSTRACTS/MSFC-0300165.html.

  15. Droplet Combustion Experiment

    NASA Technical Reports Server (NTRS)

    2003-01-01

    The Droplet Combustion Experiment (DCE) was designed to investigate the fundamental combustion aspects of single, isolated droplets under different pressures and ambient oxygen concentrations for a range of droplet sizes varying between 2 and 5 mm. The DCE principal investigator was Forman Williams, University of California, San Diego. The experiment was part of the space research investigations conducted during the Microgravity Science Laboratory-1R mission (STS-94, July 1-17 1997). Advanced combustion experiments will be a part of investigations plarned for the International Space Station. (120KB JPEG, 655 x 736 pixels; downlinked video, higher quality not available) The MPG from which this composite was made is available at http://mix.msfc.nasa.gov/ABSTRACTS/MSFC-0300167.html.

  16. The mayonnaise droplet

    NASA Astrophysics Data System (ADS)

    Terwagne, Denis; Gilet, Tristan; Vandewalle, Nicolas; Dorbolo, Stéphane

    2009-11-01

    A compound drop is made of a millimetric water drop encapsulated by an oil shell. They are obtained by merging one drop of each component (water and oil). Afterwards, they are laid on a high viscosity oil bath which is vertically vibrated. When the forcing acceleration is higher than a given threshold, compound drops can bounce on the surface. We show that above a second threshold some oil contained in the shell enters in the inner water droplet. In a second experiment, we drop the compound droplet on the oil bath at rest. We can determine the range of impact speed in which capillary waves developed on the surface are able to generate an oil drop (coming from the shell) in the water drop. When the bouncing trajectories of the droplets are analyzed a correlation between the emulsion threshold and the static analysis can be made.

  17. 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.

  18. Chip-based droplet sorting

    SciTech Connect

    Beer, Neil Reginald; Lee, Abraham; Hatch, Andrew

    2014-07-01

    A non-contact system for sorting monodisperse water-in-oil emulsion droplets in a microfluidic device based on the droplet's contents and their interaction with an applied electromagnetic field or by identification and sorting.

  19. Electrofreezing of water droplets under electrowetting fields.

    PubMed

    Carpenter, Katherine; Bahadur, Vaibhav

    2015-02-24

    Electrofreezing is the electrically induced nucleation of ice from supercooled water. This work studies ice nucleation in electrowetted water droplets, wherein there is no electric field inside the droplet resting on a dielectric layer. Instead, there is an interfacial electric field and charge buildup at the solid-liquid interface. This situation is in contrast to most previous electrofreezing studies, which have used bare electrodes, involve current flow, and have a volumetric electric field inside the liquid. Infrared and high-speed visualizations of static water droplets are used to analyze surface electrofreezing. Ultrahigh electric fields of up to 80 V/μm are applied, which is one order of magnitude higher than in previous studies. The results facilitate an in-depth understanding of various mechanisms underlying electrofreezing. First, it is seen that interfacial electric fields alone can significantly elevate freezing temperatures by more than 15 °C, in the absence of current flow. Second, the magnitude of electrofreezing induced temperature elevation saturates at high electric field strengths. Third, the polarity of the interfacial charge does not significantly influence electrofreezing. Overall, it is seen that electrofreezing nucleation kinetics is primarily influenced by the three-phase boundary and not the solid-liquid interface. Through careful electrofreezing measurements on dielectric layers with pinholes to allow current flow, the individual role of electric fields and electric currents on electrofreezing is isolated. It is seen that both the electric field and the electric current influence electrofreezing; however, the physical mechanisms are very different.

  20. Charge effects and nanoparticle pattern formation in electrohydrodynamic NanoDrip printing of colloids

    NASA Astrophysics Data System (ADS)

    Richner, Patrizia; Kress, Stephan J. P.; Norris, David J.; Poulikakos, Dimos

    2016-03-01

    Advancing open atmosphere printing technologies to produce features in the nanoscale range has important and broad applications ranging from electronics to photonics, plasmonics and biology. Recently an electrohydrodynamic printing regime has been demonstrated in a rapid dripping mode (termed NanoDrip), where the ejected colloidal droplets from nozzles of diameters of O (1 μm) can controllably reach sizes an order of magnitude smaller than the nozzle and can generate planar and out-of-plane structures of similar sizes. Despite the demonstrated capabilities, our fundamental understanding of important aspects of the physics of NanoDrip printing needs further improvement. Here we address the topics of charge content and transport in NanoDrip printing. We employ quantum dot and gold nanoparticle dispersions in combination with a specially designed, auxiliary, asymmetric electric field, targeting the understanding of charge locality (particles vs. solvent) and particle distribution in the deposits as indicated by the dried nanoparticle patterns (footprints) on the substrate. We show that droplets of alternating charge can be spatially separated when applying an ac field to the nozzle. The nanoparticles within a droplet are distributed asymmetrically under the influence of the auxiliary lateral electric field, indicating that they are the main carriers. We also show that the ligand length of the nanoparticles in the colloid affects their mobility after deposition (in the sessile droplet state).Advancing open atmosphere printing technologies to produce features in the nanoscale range has important and broad applications ranging from electronics to photonics, plasmonics and biology. Recently an electrohydrodynamic printing regime has been demonstrated in a rapid dripping mode (termed NanoDrip), where the ejected colloidal droplets from nozzles of diameters of O (1 μm) can controllably reach sizes an order of magnitude smaller than the nozzle and can generate planar and

  1. Sessile nanofluid droplet drying.

    PubMed

    Zhong, Xin; Crivoi, Alexandru; Duan, Fei

    2015-03-01

    Nanofluid droplet evaporation has gained much audience nowadays due to its wide applications in painting, coating, surface patterning, particle deposition, etc. This paper reviews the drying progress and deposition formation from the evaporative sessile droplets with the suspended insoluble solutes, especially nanoparticles. The main content covers the evaporation fundamental, the particle self-assembly, and deposition patterns in sessile nanofluid droplet. Both experimental and theoretical studies are presented. The effects of the type, concentration and size of nanoparticles on the spreading and evaporative dynamics are elucidated at first, serving the basis for the understanding of particle motion and deposition process which are introduced afterward. Stressing on particle assembly and production of desirable residue patterns, we express abundant experimental interventions, various types of deposits, and the effects on nanoparticle deposition. The review ends with the introduction of theoretical investigations, including the Navier-Stokes equations in terms of solutions, the Diffusion Limited Aggregation approach, the Kinetic Monte Carlo method, and the Dynamical Density Functional Theory. Nanoparticles have shown great influences in spreading, evaporation rate, evaporation regime, fluid flow and pattern formation of sessile droplets. Under different experimental conditions, various deposition patterns can be formed. The existing theoretical approaches are able to predict fluid dynamics, particle motion and deposition patterns in the particular cases. On the basis of further understanding of the effects of fluid dynamics and particle motion, the desirable patterns can be obtained with appropriate experimental regulations. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. 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.

  3. 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.

  4. 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

  5. An interface tracking model for droplet electrocoalescence.

    SciTech Connect

    Erickson, Lindsay Crowl

    2013-09-01

    This report describes an Early Career Laboratory Directed Research and Development (LDRD) project to develop an interface tracking model for droplet electrocoalescence. Many fluid-based technologies rely on electrical fields to control the motion of droplets, e.g. microfluidic devices for high-speed droplet sorting, solution separation for chemical detectors, and purification of biodiesel fuel. Precise control over droplets is crucial to these applications. However, electric fields can induce complex and unpredictable fluid dynamics. Recent experiments (Ristenpart et al. 2009) have demonstrated that oppositely charged droplets bounce rather than coalesce in the presence of strong electric fields. A transient aqueous bridge forms between approaching drops prior to pinch-off. This observation applies to many types of fluids, but neither theory nor experiments have been able to offer a satisfactory explanation. Analytic hydrodynamic approximations for interfaces become invalid near coalescence, and therefore detailed numerical simulations are necessary. This is a computationally challenging problem that involves tracking a moving interface and solving complex multi-physics and multi-scale dynamics, which are beyond the capabilities of most state-of-the-art simulations. An interface-tracking model for electro-coalescence can provide a new perspective to a variety of applications in which interfacial physics are coupled with electrodynamics, including electro-osmosis, fabrication of microelectronics, fuel atomization, oil dehydration, nuclear waste reprocessing and solution separation for chemical detectors. We present a conformal decomposition finite element (CDFEM) interface-tracking method for the electrohydrodynamics of two-phase flow to demonstrate electro-coalescence. CDFEM is a sharp interface method that decomposes elements along fluid-fluid boundaries and uses a level set function to represent the interface.

  6. Multilayered silicone oil droplets of narrow size distribution: preparation and improved deposition on hair.

    PubMed

    Nazir, Habiba; Wang, Lianyan; Lian, Guoping; Zhu, Shiping; Zhang, Yueling; Liu, Yuan; Ma, Guanghui

    2012-12-01

    Silicone oil droplets have limited deposition on hair due to electrostatic repulsion with negative surface charge of hair substrates. Aiming to improve silicone deposition on hair substrates, surface properties of uniform-sized silicone oil droplets (produced by membrane emulsification) were modified using layer-by-layer electrostatic deposition. By using this method, silicone oil droplets were coated with large molecular weight polymers, i.e. quaternized chitosan and alginate, and low molecular weight compounds, i.e. diallyl dimethyl ammonium chloride and glycerol to obtain six alternate layers of different surface charges. It was found that the dispersion of coated silicone oil droplets of narrow size distribution exhibited much improved mechanical strength and increased viscosity against shear compared to uncoated droplets. These multilayered silicone oil droplets were then added into model shampoos and conditioners to study the effect of charge and molecular weight of coating materials on silicone oil deposition on hair. The results clearly demonstrated that surface charge and charge density have significant influence on silicone oil deposition. Droplets with higher positive charge density resulted in increased deposition of silicone on hair due to electrostatic attraction. Characterization of the hair surface potential, wetting properties and friction certified the results further, showing reduced friction, decreased wetting angle and positive surface potential of high density positively charged silicone oil droplets. Therefore, LBL surface modification combined with membrane emulsification is a promising method for preparing multilayered silicone oil droplets of increased mechanical strength, viscosity and deposition on hair. Copyright © 2012 Elsevier B.V. All rights reserved.

  7. 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.

  8. Lysozyme pattern formation in evaporating droplets

    NASA Astrophysics Data System (ADS)

    Gorr, Heather Meloy

    Liquid droplets containing suspended particles deposited on a solid, flat surface generally form ring-like structures due to the redistribution of solute during evaporation (the "coffee ring effect"). The forms of the deposited patterns depend on complex interactions between solute(s), solvent, and substrate in a rapidly changing, far from equilibrium system. Solute self-organization during evaporation of colloidal sessile droplets has attracted the attention of researchers over the past few decades due to a variety of technological applications. Recently, pattern formation during evaporation of various biofluids has been studied due to potential applications in medical screening and diagnosis. Due to the complexity of 'real' biological fluids and other multicomponent systems, a comprehensive understanding of pattern formation during droplet evaporation of these fluids is lacking. In this PhD dissertation, the morphology of the patterns remaining after evaporation of droplets of a simplified model biological fluid (aqueous lysozyme solutions + NaCl) are examined by atomic force microscopy (AFM) and optical microscopy. Lysozyme is a globular protein found in high concentration, for example, in human tears and saliva. The drop diameters, D, studied range from the micro- to the macro- scale (1 microm -- 2 mm). In this work, the effect of evaporation conditions, solution chemistry, and heat transfer within the droplet on pattern formation is examined. In micro-scale deposits of aqueous lysozyme solutions (1 microm < D < 50 microm), the protein motion and the resulting dried residue morphology are highly influenced by the decreased evaporation time of the drop. The effect of electrolytes on pattern formation is also investigated by adding varying concentrations NaCl to the lysozyme solutions. Finally, a novel pattern recognition program is described and implemented which classifies deposit images by their solution chemistries. The results presented in this Ph

  9. Reflectivity of NaK Droplets

    NASA Astrophysics Data System (ADS)

    Wiedemann, C.; Oswald, M.; Stabroth, S.; Klinkrad, H.; Vörsmann, P.

    visible and the near infrared. This absorption can be determined using a model according to Overhauser who assumes charge-density waves (CDW). But the existence of the anomalous absorption is controversial. The influence of the different models on the reflectivity is discussed. The reflectivity is calculated depending on the alloy composition and the temperature at the surface of a droplet. The results are compared to measurement data from the literature. It is shown that NaK droplets have a very high total reflectivity.

  10. Expanding roles for lipid droplets

    PubMed Central

    Welte, Michael A.

    2015-01-01

    Summary Lipid droplets are the intracellular sites for neutral lipid storage. They are critical for lipid metabolism and energy homeostasis, and their dysfunction has been linked to many diseases. Accumulating evidence suggests that the roles lipid droplets play in biology are significantly broader than previously anticipated. Lipid droplets are the source of molecules important in the nucleus: they can sequester transcription factors and chromatin components and generate the lipid ligands for certain nuclear receptors. Lipid droplets have also emerged as important nodes for fatty acid trafficking, both inside the cell and between cells. In immunity, new roles for droplets, not directly linked to lipid metabolism, have been uncovered, as assembly platforms for specific viruses and as reservoirs for proteins that fight intracellular pathogens. Until recently, knowledge about droplets in the nervous system has been minimal, but now there are multiple links between lipid droplets and neurodegeneration: Many candidate genes for Hereditary Spastic Paraplegia also have central roles in lipid-droplet formation and maintenance, and mitochondrial dysfunction in neurons can lead to transient accumulating of lipid droplets in neighboring glial cells, an event that may, in turn, contribute to neuronal damage. As the cell biology and biochemistry of lipid droplets are increasingly well understood, the next few years should yield many new mechanistic insights into these novel functions of lipid droplets. PMID:26035793

  11. Glass transition accelerates the spreading of polar solvents on a soluble polymer.

    PubMed

    Dupas, Julien; Verneuil, Emilie; Van Landeghem, Maxime; Bresson, Bruno; Forny, Laurent; Ramaioli, Marco; Lequeux, Francois; Talini, Laurence

    2014-05-09

    We study the wetting of polymer layers by polar solvents. As previously observed, when a droplet of solvent spreads, both its contact angle and velocity decrease with time as a result of solvent transfers from the droplet to the substrate. We show that, when the polymer is initially glassy, the angle decreases steeply for a given value of the velocity, Ug. We demonstrate that those variations result from a plasticization, i.e., a glass transition, undergone by the polymer layer during spreading, owing to the increase of its solvent content. By analyzing previous predictions on the wetting of rigid and soft viscoelastic substrates, we relate Ug to the viscosity of the polymer gel close to the glass transition. Finally, we derive an analytical prediction for Ug based on existing predictions for the water transfer from the droplet to the substrate. Using polar solvents of different natures, we show that the experimental data compare well to the predicted expression for Ug.

  12. 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.

  13. Surface Modification of Droplet Polymeric Microfluidic Devices for the Stable and Continuous Generation of Aqueous Droplets

    PubMed Central

    Subramanian, Balamurugan; Kim, Namwon; Lee, Wonbae; Spivak, David A.; Nikitopoulos, Dimitris E.; McCarley, Robin L.; Soper, Steven A.

    2012-01-01

    Droplet microfluidics performed in poly(methylmethacrylate), PMMA, microfluidic devices resulted in significant wall wetting by water droplets formed in a liquid-liquid segmented flow when using a hydrophobic carrier fluid, such as perfluorotripropylamine (FC-3283). This wall wetting led to water droplets with non-uniform sizes that were often trapped on the wall surfaces leading to unstable and poorly controlled liquid-liquid segmented flow. To circumvent this problem, we developed a two-step procedure to hydrophobically modify the surfaces of PMMA and other thermoplastic materials commonly used for making microfluidic devices. The surface modification route involved the introduction of hydroxyl groups by oxygen plasma treatment of the polymer surface followed by a solution phase reaction with heptadecafluoro-1,1,2,2–tetrahydrodecyl trichlorosilane dissolved in the fluorocarbon solvent FC-3283. This procedure was found to be useful for the modification of PMMA and other thermoplastic surfaces, including polycyclic olefin copolymer (COC) and polycarbonate (PC). Angle-resolved X-ray photoelectron spectroscopy indicated that the fluorination of these polymers took place with high surface selectivity. This procedure was used to modify the surface of a PMMA droplet microfluidic device (DMFD) and was shown to be useful to reduce the wetting problem during the generation of aqueous droplets in a perfluorotripropylamine (FC-3283) carrier fluid and could generate stable segmented flows for hours of operation. In the case of the PMMA DMFD, oxygen plasma treatment was carried out after the PMMA cover plate was thermally fusion bonded to the PMMA microfluidic chip. Because the appended chemistry to the channel wall created a hydrophobic surface, it will accommodate the use of other carrier fluids that are hydrophobic as well, such as hexadecane or mineral oils. PMID:21608975

  14. Surface modification of droplet polymeric microfluidic devices for the stable and continuous generation of aqueous droplets.

    PubMed

    Subramanian, Balamurugan; Kim, Namwon; Lee, Wonbae; Spivak, David A; Nikitopoulos, Dimitris E; McCarley, Robin L; Soper, Steven A

    2011-06-21

    Droplet microfluidics performed in poly(methyl methacrylate) (PMMA) microfluidic devices resulted in significant wall wetting by water droplets formed in a liquid-liquid segmented flow when using a hydrophobic carrier fluid such as perfluorotripropylamine (FC-3283). This wall wetting led to water droplets with nonuniform sizes that were often trapped on the wall surfaces, leading to unstable and poorly controlled liquid-liquid segmented flow. To circumvent this problem, we developed a two-step procedure to hydrophobically modify the surfaces of PMMA and other thermoplastic materials commonly used to make microfluidic devices. The surface-modification route involved the introduction of hydroxyl groups by oxygen plasma treatment of the polymer surface followed by a solution-phase reaction with heptadecafluoro-1,1,2,2-tetrahydrodecyl trichlorosilane dissolved in fluorocarbon solvent FC-3283. This procedure was found to be useful for the modification of PMMA and other thermoplastic surfaces, including polycyclic olefin copolymer (COC) and polycarbonate (PC). Angle-resolved X-ray photoelectron spectroscopy indicated that the fluorination of these polymers took place with high surface selectivity. This procedure was used to modify the surface of a PMMA droplet microfluidic device (DMFD) and was shown to be useful in reducing the wetting problem during the generation of aqueous droplets in a perfluorotripropylamine (FC-3283) carrier fluid and could generate stable segmented flows for hours of operation. In the case of PMMA DMFD, oxygen plasma treatment was carried out after the PMMA cover plate was thermally fusion bonded to the PMMA microfluidic chip. Because the appended chemistry to the channel wall created a hydrophobic surface, it will accommodate the use of other carrier fluids that are hydrophobic as well, such as hexadecane or mineral oils.

  15. Diffraction of walking droplets

    NASA Astrophysics Data System (ADS)

    Harris, Daniel M.; Pucci, Giuseppe; Bush, John W. M.

    2014-11-01

    We present results from our revisitation of the experiment of a walking droplet passing through a single slit, originally investigated by Couder & Fort (PRL, 2006). On each passage, the walker's trajectory is deviated as a result of the spatial confinement of its guiding wave. We explore the role of the droplet size and the bath's vibration amplitude on both the dynamics and statistics. We find the behavior to be remarkably sensitive to these control parameters. A complex physical picture emerges. The authors gratefully acknowledge the financial support of the NSF through Grant CMMI-1333242, DMH through the NSF Graduate Research Fellowship Program, and GP through the Programma Operativo Regionale (POR) Calabria - FSE 2007/2013.

  16. Droplet monitoring probe

    NASA Technical Reports Server (NTRS)

    Baughman, J. R.; Thys, P. C.

    1973-01-01

    A droplet monitoring system is disclosed for analysis of mixed-phase fluid flow in development of gas turbines. The system uses a probe comprising two electrical wires spaced a known distance apart and connected at one end to means for establishing a dc potential between the wires. A drop in the fluid stream momentarily contacting both wires simultaneously causes and electrical signal which is amplified, detected and counted.

  17. 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.

  18. Dynamics of Droplet Collision and Flamefront Motion

    DTIC Science & Technology

    2005-12-01

    effecting droplet bouncing versus absorption. (4) The dynamics of flame motion when it is subjected to the combined hydrodynamic and body-force instabilities...and freestream vortical motion. 15. SUBJECT TERMS Droplet collision; droplet-film collision; van der Waals force; droplet bouncing ; droplet...collision of two droplets. For example, they can either merge to form a larger droplet, or bounce away from each other. Furthermore, the collision event has

  19. Burning Fuel Droplet

    NASA Technical Reports Server (NTRS)

    2003-01-01

    Fuel ignites and burns in the Droplet Combustion Experiment (DCE) on STS-94 on July 4 1997, MET:2/05:40 (approximate). The DCE was designed to investigate the fundamental combustion aspects of single, isolated droplets under different pressures and ambient oxygen concentrations for a range of droplet sizes varying between 2 and 5 mm. DCE used various fuels -- in drops ranging from 1 mm (0.04 inches) to 5 mm (0.2 inches) -- and mixtures of oxidizers and inert gases to learn more about the physics of combustion in the simplest burning configuration, a sphere. The experiment elapsed time is shown at the bottom of the composite image. The DCE principal investigator was Forman Williams, University of California, San Diego. The experiment was part of the space research investigations conducted during the Microgravity Science Laboratory-1R mission (STS-94, July 1-17 1997). Advanced combustion experiments will be a part of investigations plarned for the International Space Station. (121KB JPEG, 654 x 977 pixels; downlinked video, higher quality not available) The MPG from which this composite was made is available at http://mix.msfc.nasa.gov/ABSTRACTS/MSFC-0300169.html.

  20. Droplet Combustion Experiment Operates

    NASA Technical Reports Server (NTRS)

    2003-01-01

    Fuel ignites and burns in the Droplet Combustion Experiment (DCE) on STS-94 on July 12, 1997, MET:11/07:00 (approximate). DCE used various fuels -- in drops ranging from 1 mm (0.04 inches) to 5 mm (0.2 inches) -- and mixtures of oxidizers and inert gases to learn more about the physics of combustion in the simplest burning configuration, a sphere. The DCE was designed to investigate the fundamental combustion aspects of single, isolated droplets under different pressures and ambient oxygen concentrations for a range of droplet sizes varying between 2 and 5 mm. The experiment elapsed time is shown at the bottom of the composite image. The DCE principal investigator was Forman Williams, University of California, San Diego. The experiment was part of the space research investigations conducted during the Microgravity Science Laboratory-1R mission (STS-94, July 1-17 1997). Advanced combustion experiments will be a part of investigations plarned for the International Space Station. (119KB JPEG, 658 x 982 pixels; downlinked video, higher quality not available) The MPG from which this composite was made is available at http://mix.msfc.nasa.gov/ABSTRACTS/MSFC-0300171.html.

  1. Burning Fuel Droplet

    NASA Technical Reports Server (NTRS)

    2003-01-01

    Fuel ignites and burns in the Droplet Combustion Experiment (DCE) on STS-94 on July 4 1997, MET:2/05:40 (approximate). The DCE was designed to investigate the fundamental combustion aspects of single, isolated droplets under different pressures and ambient oxygen concentrations for a range of droplet sizes varying between 2 and 5 mm. DCE used various fuels -- in drops ranging from 1 mm (0.04 inches) to 5 mm (0.2 inches) -- and mixtures of oxidizers and inert gases to learn more about the physics of combustion in the simplest burning configuration, a sphere. The experiment elapsed time is shown at the bottom of the composite image. The DCE principal investigator was Forman Williams, University of California, San Diego. The experiment was part of the space research investigations conducted during the Microgravity Science Laboratory-1R mission (STS-94, July 1-17 1997). Advanced combustion experiments will be a part of investigations plarned for the International Space Station. (121KB JPEG, 654 x 977 pixels; downlinked video, higher quality not available) The MPG from which this composite was made is available at http://mix.msfc.nasa.gov/ABSTRACTS/MSFC-0300169.html.

  2. Experimental determination of layer cloud edge charging from cosmic ray ionisation

    NASA Astrophysics Data System (ADS)

    Nicoll, K. A.; Harrison, R. G.

    2010-07-01

    The cloud-air transition zone at stratiform cloud edges is an electrically active region where droplet charging has been predicted. Cloud edge droplet charging is expected from vertical flow of cosmic ray generated atmospheric ions in the global electric circuit. Experimental confirmation of stratiform cloud edge electrification is presented here, through charge and droplet measurements made within an extensive layer of supercooled stratiform cloud, using a specially designed electrostatic sensor. Negative space charge up to 35 pC m-3 was found in a thin (<100 m) layer at the lower cloud boundary associated with the clear air-cloud conductivity gradient, agreeing closely with space charge predicted from the measured droplet concentration using ion-aerosol theory. Such charge levels carried by droplets are sufficient to influence collision processes between cloud droplets.

  3. Acoustic droplet vaporization of vascular droplets in gas embolotherapy

    NASA Astrophysics Data System (ADS)

    Bull, Joseph

    2016-11-01

    This work is primarily motivated by a developmental gas embolotherapy technique for cancer treatment. In this methodology, infarction of tumors is induced by selectively formed vascular gas bubbles that arise from the acoustic vaporization of vascular droplets. Additionally, micro- or nano-droplets may be used as vehicles for localized drug delivery, with or without flow occlusion. In this talk, we examine the dynamics of acoustic droplet vaporization through experiments and theoretical/computational fluid mechanics models, and investigate the bioeffects of acoustic droplet vaporization on endothelial cells and in vivo. Functionalized droplets that are targeted to tumor vasculature are examined. The influence of fluid mechanical and acoustic parameters, as well as droplet functionalization, is explored. This work was supported by NIH Grant R01EB006476.

  4. The safety of a cell in a droplet under high electric field

    NASA Astrophysics Data System (ADS)

    Noh, Jihoon; Im, Do Jin; Kang, In Seok

    2010-11-01

    Electrically charged aqueous droplet can be transported by electrical field in a dielectric fluid without the flow of medium (Jung et al. J. Colloid Interface Sci. 2008). This phenomenon can be used to transport a single nanoliter droplet in a micro channel, which can serve as biochemical micro-reactor. Because an aqueous droplet is much conductive than the dielectric fluid, there is effectively no electric field inside the droplet suspended in dielectric fluid. Therefore bio-materials are protected from electricity even under high electric field. However, when the droplet is charged near an electrode by direct contact to the electrode, there is possibility that electric field can hurt bio-materials like DNA molecules, microorganisms, cells, protein in droplet. Because of this concern, we should confirm that bio-materials in droplet moving by direct charging are safe under strong external electric field especially to organism cells. Therefore we examine the effect of electric field on the cells such as yeast, E.coli., and sperm in droplet experimentally.

  5. Finger-powered electrophoretic transport of discrete droplets for portable digital microfluidics.

    PubMed

    Peng, Cheng; Wang, Yide; Sungtaek Ju, Y

    2016-07-07

    We report a finger-powered digital microfluidic device based on the electrophoretic transport of discrete droplets (EPD). An array of piezoelectric elements is connected in parallel to metal electrodes immersed in dielectric fluids. When deflected in a controlled sequence via human finger power, the piezoelectric elements charge and actuate droplets across each electrode pair through electrophoretic force. Successful droplet transportation requires the piezoelectric elements to provide both sufficient charge and voltage pulse duration. We quantify these requirements using numerical models to predict the electrical charges induced on the droplets and the corresponding electrophoretic forces. The models are experimentally validated by comparing the predicted and measured droplet translational velocities. We successfully demonstrated transport and merging of aqueous droplets over a range of droplet radii (0.6-0.9 mm). We further showed direct manipulation of body fluids, including droplets of saliva and urine, using our finger-powered EPD device. To facilitate practical implementation of multistep assays based on the approach, a hand/finger-rotated drum system with a programmable pattern of protrusions is designed to induce deflections of multiple piezoelectric elements and demonstrate programmable fluidic functions. An electrode-to-piezoelectric element connection scheme to minimize the number of piezoelectric elements necessary for a sequence of microfluidic functions is also explored. The present work establishes an engineering foundation to enable design and implementation of finger-powered portable EPD microfluidic devices.

  6. Solvent reorganization of electron transitions in viscous solvents

    SciTech Connect

    Ghorai, Pradip K.; Matyushov, Dmitry V.

    2006-04-14

    We develop a model of electron transfer reactions at conditions of nonergodicity when the time of solvent relaxation crosses the observation time window set up by the reaction rate. Solvent reorganization energy of intramolecular electron transfer in a charge-transfer molecule dissolved in water and acetonitrile is studied by molecular dynamics simulations at varying temperatures. We observe a sharp decrease of the reorganization energy at a temperature identified as the temperature of structural arrest due to cage effect, as discussed by the mode-coupling theory. This temperature also marks the onset of the enhancement of translational diffusion relative to rotational relaxation signaling the breakdown of the Stokes-Einstein relation. The change in the reorganization energy at the transition temperature reflects the dynamical arrest of the slow, collective relaxation of the solvent related to the relaxation of the solvent dipolar polarization. An analytical theory proposed to describe this effect agrees well with both the simulations and experimental Stokes shift data. The theory is applied to the analysis of charge-transfer kinetics in a low-temperature glass former. We show that the reorganization energy is substantially lower than its equilibrium value for the low-temperature portion of the data. The theory predicts the possibility of discontinuous changes in the dependence of the electron transfer rate on the free energy gap when the reaction switches between ergodic and nonergodic regimes.

  7. Thermophoresis of microemulsion droplets: size dependence of the Soret effect.

    PubMed

    Vigolo, Daniele; Brambilla, Giovanni; Piazza, Roberto

    2007-04-01

    Thermophoresis, akin to thermal diffusion in simple fluid mixtures, consists of particle drift induced by a temperature gradient. Notwithstanding its practical interest, the dependence of thermophoretic effects on particle size R is still theoretically and experimentally debated. By performing measurements of water-in-oil microemulsion droplets with tunable size, we show that the thermal diffusion coefficient, at least for a suspension of small particles in a nonpolar solvent, does not appreciably depend on R .

  8. Laserspray Ionization, a New Atmospheric Pressure MALDI Method for Producing Highly Charged Gas-phase Ions of Peptides and Proteins Directly from Solid Solutions*

    PubMed Central

    Trimpin, Sarah; Inutan, Ellen D.; Herath, Thushani N.; McEwen, Charles N.

    2010-01-01

    The first example of a matrix-assisted laser desorption/ionization (MALDI) process producing multiply charged mass spectra nearly identical to those observed with electrospray ionization (ESI) is presented. MALDI is noted for its ability to produce singly charged ions, but in the experiments described here multiply charged ions are produced by laser ablation of analyte incorporated into a common MALDI matrix, 2,5-dihydroxybenzoic acid, using standard solvent-based sample preparation protocols. Laser ablation is known to produce matrix clusters in MALDI provided a threshold energy is achieved. We propose that these clusters (liquid droplets) are highly charged, and under conditions that produce sufficient matrix evaporation, ions are field-evaporated from the droplets similarly to ESI. Because of the multiple charging, advanced mass spectrometers with limited mass-to-charge range can be used for protein characterization. Thus, using an Orbitrap mass spectrometer, low femtomole quantities of proteins produce full-range mass spectra at 100,000 mass resolution with <5-ppm mass accuracy and with 1-s acquisition. Furthermore, the first example of protein fragmentation using electron transfer dissociation with MALDI is presented. PMID:19955086

  9. Laserspray ionization, a new atmospheric pressure MALDI method for producing highly charged gas-phase ions of peptides and proteins directly from solid solutions.

    PubMed

    Trimpin, Sarah; Inutan, Ellen D; Herath, Thushani N; McEwen, Charles N

    2010-02-01

    The first example of a matrix-assisted laser desorption/ionization (MALDI) process producing multiply charged mass spectra nearly identical to those observed with electrospray ionization (ESI) is presented. MALDI is noted for its ability to produce singly charged ions, but in the experiments described here multiply charged ions are produced by laser ablation of analyte incorporated into a common MALDI matrix, 2,5-dihydroxybenzoic acid, using standard solvent-based sample preparation protocols. Laser ablation is known to produce matrix clusters in MALDI provided a threshold energy is achieved. We propose that these clusters (liquid droplets) are highly charged, and under conditions that produce sufficient matrix evaporation, ions are field-evaporated from the droplets similarly to ESI. Because of the multiple charging, advanced mass spectrometers with limited mass-to-charge range can be used for protein characterization. Thus, using an Orbitrap mass spectrometer, low femtomole quantities of proteins produce full-range mass spectra at 100,000 mass resolution with <5-ppm mass accuracy and with 1-s acquisition. Furthermore, the first example of protein fragmentation using electron transfer dissociation with MALDI is presented.

  10. Chiral partition functions of quantum Hall droplets

    SciTech Connect

    Cappelli, Andrea Viola, Giovanni; Zemba, Guillermo R.

    2010-02-15

    Chiral partition functions of conformal field theory describe the edge excitations of isolated Hall droplets. They are characterized by an index specifying the quasiparticle sector and transform among themselves by a finite-dimensional representation of the modular group. The partition functions are derived and used to describe electron transitions leading to Coulomb blockade conductance peaks. We find the peak patterns for Abelian hierarchical states and non-Abelian Read-Rezayi states, and compare them. Experimental observation of these features can check the qualitative properties of the conformal field theory description, such as the decomposition of the Hilbert space into sectors, involving charged and neutral parts, and the fusion rules.

  11. 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.

  12. 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

    2017-07-01

    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.

  13. Stoddard solvent poisoning

    MedlinePlus

    These products contain Stoddard solvent: Dry cleaning fluids Paints Paint thinner Stoddard solvent ( mineral spirits ) Toners used in copy machines This list may not include all products containing Stoddard solvent.

  14. Rapidly pulsed helium droplet source

    SciTech Connect

    Pentlehner, Dominik; Riechers, Ricarda; Dick, Bernhard; Slenczka, Alkwin; Even, Uzi; Lavie, Nachum; Brown, Raviv; Luria, Kfir

    2009-04-15

    A pulsed valve connected to a closed-cycle cryostat was optimized for producing helium droplets. The pulsed droplet beam appeared with a bimodal size distribution. The leading part of the pulse consists of droplets suitable for doping with molecules. The average size of this part can be varied between 10{sup 4} and 10{sup 6} helium atoms, and the width of the distribution is smaller as compared to a continuous-flow droplet source. The system has been tested in a single pulse mode and at repetition rates of up to 500 Hz with almost constant intensity. The droplet density was found to be increased by more than an order of magnitude as compared to a continuous-flow droplet source.

  15. Evaporation of inclined water droplets

    NASA Astrophysics Data System (ADS)

    Kim, Jin Young; Hwang, In Gyu; Weon, Byung Mook

    2017-02-01

    When a drop is placed on a flat substrate tilted at an inclined angle, it can be deformed by gravity and its initial contact angle divides into front and rear contact angles by inclination. Here we study on evaporation dynamics of a pure water droplet on a flat solid substrate by controlling substrate inclination and measuring mass and volume changes of an evaporating droplet with time. We find that complete evaporation time of an inclined droplet becomes longer as gravitational influence by inclination becomes stronger. The gravity itself does not change the evaporation dynamics directly, whereas the gravity-induced droplet deformation increases the difference between front and rear angles, which quickens the onset of depinning and consequently reduces the contact radius. This result makes the evaporation rate of an inclined droplet to be slow. This finding would be important to improve understanding on evaporation dynamics of inclined droplets.

  16. Evaporation of inclined water droplets.

    PubMed

    Kim, Jin Young; Hwang, In Gyu; Weon, Byung Mook

    2017-02-16

    When a drop is placed on a flat substrate tilted at an inclined angle, it can be deformed by gravity and its initial contact angle divides into front and rear contact angles by inclination. Here we study on evaporation dynamics of a pure water droplet on a flat solid substrate by controlling substrate inclination and measuring mass and volume changes of an evaporating droplet with time. We find that complete evaporation time of an inclined droplet becomes longer as gravitational influence by inclination becomes stronger. The gravity itself does not change the evaporation dynamics directly, whereas the gravity-induced droplet deformation increases the difference between front and rear angles, which quickens the onset of depinning and consequently reduces the contact radius. This result makes the evaporation rate of an inclined droplet to be slow. This finding would be important to improve understanding on evaporation dynamics of inclined droplets.

  17. Droplet microfluidics based microseparation systems.

    PubMed

    Xiao, Zhiliang; Niu, Menglei; Zhang, Bo

    2012-06-01

    Lab on a chip (LOC) technology is a promising miniaturization approach. The feature that it significantly reduced sample consumption makes great sense in analytical and bioanalytical chemistry. Since the start of LOC technology, much attention has been focused on continuous flow microfluidic systems. At the turn of the century, droplet microfluidics, which was also termed segmented flow microfluidics, was introduced. Droplet microfluidics employs two immiscible phases to form discrete droplets, which are ideal vessels with confined volume, restricted dispersion, limited cross-contamination, and high surface area. Due to these unique features, droplet microfluidics proves to be a versatile tool in microscale sample handling. This article reviews the utility of droplet microfluidics in microanalytical systems with an emphasize on separation science, including sample encapsulation at ultra-small volume, compartmentalization of separation bands, isolation of droplet contents, and related detection techniques.

  18. Evaporation of inclined water droplets

    PubMed Central

    Kim, Jin Young; Hwang, In Gyu; Weon, Byung Mook

    2017-01-01

    When a drop is placed on a flat substrate tilted at an inclined angle, it can be deformed by gravity and its initial contact angle divides into front and rear contact angles by inclination. Here we study on evaporation dynamics of a pure water droplet on a flat solid substrate by controlling substrate inclination and measuring mass and volume changes of an evaporating droplet with time. We find that complete evaporation time of an inclined droplet becomes longer as gravitational influence by inclination becomes stronger. The gravity itself does not change the evaporation dynamics directly, whereas the gravity-induced droplet deformation increases the difference between front and rear angles, which quickens the onset of depinning and consequently reduces the contact radius. This result makes the evaporation rate of an inclined droplet to be slow. This finding would be important to improve understanding on evaporation dynamics of inclined droplets. PMID:28205642

  19. a Theoretical Model of a Superheated Liquid Droplet Neutron Detector.

    NASA Astrophysics Data System (ADS)

    Harper, Mark Joseph

    Neutrons can interact with the atoms in superheated liquid droplets which are suspended in a viscous matrix material, resulting in the formation of charged recoil ions. These ions transfer energy to the liquid, sometimes resulting in the droplets vaporizing and producing observable bubbles. Devices employing this mechanism are known as superheated liquid droplet detectors, or bubble detectors. The basis of bubble detector operation is identical to that of bubble chambers, which have been well characterized by researchers such as Wilson, Glaser, Seitz, and others since the 1950's. Each of the microscopic superheated liquid droplets behaves like an independent bubble chamber. This dissertation presents a theoretical model which considers the three principal aspects of detector operation: nuclear reactions, charged particle energy deposition, and thermodynamic bubble formation. All possible nuclear reactions were examined and those which could reasonably result in recoil ions sufficiently energetic to vaporize a droplet were analyzed in detail. Feasible interactions having adequate cross sections include elastic and inelastic scattering, n-proton, and n-alpha reactions. Ziegler's TRansport of Ions in Matter (TRIM) code was used to calculate the ions' stopping powers in various compounds based on the ionic energies predicted by standard scattering distributions. If the ions deposit enough energy in a small enough volume then the entire droplet will vaporize without further energy input. Various theories as to the vaporization of droplets by ionizing radiation were studied and a novel method of predicting the critical (minimum) energy was developed. This method can be used to calculate the minimum required stopping power for the ion, from which the threshold neutron energy is obtainable. Experimental verification of the model was accomplished by measuring the response of two different types of bubble detectors to monoenergetic thermal neutrons, as well as to neutrons

  20. Anisotropic particle synthesis inside droplet templates on superhydrophobic surfaces.

    PubMed

    Rastogi, Vinayak; García, Antonio A; Marquez, Manuel; Velev, Orlin D

    2010-01-18

    We demonstrate how droplet templates dispensed on superhydrophobic substrates can be used to fabricate both shape-anisotropic ("doughnut") and composition-anisotropic ("patchy magnetic") supraparticles. The macroscopic shape of the closely-packed particle assemblies is guided by the droplet meniscus. Aqueous droplets of monodisperse microsphere suspensions dispensed on the substrates initially acquire near-spherical shape due to a high contact angle. During the solvent evaporation, however, silica suspension droplets undergo shape transitions (concaving) guiding the structure of the final assemblies into doughnut supraparticles. Composition anisotropy is achieved by drying a droplet containing a mixed suspension of latex and magnetic nanoparticles, while exposing it to magnetic field gradients. Depending on the pattern of the magnetic fields, the magnetic nanoparticles segregate into single, bilateral, or trilateral, patched spherical supraparticles. The physical effects leading to the development of anisotropy are discussed. Unlike the conventional wet self-assembly (WSA) methods where the final structures need to be extracted from the liquid environment, this efficient one-step procedure produces ready to use "dry" supraparticles. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Analyzing Benzene and Cyclohexane Emulsion Droplet Collisions on Ultramicroelectrodes.

    PubMed

    Li, Yan; Deng, Haiqiang; Dick, Jeffrey E; Bard, Allen J

    2015-11-03

    We report the collisions of single emulsion oil droplets with extremely low dielectric constants (e.g., benzene, ε of 2.27, or cyclohexane, ε of 2.02) as studied via emulsion droplet reactor (EDR) on an ultramicroelectrode (UME). By applying appropriate potentials to the UME, we observed the electrochemical effects of single-collision signals from the bulk electrolysis of single emulsion droplets. Different hydrophobic redox species (ferrocene, decamethyl-ferrocene, or metalloporphyrin) were trapped in a mixed benzene (or cyclohexane) oil-in-water emulsion using an ionic liquid as the supporting electrolyte and emulsifier. The emulsions were prepared using ultrasonic processing. Spike-like responses were observed in each i-t response due to the complete electrolysis of all of the above-mentioned redox species within the droplet. On the basis of these single-particle collision results, the collision frequency, size distribution, i-t decay behavior of the emulsion droplets, and possible mechanisms are analyzed and discussed. This work demonstrated that bulk electrolysis can be achieved in a few seconds in these attoliter reactors, suggesting many applications, such as analysis and electrosynthesis in low dielectric constant solvents, which have a much broader potential window.

  2. Maze solving by chemotactic droplets.

    PubMed

    Lagzi, István; Soh, Siowling; Wesson, Paul J; Browne, Kevin P; Grzybowski, Bartosz A

    2010-02-03

    Droplets emitting surface-active chemicals exhibit chemotaxis toward low-pH regions. Such droplets are self-propelled and navigate through a complex maze to seek a source of acid placed at one of the maze's exits. In doing so, the droplets find the shortest path through the maze. Chemotaxis and maze solving are due to an interplay between acid/base chemistry and surface tension effects.

  3. Maze Solving by Chemotactic Droplets

    SciTech Connect

    Lagzi, Istvan; Soh, Siowling; Wesson, Paul J.; Browne, Kevin P.; Grzybowski, Bartosz A.

    2010-01-11

    Droplets emitting surface-active chemicals exhibit chemotaxis toward low-pH regions. Such droplets are self-propelled and navigate through a complex maze to seek a source of acid placed at one of the maze’s exits. In doing so, the droplets find the shortest path through the maze. Chemotaxis and maze solving are due to an interplay between acid/base chemistry and surface tension effects.

  4. Monodisperse, submicrometer droplets via condensation of microfluidic-generated gas bubbles.

    PubMed

    Seo, Minseok; Matsuura, Naomi

    2012-09-10

    Microfluidics (MFs) can produce monodisperse droplets with precise size control. However, the synthesis of monodisperse droplets much smaller than the minimum feature size of the microfluidic device (MFD) remains challenging, thus limiting the production of submicrometer droplets. To overcome the minimum micrometer-scale droplet sizes that can be generated using typical MFDs, the droplet material is heated above its boiling point (bp), and then MFs is used to produce monodisperse micrometer-scale bubbles (MBs) that are easily formed in the size regime where standard MFDs have excellent size control. After MBs are formed, they are cooled, condensing into dramatically smaller droplets that are beyond the size limit achievable using the original MFD, with a size decrease corresponding to the density difference between the gas and liquid phases of the droplet material. Herein, it is shown experimentally that monodisperse, submicrometer droplets of predictable sizes can be condensed from a monodisperse population of MBs as generated by MFs. Using perfluoropentane (PFP) as a representative solvent due to its low bp (29.2 °C), it is demonstrated that monodisperse PFP MBs can be produced at MFD temperatures >3.6 °C above the bp of PFP over a wide range of sizes (i.e., diameters from 2 to 200 μm). Independent of initial size, the generated MBs shrink rapidly in size from about 3 to 0 °C above the bp of PFP, corresponding to a phase change from gas to liquid, after which they shrink more slowly to form fully condensed droplets with diameters 5.0 ± 0.1 times smaller than the initial size of the MBs, even in the submicrometer size regime. This new method is versatile and flexible, and may be applied to any type of low-bp solvent for the manufacture of different submicrometer droplets for which precisely controlled dimensions are required.

  5. Patterned surface anchoring of nematic droplets at miscible liquid-liquid interfaces.

    PubMed

    Wang, Xiaoguang; Zhou, Ye; Kim, Young-Ki; Miller, Daniel S; Zhang, Rui; Martinez-Gonzalez, Jose A; Bukusoglu, Emre; Zhang, Bo; Brown, Thaddeus M; de Pablo, Juan J; Abbott, Nicholas L

    2017-08-30

    We report on the internal configurations of droplets of nematic liquid crystals (LCs; 10-50 μm-in-diameter; comprised of 4-cyano-4'-pentylbiphenyl and 4-(3-acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester) sedimented from aqueous solutions of sodium dodecyl sulfate (SDS) onto interfaces formed with pure glycerol. We observed a family of internal LC droplet configurations and topological defects consistent with a remarkably abrupt transition from homeotropic (perpendicular) to tangential anchoring on the surface of the LC droplets in the interfacial environment. Calculations of the interdiffusion of water and glycerol at the aqueous-glycerol interface revealed the thickness of the diffuse interfacial region of the two miscible liquids to be small (0.2-0.5 μm) compared to the diameters of the LC droplets on the experimental time-scale (15-120 minutes), leading us to hypothesize that the patterned surface anchoring was induced by gradients in concentration of SDS and glycerol across the diameter of the LC droplets in the interfacial region. This hypothesis received additional support from experiments in which the time of sedimentation of the LC droplets onto the interface was systematically increased and the droplets were photo-polymerized to preserve their configurations: the configurations of the LC droplets were consistent with a time-dependent decrease in the fraction of the surface area of each droplet exhibiting homeotropic anchoring. Specifically, LC droplets with <10% surface area with tangential anchoring exhibited a bulk point defect within the LC droplet, whereas droplets with >10% surface area with tangential anchoring exhibited a boojum defect within the tangential region and a disclination loop separated the regions with tangential and homeotropic anchoring. The topological charge of these LC droplet configurations was found to be consistent with the geometrical theorems of Poincaré and Gauss and also well-described by computer

  6. Gelled MMH hypergolic droplet investigation

    NASA Astrophysics Data System (ADS)

    Solomon, Yair

    Gelled propellants are promising candidates for certain future rocket applications, offering potential improvements in performance and/or safety over conventional liquid and solid systems. In particular, gelled hypergolic propellants can eliminate some handling difficulties by reducing leakage hazard. Before such systems can be developed, however, a fundamental understanding of combustion of the gel droplet is required. This study addresses the combustion behavior of monomethyl hydrazine (MMH) droplet gelled with both hydroxypropyl cellulose (HPC) and fumed silica in an environment of gaseous nitrogen dioxide. All MMH/HPC gel droplets displayed swelling and jetting that are typical to hydrocarbon gels with an organic gelling agent. Burning rates were measured for droplet diameters from 1.8 to 3.2 mm at three ambient pressures of 1.72, 2.06 and 2.89 bar. It was found that the droplet burning rate is dependent on the droplet diameter similarly to liquid MMH. Over the investigated pressure range, no dependence of burning rate on pressure was found. The combustion of MMH/HPC gel was compared to MMH/tetraglyme to examine the influence the type of gelling agent. Droplets of MMH and liquid tetraglyme showed increasing swelling frequencies and volume fluctuations during combustion while the MMH and HPC droplets exhibited a more constant burning history. The MMH/Silica gels showed a different combustion mechanism with the formation of a rigid silica structure, micro-explosions, and up to a 50% reduction in droplet volume during combustion.

  7. Uranium droplet core nuclear rocket

    NASA Technical Reports Server (NTRS)

    Anghaie, Samim

    1991-01-01

    Uranium droplet nuclear rocket is conceptually designed to utilize the broad temperature range ofthe liquid phase of metallic uranium in droplet configuration which maximizes the energy transfer area per unit fuel volume. In a baseline system dissociated hydrogen at 100 bar is heated to 6000 K, providing 2000 second of Isp. Fission fragments and intense radian field enhance the dissociation of molecular hydrogen beyond the equilibrium thermodynamic level. Uranium droplets in the core are confined and separated by an axisymmetric vortex flow generated by high velocity tangential injection of hydrogen in the mid-core regions. Droplet uranium flow to the core is controlled and adjusted by a twin flow nozzle injection system.

  8. Uranium droplet core nuclear rocket

    NASA Technical Reports Server (NTRS)

    Anghaie, Samim

    1991-01-01

    Uranium droplet nuclear rocket is conceptually designed to utilize the broad temperature range ofthe liquid phase of metallic uranium in droplet configuration which maximizes the energy transfer area per unit fuel volume. In a baseline system dissociated hydrogen at 100 bar is heated to 6000 K, providing 2000 second of Isp. Fission fragments and intense radian field enhance the dissociation of molecular hydrogen beyond the equilibrium thermodynamic level. Uranium droplets in the core are confined and separated by an axisymmetric vortex flow generated by high velocity tangential injection of hydrogen in the mid-core regions. Droplet uranium flow to the core is controlled and adjusted by a twin flow nozzle injection system.

  9. Small droplets on superhydrophobic substrates.

    PubMed

    Gross, Markus; Varnik, Fathollah; Raabe, Dierk; Steinbach, Ingo

    2010-05-01

    We investigate the wetting behavior of liquid droplets on rough hydrophobic substrates for the case of droplets that are of comparable size to the surface asperities. Using a simple three-dimensional analytical free-energy model, we have shown in a recent letter [M. Gross, F. Varnik, and D. Raabe, EPL 88, 26002 (2009)] that, in addition to the well-known Cassie-Baxter and Wenzel states, there exists a further metastable wetting state where the droplet is immersed into the texture to a finite depth, yet not touching the bottom of the substrate. Due to this new state, a quasistatically evaporating droplet can be saved from going over to the Wenzel state and instead remains close to the top of the surface. In the present paper, we give an in-depth account of the droplet behavior based on the results of extensive computer simulations and an improved theoretical model. In particular, we show that releasing the assumption that the droplet is pinned at the outer edges of the pillars improves the analytical results for larger droplets. Interestingly, all qualitative aspects, such as the existence of an intermediate minimum and the "reentrant transition," remain unchanged. We also give a detailed description of the evaporation process for droplets of varying sizes. Our results point out the role of droplet size for superhydrophobicity and give hints for achieving the desired wetting properties of technically produced materials.

  10. Bending instability of electrically charged liquid jets of polymer solutions in electrospinning

    NASA Astrophysics Data System (ADS)

    Reneker, Darrell H.; Yarin, Alexander L.; Fong, Hao; Koombhongse, Sureeporn

    2000-05-01

    Nanofibers of polymers were electrospun by creating an electrically charged jet of polymer solution at a pendent droplet. After the jet flowed away from the droplet in a nearly straight line, it bent into a complex path and other changes in shape occurred, during which electrical forces stretched and thinned it by very large ratios. After the solvent evaporated, birefringent nanofibers were left. In this article the reasons for the instability are analyzed and explained using a mathematical model. The rheological complexity of the polymer solution is included, which allows consideration of viscoelastic jets. It is shown that the longitudinal stress caused by the external electric field acting on the charge carried by the jet stabilized the straight jet for some distance. Then a lateral perturbation grew in response to the repulsive forces between adjacent elements of charge carried by the jet. The motion of segments of the jet grew rapidly into an electrically driven bending instability. The three-dimensional paths of continuous jets were calculated, both in the nearly straight region where the instability grew slowly and in the region where the bending dominated the path of the jet. The mathematical model provides a reasonable representation of the experimental data, particularly of the jet paths determined from high speed videographic observations.

  11. 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.

  12. Interface-tracking electro-hydrodynamic model for droplet coalescence

    NASA Astrophysics Data System (ADS)

    Crowl Erickson, Lindsay; Noble, David

    2012-11-01

    Many fluid-based technologies rely on electrical fields to control the motion of droplets, e.g. micro-fluidic devices for high-speed droplet sorting, solution separation for chemical detectors, and purification of biodiesel fuel. Precise control over droplets is crucial to these applications. However, electric fields can induce complex and unpredictable fluid dynamics. Recent experiments (Ristenpart et al. 2009) have demonstrated that oppositely charged droplets bounce rather than coalesce in the presence of strong electric fields. Analytic hydrodynamic approximations for interfaces become invalid near coalescence, and therefore detailed numerical simulations are necessary. We present a conformal decomposition finite element (CDFEM) interface-tracking method for two-phase flow to demonstrate electro-coalescence. CDFEM is a sharp interface method that decomposes elements along fluid-fluid boundaries and uses a level set function to represent the interface. The electro-hydrodynamic equations solved allow for convection of charge and charge accumulation at the interface, both of which may be important factors for the pinch-off dynamics in this parameter regime.

  13. Droplet formation and scaling in dense suspensions

    PubMed Central

    Miskin, Marc Z.; Jaeger, Heinrich M.

    2012-01-01

    When a dense suspension is squeezed from a nozzle, droplet detachment can occur similar to that of pure liquids. While in pure liquids the process of droplet detachment is well characterized through self-similar profiles and known scaling laws, we show here the simple presence of particles causes suspensions to break up in a new fashion. Using high-speed imaging, we find that detachment of a suspension drop is described by a power law; specifically we find the neck minimum radius, rm, scales like near breakup at time τ = 0. We demonstrate data collapse in a variety of particle/liquid combinations, packing fractions, solvent viscosities, and initial conditions. We argue that this scaling is a consequence of particles deforming the neck surface, thereby creating a pressure that is balanced by inertia, and show how it emerges from topological constraints that relate particle configurations with macroscopic Gaussian curvature. This new type of scaling, uniquely enforced by geometry and regulated by the particles, displays memory of its initial conditions, fails to be self-similar, and has implications for the pressure given at generic suspension interfaces. PMID:22392979

  14. Coalescence-induced droplet actuation

    NASA Astrophysics Data System (ADS)

    Sellier, Mathieu; Verdier, Claude; Nock, Volker

    2011-11-01

    This work investigates a little explored driving mechanism to actuate droplets: the surface tension gradient which arises during the coalescence of two droplets of liquid having different compositions and therefore surface tensions. The resulting surface tension gradient gives rise to a Marangoni flow which, if sufficiently large, can displace the droplet. In order to understand, the flow dynamics arising during the coalescence of droplets of different fluids, a model has been developed in the lubrication framework. The numerical results confirm the existence of a self-propulsion window which depends on two dimensionless groups representing competing effects during the coalescence: the surface tension contrast between the droplets which promotes actuation and species diffusion which tends to make the mixture uniform thereby anihilating Marangoni flow and droplet motion. In parallel, experiments have been conducted to confirm this self-propulsion behaviour. The experiment consists in depositing a droplet of distilled water on a ``hydrophilic highway.'' This stripe was obtained by plasma-treating a piece of PDMS shielded in some parts by glass coverslips. This surface functionalization was found to be the most convenient way to control the coalescence. When a droplet of ethanol is deposited near the ``water slug,'' coalescence occurs and a rapid motion of the resulting mixture is observed. The support of the Dumont d'Urville NZ-France Science & Technology program is gratefully acknowledged.

  15. 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

  16. Experiments examining drag in linear droplet packets

    NASA Astrophysics Data System (ADS)

    Nguyen, Q. V.; Dunn-Rankin, D.

    1992-01-01

    This paper presents an experimental study of vertically traveling droplet packets, where the droplets in each packet are aligned linearly, one behind another. The paper describes in detail, an experimental apparatus that produces repeatable, linearly aligned, and isolated droplet packets containing 1 6 droplets per packet. The apparatus is suitable for examining aerodynamic interactions between droplets within each packet. This paper demonstrates the performance of the apparatus by examining the drag reduction and collision of droplets traveling in the wake of a lead droplet. Comparison of a calculated single droplet trajectory with the detailed droplet position versus time data for a droplet packet provides the average drag reduction experienced by the trailing droplets due to the aerodynamic wake of the lead droplet. For the conditions of our experiment (4 droplet packet, 145 μm methanol droplets, 10 m/s initial velocity, initial droplet spacing of 5.2 droplet diameters, Reynolds number approx. 80) the average drag on the first trailing droplet was found to be 75% of the drag on the lead droplet.

  17. Leidenfrost boiling of water droplet

    NASA Astrophysics Data System (ADS)

    Orzechowski, Tadeusz

    The investigations concerned a large water droplet at the heating surface temperature above the Leidenfrost point. The heating cylinder was the main component of experimental stand on which investigations were performed. The measurement system was placed on the high-sensitivity scales. Data transmission was performed through RS232 interface. The author-designed program, with extended functions to control the system, was applied. The present paper examines the behaviour of a large single drop levitating over a hot surface, unsteady mass of the drop, and heat transfer. In computations, the dependence, available in the literature, for the orthogonal droplet projection on the heating surface as a function of time was employed. It was confirmed that the local value of the heat transfer coefficient is a power function of the area of the droplet surface projection. Also, a linear relationship between the flux of mass evaporated from the droplet and the droplet orthogonal projection was observed.

  18. Solvent wash solution

    DOEpatents

    Neace, James C.

    1986-01-01

    Process for removing diluent degradation products from a solvent extraction solution, which has been used to recover uranium and plutonium from spent nuclear fuel. A wash solution and the solvent extraction solution are combined. The wash solution contains (a) water and (b) up to about, and including, 50 volume percent of at least one-polar water-miscible organic solvent based on the total volume of the water and the highly-polar organic solvent. The wash solution also preferably contains at least one inorganic salt. The diluent degradation products dissolve in the highly-polar organic solvent and the organic solvent extraction solvent do not dissolve in the highly-polar organic solvent. The highly-polar organic solvent and the extraction solvent are separated.

  19. Solvent wash solution

    DOEpatents

    Neace, J.C.

    1984-03-13

    A process is claimed for removing diluent degradation products from a solvent extraction solution, which has been used to recover uranium and plutonium from spent nuclear fuel. A wash solution and the solvent extraction solution are combined. The wash solution contains (a) water and (b) up to about, and including, 50 vol % of at least one-polar water-miscible organic solvent based on the total volume of the water and the highly-polar organic solvent. The wash solution also preferably contains at least one inorganic salt. The diluent degradation products dissolve in the highly-polar organic solvent and the organic solvent extraction solvent do not dissolve in the highly-polar organic solvent. The highly-polar organic solvent and the extraction solvent are separated.

  20. Points, skyrmions and torons in chiral nematic droplets

    PubMed Central

    Posnjak, Gregor; Čopar, Simon; Muševič, Igor

    2016-01-01

    Chiral nematic droplets with perpendicular surface alignment of liquid crystalline molecules frustrate the helical structure into convoluted 3D textures with complex topology. We observe the droplets with fluorescent confocal polarising microscopy (FCPM), and reconstruct and analyse for the first time the topology of the 3D director field using a novel method of director reconstruction from raw data. We always find an odd number of topological defects, which preserve the total topological charge of the droplet of +1 regardless of chirality. At higher chirality, we observe up to 5 point hedgehog defects, which are elastically stabilized with convoluted twisted structures, reminiscent of 2D skyrmions and toron-like structure, nested into a sphere. PMID:27198649

  1. Points, skyrmions and torons in chiral nematic droplets

    NASA Astrophysics Data System (ADS)

    Posnjak, Gregor; Čopar, Simon; Muševič, Igor

    2016-05-01

    Chiral nematic droplets with perpendicular surface alignment of liquid crystalline molecules frustrate the helical structure into convoluted 3D textures with complex topology. We observe the droplets with fluorescent confocal polarising microscopy (FCPM), and reconstruct and analyse for the first time the topology of the 3D director field using a novel method of director reconstruction from raw data. We always find an odd number of topological defects, which preserve the total topological charge of the droplet of +1 regardless of chirality. At higher chirality, we observe up to 5 point hedgehog defects, which are elastically stabilized with convoluted twisted structures, reminiscent of 2D skyrmions and toron-like structure, nested into a sphere.

  2. Droplet Burns in the Fiber-Supported Droplet Combustion Experiment

    NASA Technical Reports Server (NTRS)

    2003-01-01

    A fuel droplet burns in the Fiber-Supported Droplet Combustion (FSDC) Experiment on STS-94, July 4 1997, MET:02/19:20 (approximate). This experiment, performed in the Middeck Glovebox, allows us to study the burning of fuels such as n-heptane, n-decane, methanol, ethanol, methanol/water mixtures, and heptane/hexadecane mixtures in droplets as large as 6 mm (nearly 1/4 inch). In this sequence, you see the burn of a 5mm droplet of n-heptane, in a 30% O2/He environment at 1 atmosphere pressure. The droplet (looking bright pink because of reflected light) hangs suspended from the supporting fiber. FSDC-2 studied fundamental phenomena related to liquid fuel droplet combustion in air. Pure fuels and mixtures of fuels were burned as isolated single and dual droplets with and without forced air convection. The FSDC guest investigator was Forman Williams, University of California, San Diego. The experiment was part of the space research investigations conducted during the Microgravity Science Laboratory-1R mission (STS-94, July 1-17 1997). Advanced combustion experiments will be a part of investigations plarned for the International Space Station. (279KB JPEG, 1350 x 2026 pixels; downlinked video, higher quality not available) The MPG from which this composite was made is available at http://mix.msfc.nasa.gov/ABSTRACTS/MSFC-0300175.html.

  3. Surface Interaction of Water-in-Oil Emulsion Droplets with Interfacially Active Asphaltenes.

    PubMed

    Shi, Chen; Zhang, Ling; Xie, Lei; Lu, Xi; Liu, Qingxia; He, Jiajun; Mantilla, Cesar A; Van den Berg, Frans G A; Zeng, Hongbo

    2017-02-07

    Adsorption of interfacially active components at the water/oil interface plays critical roles in determining the properties and behaviors of emulsion droplets. In this study, the droplet probe atomic force microscopy (AFM) technique was applied, for the first time, to quantitatively study the interaction mechanism between water-in-oil (W/O) emulsion droplets with interfacially adsorbed asphaltenes. The behaviors and stability of W/O emulsion droplets were demonstrated to be significantly influenced by the asphaltene concentration of organic solution where the emulsions were aged, aging time, force load, contact time, and solvent type. Bare water droplets could readily coalesce with each other in oil (i.e., toluene), while interfacially adsorbed asphaltenes could sterically inhibit droplet coalescence and induce interfacial adhesion during separation of the water droplets. For low asphaltene concentration cases, the adhesion increased with increasing asphaltene concentration (≤100 mg/L), but it significantly decreased at relatively high asphaltene concentration (e.g., 500 mg/L). Experiments in Heptol (i.e., mixture of toluene and heptane) showed that the addition of a poor solvent for asphaltenes (e.g., heptane) could enhance the interfacial adhesion between emulsion droplets at relatively low asphaltene concentration but could weaken the adhesion at relatively high asphaltene concentration. This work has quantified the interactions between W/O emulsion droplets with interfacially adsorbed asphaltenes, and the results provide useful implications into the stabilization mechanisms of W/O emulsions in oil production. The methodology in this work can be readily extended to other W/O emulsion systems with interfacially active components.

  4. Spontaneous Formation of Water Droplets at Oil-Solid Interfaces

    PubMed Central

    Yang, Zhongqiang; Abbott, Nicholas L.

    2010-01-01

    We report observations of spontaneous formation of micrometer-sized water droplets within micrometer-thick films of a range of different oils (isotropic and nematic 4-cyano-4’-pentylbiphenyl (5CB), and silicone, olive and corn oil) that are supported on glass substrates treated with octadecyltrichlorosilane (OTS) and immersed under water. Confocal imaging was used to determine that the water droplets nucleate and grow at the interface between the oils and OTS-treated glass with a contact angle of ~130°. A simple thermodynamic model based on macroscopic interfacial energetic arguments consistent with the contact angle of 130°, however, fails to account for the spontaneous formation of the water droplets. ζ-potential measurements performed with OTS-treated glass (− 59.0 ± 16.4 mV) and hydrophobic monolayers formed on gold films (2.0 ± 0.7 mV), when combined with the observed absence of droplet formation under films of oil supported on the latter surfaces, suggest that the charge of the oil-solid interface promotes partitioning of water to the interfacial region. The hydrophobic nature of the OTS-treated glass promotes dewetting of water accumulated in the interfacial region into droplets (a thin film of water is seen to form on bare glass). The inhibitory effect on droplet formation of both salt (NaCl) and sucrose (0.1mM to 500mM) added to the aqueous phase was similar, indicating that both solutes lower the chemical potential of the bulk water (osmotic effect) sufficiently to prevent partitioning of the water to the interface between the oil and supporting substrates. These results suggest that charged, hydrophobic surfaces can provide routes to spontaneous formation of surface-supported, water-in-oil emulsions. PMID:20712383

  5. Investigation of droplet collisions for solutions with different solids content

    NASA Astrophysics Data System (ADS)

    Kuschel, Matthias; Sommerfeld, Martin

    2013-02-01

    The collision behaviour of droplets and the collision outcome are investigated for high viscous polymer solutions. For that purpose, two droplet chains produced by piezoelectric droplet generators are directed towards each other at a certain angle so that individual droplet pairs collide. For recording the collision event, one double-image and one high-speed CCD camera were used. One camera is positioned perpendicular to the collision plane recording the outcome of the collision, and the second camera is aligned parallel to the collision plane to assure that the droplet chains are exactly in one plane. A new approach for tracking droplets in combination with an extended particle tracking velocimetry algorithm has been developed. Time-resolved series of pictures were used to analyse the dynamics of droplet collisions. The three different water soluble substances were saccharose and 1-Ethenyl-2-pyrrolidone (PVP) with different molecular weights (K17, K30). The solvent was demineralised water. The solids contents ranged from 20 to 60 %, 5 to 25 % and 5 to 35 %, yielding dynamic viscosities in the range of 2-60 mPa s. Results were collected for different pairs of impact angles and Weber numbers in order to establish common collision maps for characterising the outcomes. Here, relative velocities between 0.5 and 4 m/s and impact parameters in the interval from 0 to 1 for equal-sized droplets (Δ = 1) have been investigated. Additionally, satellite formation will be discussed exemplarily for K30. A comparison with common models of different authors (Ashgriz and Poo in J Fluid Mech 221:183-204, 1990; Estrade et al. in Int J Heat Fluid Flow 20:486-491, 1999) mainly derived for low viscous droplets revealed that the upper limit of their validity is given by an Ohnesorge number of Oh = 0.115 and a capillary number of Ca = 0.577. For higher values of these non-dimensional parameters and hence higher dynamic viscosities, these models are unable to predict correctly the

  6. Lossless droplet transfer of droplet-based microfluidic analysis

    SciTech Connect

    Kelly, Ryan T; Tang, Keqi; Page, Jason S; Smith, Richard D

    2011-11-22

    A transfer structure for droplet-based microfluidic analysis is characterized by a first conduit containing a first stream having at least one immiscible droplet of aqueous material and a second conduit containing a second stream comprising an aqueous fluid. The interface between the first conduit and the second conduit can define a plurality of apertures, wherein the apertures are sized to prevent exchange of the first and second streams between conduits while allowing lossless transfer of droplets from the first conduit to the second conduit through contact between the first and second streams.

  7. 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.

  8. Leidenfrost levitation: beyond droplets

    PubMed Central

    Hashmi, Ali; Xu, Yuhao; Coder, Benjamin; Osborne, Paul A.; Spafford, Jonathon; Michael, Grant E.; Yu, Gan; Xu, Jie

    2012-01-01

    Friction is a major inhibitor in almost every mechanical system. Enlightened by the Leidenfrost effect – a droplet can be levitated by its own vapor layer on a sufficiently hot surface – we demonstrate for the first time that a small cart can also be levitated by Leidenfrost vapor. The levitated cart can carry certain amount of load and move frictionlessly over the hot surface. The maximum load that the cart can carry is experimentally tested over a range of surface temperatures. We show that the levitated cart can be propelled not only by gravitational force over a slanted flat surface, but also self-propelled over a ratchet shaped horizontal surface. In the end, we experimentally tested water consumption rate for sustaining the levitated cart, and compared the results to theoretical calculations. If perfected, this frictionless Leidenfrost cart could be used in numerous engineering applications where relative motion exists between surfaces. PMID:23150770

  9. Leidenfrost levitation: beyond droplets.

    PubMed

    Hashmi, Ali; Xu, Yuhao; Coder, Benjamin; Osborne, Paul A; Spafford, Jonathon; Michael, Grant E; Yu, Gan; Xu, Jie

    2012-01-01

    Friction is a major inhibitor in almost every mechanical system. Enlightened by the Leidenfrost effect - a droplet can be levitated by its own vapor layer on a sufficiently hot surface - we demonstrate for the first time that a small cart can also be levitated by Leidenfrost vapor. The levitated cart can carry certain amount of load and move frictionlessly over the hot surface. The maximum load that the cart can carry is experimentally tested over a range of surface temperatures. We show that the levitated cart can be propelled not only by gravitational force over a slanted flat surface, but also self-propelled over a ratchet shaped horizontal surface. In the end, we experimentally tested water consumption rate for sustaining the levitated cart, and compared the results to theoretical calculations. If perfected, this frictionless Leidenfrost cart could be used in numerous engineering applications where relative motion exists between surfaces.

  10. Single Stage Contactor Testing Of The Next Generation Solvent Blend

    SciTech Connect

    Herman, D. T.; Peters, T. B.; Duignan, M. R.; Williams, M. R.; Poirier, M. R.; Brass, E. A.; Garrison, A. G.; Ketusky, E. T.

    2014-01-06

    The Modular Caustic Side Solvent Extraction (CSSX) Unit (MCU) facility at the Savannah River Site (SRS) is actively pursuing the transition from the current BOBCalixC6 based solvent to the Next Generation Solvent (NGS)-MCU solvent to increase the cesium decontamination factor. To support this integration of NGS into the MCU facility the Savannah River National Laboratory (SRNL) performed testing of a blend of the NGS (MaxCalix based solvent) with the current solvent (BOBCalixC6 based solvent) for the removal of cesium (Cs) from the liquid salt waste stream. This testing utilized a blend of BOBCalixC6 based solvent and the NGS with the new extractant, MaxCalix, as well as a new suppressor, tris(3,7dimethyloctyl) guanidine. Single stage tests were conducted using the full size V-05 and V-10 liquid-to-liquid centrifugal contactors installed at SRNL. These tests were designed to determine the mass transfer and hydraulic characteristics with the NGS solvent blended with the projected heel of the BOBCalixC6 based solvent that will exist in MCU at time of transition. The test program evaluated the amount of organic carryover and the droplet size of the organic carryover phases using several analytical methods. The results indicate that hydraulically, the NGS solvent performed hydraulically similar to the current solvent which was expected. For the organic carryover 93% of the solvent is predicted to be recovered from the stripping operation and 96% from the extraction operation. As for the mass transfer, the NGS solvent significantly improved the cesium DF by at least an order of magnitude when extrapolating the One-stage results to actual Seven-stage extraction operation with a stage efficiency of 95%.

  11. Droplet resonator based optofluidic microlasers

    NASA Astrophysics Data System (ADS)

    Kiraz, Alper; Jonáš, Alexandr; Aas, Mehdi; Karadag, Yasin; Brzobohatý, Oto; Ježek, Jan; Pilát, Zdeněk.; Zemánek, Pavel; Anand, Suman; McGloin, David

    2014-03-01

    We introduce tunable optofluidic microlasers based on active optical resonant cavities formed by optically stretched, dye-doped emulsion droplets confined in a dual-beam optical trap. To achieve tunable dye lasing, optically pumped droplets of oil dispersed in water are stretched by light in the dual-beam trap. Subsequently, resonant path lengths of whispering gallery modes (WGMs) propagating in the droplet are modified, leading to shifts in the microlaser emission wavelengths. We also report lasing in airborne, Rhodamine B-doped glycerolwater droplets which were localized using optical tweezers. While being trapped near the focal point of an infrared laser, the droplets were pumped with a Q-switched green laser. Furthermore, biological lasing in droplets supported by a superhydrophobic surface is demonstrated using a solution of Venus variant of the yellow fluorescent protein or E. Coli bacterial cells expressing stably the Venus protein. Our results may lead to new ways of probing airborne particles, exploiting the high sensitivity of stimulated emission to small perturbations in the droplet laser cavity and the gain medium.

  12. Droplets, Bubbles and Ultrasound Interactions.

    PubMed

    Shpak, Oleksandr; Verweij, Martin; de Jong, Nico; Versluis, Michel

    2016-01-01

    The interaction of droplets and bubbles with ultrasound has been studied extensively in the last 25 years. Microbubbles are broadly used in diagnostic and therapeutic medical applications, for instance, as ultrasound contrast agents. They have a similar size as red blood cells, and thus are able to circulate within blood vessels. Perfluorocarbon liquid droplets can be a potential new generation of microbubble agents as ultrasound can trigger their conversion into gas bubbles. Prior to activation, they are at least five times smaller in diameter than the resulting bubbles. Together with the violent nature of the phase-transition, the droplets can be used for local drug delivery, embolotherapy, HIFU enhancement and tumor imaging. Here we explain the basics of bubble dynamics, described by the Rayleigh-Plesset equation, bubble resonance frequency, damping and quality factor. We show the elegant calculation of the above characteristics for the case of small amplitude oscillations by linearizing the equations. The effect and importance of a bubble coating and effective surface tension are also discussed. We give the main characteristics of the power spectrum of bubble oscillations. Preceding bubble dynamics, ultrasound propagation is introduced. We explain the speed of sound, nonlinearity and attenuation terms. We examine bubble ultrasound scattering and how it depends on the wave-shape of the incident wave. Finally, we introduce droplet interaction with ultrasound. We elucidate the ultrasound-focusing concept within a droplets sphere, droplet shaking due to media compressibility and droplet phase-conversion dynamics.

  13. Bacterial encountering with oil droplet

    NASA Astrophysics Data System (ADS)

    Sheng, Jian; Molaei, Mehdi

    2014-11-01

    Encountering of microorganisms with rising oil droplets in aqueous environments is the first and one of the critical steps in the biodegradation of crude oil. Several factors such as droplet sizes, rising velocity, surfactant, and motility of bacteria are expected to affect the encounter rate. We establish well controlled microfluidic devices by applying layer-by-layer technique that allows us to produce horizontal micro droplets with different sizes. The encounter rates of passive particles, motile and non-motile bacteria with these droplets are measured by high speed microscopy. The effects of mobility and motility of these particles on encounter rates are assessed quantitatively. Meanwhile, we visualize reorientation of the particle due to flow filed around the oil droplet. Results show that the motile bacteria have higher probabilities to interact with an oil droplet compare to the passive particles. Ongoing analyses focus on the effect of shear rates, angular dispersion, curvatures of streamlines, and the swimming velocity of bacteria. The ratios of the encounter area to the entire droplet surface at various flow regimes will also been measured. GoMRI.

  14. Asymmetric Wettability Directs Leidenfrost Droplets

    SciTech Connect

    Agapov, Rebecca L; Boreyko, Jonathan B; Briggs, Dayrl P; Srijanto, Bernadeta R; Retterer, Scott T; Collier, Pat; Lavrik, Nickolay V

    2014-01-01

    Leidenfrost phenomena on nano- and microstructured surfaces are of great importance for increasing control over heat transfer in high power density systems utilizing boiling phenomena. They also provide an elegant means to direct droplet motion in a variety of recently emerging fluidic systems. Here, we report the fabrication and characterization of tilted nanopillar arrays (TNPAs) that exhibit directional Leidenfrost water droplets under dynamic conditions, namely on impact with Weber numbers 40 at T 325 C. The batch fabrication of the TNPAs was achieved by glancing-angle anisotropic reactive ion etching of a thermally dewet platinum mask, with mean pillar diameters of 100 nm and heights of 200-500 nm. In contrast to previously implemented macro- and microscopic Leidenfrost ratchets, our TNPAs induce no preferential directional movement of Leidenfrost droplets under conditions approaching steady-state film boiling, suggesting that the observed droplet directionality is not a result of asymmetric vapor flow. Using high-speed imaging, phase diagrams were constructed for the boiling behavior upon impact for droplets falling onto TNPAs, straight nanopillar arrays, and smooth silicon surfaces. The asymmetric impact and directional trajectory of droplets was exclusive to the TNPAs for impacts corresponding to the transition boiling regime, revealing that asymmetric wettability upon impact is the mechanism for the droplet directionality.

  15. Application of an integrated phase Doppler interferometer/rainbow thermometer/point-diffraction interferometer for characterizing burning droplets

    SciTech Connect

    Sankar, S.V.; Buermann, D.H.; Ibrahim, K.M.; Bachalo, W.D.

    1994-12-31

    A laser-based, nonintrusive diagnostic instrument has been developed for simultaneously measuring the velocity, size, temperature (refractive index) of burning droplets, and the gas-phase temperature field surrounding the burning droplet. The developed diagnostic is suitable for experimental studies involving single droplet/droplet array combustion. The size and velocity of the droplets are measured using the well-established phase Doppler interferometric technique. The temperature/refractive index of the droplets are determined by measuring the primary rainbow location with a linear charge coupled device (CCD) array. The gas-phase temperature distribution is inferred from interferograms obtained with point-diffraction interferometry (PDI). The three diagnostic techniques have been completely integrated to yield a single diagnostic instrument. New algorithms have been developed for extracting and normalizing the interferograms from noisy digital images. Methods for unambiguous phase unwrapping were also identified. The integrated diagnostic was tested by applying it to the case of isolated burning n-heptane droplets in motion. Using a combined experimental/theoretical approach, it was possible to extract the radial temperature profile of the gas phase surrounding the droplet in addition to the droplet velocity size, and temperature. The integrated diagnostic tool has significant potential for studying fundamental droplet combustion processes and for validating state-of-the-art droplet/spray combustion models.

  16. 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

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

    PubMed

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

    2016-08-18

    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.

  18. 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

  19. 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; Im, Do Jin; Lee, Sang Joon; Kang, In Seok

    2016-08-01

    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.

  20. Thermocapillary Convection in Liquid Droplets

    NASA Technical Reports Server (NTRS)

    1986-01-01

    The purpose of this video is to understand the effects of surface tension on fluid convection. The fluid system chosen is the liquid sessile droplet to show the importance in single crystal growth, the spray drying and cooling of metal, and the advance droplet radiators of the space stations radiators. A cross sectional representation of a hemispherical liquid droplet under ideal conditions is used to show internal fluid motion. A direct simulation of buoyancy-dominant convection and surface tension-dominant convection is graphically displayed. The clear differences between two mechanisms of fluid transport, thermocapillary convection, and bouncy dominant convection is illustrated.

  1. Shrinking instability of toroidal droplets.

    PubMed

    Fragkopoulos, Alexandros A; Pairam, Ekapop; Berger, Eric; Segre, Phil N; Fernández-Nieves, Alberto

    2017-03-14

    Toroidal droplets are inherently unstable due to surface tension. They can break up, similar to cylindrical jets, but also exhibit a shrinking instability, which is inherent to the toroidal shape. We investigate the evolution of shrinking toroidal droplets using particle image velocimetry. We obtain the flow field inside the droplets and show that as the torus evolves, its cross-section significantly deviates from circular. We then use the experimentally obtained velocities at the torus interface to theoretically reconstruct the internal flow field. Our calculation correctly describes the experimental results and elucidates the role of those modes that, among the many possible ones, are required to capture all of the relevant experimental features.

  2. Miscellaneous hydrocarbon solvents.

    PubMed

    Bebarta, Vikhyat; DeWitt, Christopher

    2004-08-01

    The solvents discussed in this article are common solvents not categorized as halogenated, aromatic, or botanical. The solvents discussed are categorized into two groups: hydrocarbon mixtures and single agents. The hydrocarbon mixtures discussed are Stoddard solvent, naphtha, and kerosene. The remaining solvents described are n-hexane, methyl n-butyl ketone, dimethylformamide, dimethyl sulfoxide, and butyl mercaptans. Effects common to this group of agents and their unique effects are characterized. Treatment of exposures and toxic effects of these solvents is described, and physiochemical properties and occupational exposure levels are listed.

  3. MALDI-TOF imaging mass spectrometry of artifacts in "dried droplet" polymer samples.

    PubMed

    Weidner, Steffen; Knappe, Patrick; Panne, Ulrich

    2011-07-01

    Matrix-assisted laser desorption/ionization-time-of-flight (MALDI-TOF) imaging of polystyrenes with various molecular masses was applied to study spatial molecular mass distribution of polymers in sample spots prepared by the "dried droplet" method. When different solvents and target surfaces were examined, a segregation of single homologous polymers was observed depending upon the evaporation rate of the solvent. For the observed patterns left by the evaporating droplet, a hypothesis is offered taking into account different hydrodynamic interactions and diffusion. The results illustrate that spot preparation using the conventionally "dried droplet" method is prone to artifacts and should be avoided for reliable and reproducible MALDI mass spectrometry experiments with regards to the determination of molecular masses and mass distributions.

  4. Diffusiophoresis of a charged drop

    NASA Astrophysics Data System (ADS)

    Yang, Fan; Shin, Sangwoo; Stone, Howard

    2016-11-01

    Diffusiophoresis describes the motion of colloids in an electrolytic solution under a concentration gradient. Most of the previous studies in diffusiophoresis have dealt with motion of rigid particles. Here, we study the diffusiophoresis of fluid particles analytically and experimentally. We obtain the analytical solution of the diffusiophoretic velocity of fluid particles by perturbation methods. Using charged oil droplets, we measure the droplet speed under solute concentration gradient and compare it with the analytical solution. Our findings have potential applications for oil recovery and drug delivery.

  5. Droplet spectral broadening in marine stratus

    SciTech Connect

    Hudson, J.G.; Yum, Seong Soo

    1997-11-15

    Broadening of the cloud droplet (diameter < 50 {mu}m) spectrum with increased droplet size was found to depend on the vertical profiles of cloud water. Clouds with liquid water profiles resembling adiabatic conditions displayed constant spectral widths. Other clouds displayed broader droplet spectra and increasing broadness with mean droplet sizes. Less than adiabatic cloud liquid water profiles may be accounted for by conversion to drops (diameter > 50 {mu}m, i.e., drizzle). Broad droplet spectra were most closely associated with drizzle drops. Both the concentration, C and slope, k, of the cloud condensation nuclei (CCN) spectra were theoretically found to affect droplet spectral width. For individual cloud parcels a higher C and lower k each contributed to broader droplet spectra. When mixing among cloud parcels with different updrafts was considered, the predictions deviated especially at larger mean droplet diameters. Variations in updraft velocity result in differences in droplet concentrations and mean droplet sizes. The predictions for this internal mixing process showed greater droplet spectral widths for CCN spectra with higher k, especially at the larger mean droplet diameters. Instead of the individual parcel predictions of narrower droplet spectra at larger mean droplet sizes, internal mixing predicted increasing droplet spectral width with increasing mean droplet size. These predictions are consistent with the observations. First, when only cloud parcels with small mean droplet diameters (< 1 {mu}m) were considered, the polluted clouds that formed on CCN with higher C and lower k displayed broader droplet spectra than clean clouds. Cloud parcels with large mean droplet diameters (>12 {mu}m) and large {sigma} were observed only in clean conditions where k was high. Increasing droplet spectral width with mean droplet diameter (especially > 12 {mu}m) is typical of many observations here and elsewhere.

  6. 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.

  7. What Protein Charging (and Supercharging) Reveal about the Mechanism of Electrospray Ionization

    NASA Astrophysics Data System (ADS)

    Ogorzalek Loo, Rachel R.; Lakshmanan, Rajeswari; Loo, Joseph A.

    2014-10-01

    Understanding the charging mechanism of electrospray ionization is central to overcoming shortcomings such as ion suppression or limited dynamic range, and explaining phenomena such as supercharging. Towards that end, we explore what accumulated observations reveal about the mechanism of electrospray. We introduce the idea of an intermediate region for electrospray ionization (and other ionization methods) to account for the facts that solution charge state distributions (CSDs) do not correlate with those observed by ESI-MS (the latter bear more charge) and that gas phase reactions can reduce, but not increase, the extent of charging. This region incorporates properties (e.g., basicities) intermediate between solution and gas phase. Assuming that droplet species polarize within the high electric field leads to equations describing ion emission resembling those from the equilibrium partitioning model. The equations predict many trends successfully, including CSD shifts to higher m/z for concentrated analytes and shifts to lower m/z for sprays employing smaller emitter opening diameters. From this view, a single mechanism can be formulated to explain how reagents that promote analyte charging ("supercharging") such as m-NBA, sulfolane, and 3-nitrobenzonitrile increase analyte charge from "denaturing" and "native" solvent systems. It is suggested that additives' Brønsted basicities are inversely correlated to their ability to shift CSDs to lower m/z in positive ESI, as are Brønsted acidities for negative ESI. Because supercharging agents reduce an analyte's solution ionization, excess spray charge is bestowed on evaporating ions carrying fewer opposing charges. Brønsted basicity (or acidity) determines how much ESI charge is lost to the agent (unavailable to evaporating analyte).

  8. What Protein Charging (and Supercharging) Reveal about the Mechanism of Electrospray Ionization

    PubMed Central

    Loo, Rachel R. Ogorzalek; Lakshmanan, Rajeswari

    2014-01-01

    Understanding the charging mechanism of electrospray ionization is central to overcoming shortcomings such as ion suppression or limited dynamic range and explaining phenomena such as supercharging. Towards that end, we explore what accumulated observations reveal about the mechanism of electrospray. We introduce the idea of an intermediate region for electrospray ionization (and other ionization methods) to account for the facts that solution charge state distributions (CSDs) do not correlate to those observed by ESI– MS (the latter bear more charge) and that gas phase reactions can reduce, but not increase the extent of charging. This region incorporates properties, e.g., basicities, intermediate between solution and gas phase. Assuming that droplet species polarize within the high electric field leads to equations describing ion emission resembling those from the equilibrium partitioning model. The equations predict many trends successfully, including CSD shifts to higher m/z for concentrated analytes and shifts to lower m/z for sprays employing smaller emitter opening diameters. From this view, a single mechanism can be formulated to explain how reagents that promote analyte charging (“supercharging”) such as m–NBA, sulfolane, and 3–nitrobenzonitrile increase analyte charge from “denaturing” and “native” solvent systems. It is suggested that additives’ Brønsted basicities are inversely correlated to their ability to shift CSDs to lower m/z in positive ESI, as are Brønsted acidities for negative ESI. Because supercharging agents reduce an analyte's solution ionization, excess spray charge is bestowed on evaporating ions carryingfewer opposing charges. Brønsted basicity (or acidity) determines how much ESI charge is lost to the agent (unavailable to evaporating analyte). PMID:25135609

  9. Droplet depinning in a wake

    NASA Astrophysics Data System (ADS)

    Hooshanginejad, Alireza; Lee, Sungyon

    2017-03-01

    Pinning and depinning of a windswept droplet on a surface is familiar yet deceptively complex for it depends on the interaction of the contact line with the microscopic features of the solid substrate. This physical picture is further compounded when wind of the Reynolds number greater than 100 blows over pinned drops, leading to the boundary layer separation and wake generation. In this Rapid Communication, we incorporate the well-developed ideas of the classical boundary layer to study partially wetting droplets in a wake created by a leader object. Depending on its distance from the leader, the droplet is observed to exhibit drafting, upstream motion, and splitting, due to the wake-induced hydrodynamic coupling that is analogous to drafting of moving bodies. We successfully rationalize the onset of the upstream motion regime using a reduced model that computes the droplet shape governed by the pressure field inside the wake.

  10. Droplet combustion at reduced gravity

    NASA Technical Reports Server (NTRS)

    Dryer, F. L.; Williams, F. A.

    1988-01-01

    The current work involves theoretical analyses of the effects identified, experiments in the NASA Lewis drop towers performed in the middeck areas of the Space Shuttle. In addition, there is laboratory work associated with the design of the flight apparatus. Calculations have shown that some of the test-matrix data can be obtained in drop towers, and some are achievable only in the space experiments. The apparatus consists of a droplet dispensing device (syringes), a droplet positioning device (opposing, retractable, hollow needles), a droplet ignition device (two matched pairs of retractable spark electrodes), gas and liquid handling systems, a data acquisition system (mainly giving motion-picture records of the combustion in two orthogonal views, one with backlighting for droplet resolution), and associated electronics.

  11. Decompressing Emulsion Droplets Favors Coalescence

    NASA Astrophysics Data System (ADS)

    Bremond, Nicolas; Thiam, Abdou R.; Bibette, Jérôme

    2008-01-01

    The destabilization process of an emulsion under flow is investigated in a microfluidic device. The experimental approach enables us to generate a periodic train of droplet pairs, and thus to isolate and analyze the basic step of the destabilization, namely, the coalescence of two droplets which collide. We demonstrate a counterintuitive phenomenon: coalescence occurs during the separation phase and not during the impact. Separation induces the formation of two facing nipples in the contact area that hastens the connection of the interfaces prior to fusion. Moreover, droplet pairs initially stabilized by surfactants can be destabilized by forcing the separation. Finally, we note that the fusion mechanism is responsible for a cascade of coalescence events in a compact system of droplets where the separation is driven by surface tension.

  12. Mg impurity in helium droplets

    NASA Astrophysics Data System (ADS)

    Navarro, J.; Mateo, D.; Barranco, M.; Sarsa, A.

    2012-02-01

    Within the diffusion Monte Carlo approach, we have determined the structure of isotopically pure and mixed helium droplets doped with one magnesium atom. For pure 4He clusters, our results confirm those of Mella et al. [J. Chem. Phys. 123, 054328 (2005), 10.1063/1.1982787] that the impurity experiences a transition from a surface to a bulk location as the number of helium atoms in the droplet increases. Contrarily, for pure 3He clusters Mg resides in the bulk of the droplet due to the smaller surface tension of this isotope. Results for mixed droplets are presented. We have also obtained the absorption spectrum of Mg around the 3s3p 1P1 ← 3s2 1S0 transition.

  13. Solvents in novolak synthesis

    NASA Astrophysics Data System (ADS)

    Sobodacha, Chet J.; Lynch, Thomas J.; Durham, Dana L.; Paradis, Valerie R.

    1993-09-01

    Novolac resins may be prepared with or without a solvent present. We have found that solvent power greatly affects the properties of the finished resin and thus gives the resist chemist another variable with which to `fine-tune' resist properties. Using designed experiments, we investigated the effect of solvent power, as measured by Hansen's Solubility Parameters, of a number of solvents and solvent mixtures on the final properties of the novolac resin. We found that the relative molecular weight (RMW) and dissolution rate of a novolac resin can be varied by selection of a solvent or solvent mixture with the appropriate polarity and hydrogen- bonding characteristics. The solvent polarity and hydrogen-bonding characteristics may affect the stability of the cresol/formaldehyde transition state, thus causing the observed changes in RMW and dissolution rate.

  14. Magnetic droplets and dynamical skyrmions

    NASA Astrophysics Data System (ADS)

    Akerman, Johan

    2015-03-01

    Nanocontact spin-torque oscillators (NC-STOs) provide an excellent environment for studying nano-magnetic phenomena such as localized and propagating auto-oscillatory spin wave (SW) modes. The recent experimental observation of magnetic droplet solitons in NC-STOs with perpendicular magnetic anisotropy (PMA) free layers, and the numerical and experimental demonstrations of spin transfer torque (STT) nucleated skyrmions in similar magnetic thin films add two interesting and useful nanoscale magnetic objects. Due to the competition between exchange, anisotropy, and, in the case of skyrmions, the Dzyaloshinskii-Moriya interaction (DMI), the droplet and the skyrmion are extremely compact, on the order of 10-100 nm. One of the main differences between a magnetic dissipative droplet soliton and a skyrmion is that the former is a dynamical object with all its spins precessing around an effective field and stabilized by STT, exchange, and PMA, while the latter has static spins and an internal structure stabilized by DMI, exchange, and PMA. The dissipative droplet is furthermore a non-topological soliton, while the skyrmion is topologically protected. In this work I will report on our most recent droplet experiments, including droplet collapse at very high fields, droplets excited in nano-wire based NC-STOs, and studies of the field-current droplet nucleation boundary. I will also demonstrate numerically and analytically that STT driven precession can stabilize so-called dynamical skyrmions even in the absence of DMI, and I will describe their very promising properties in detail. From a more fundamental perspective, precession is hence a third independent possibility to stabilize a skyrmion, without the need for the conventional stabilization from either dipolar energy or DMI.

  15. Arrested of coalescence of emulsion droplets of arbitrary size

    NASA Astrophysics Data System (ADS)

    Mbanga, Badel L.; Burke, Christopher; Blair, Donald W.; Atherton, Timothy J.

    2013-03-01

    With applications ranging from food products to cosmetics via targeted drug delivery systems, structured anisotropic colloids provide an efficient way to control the structure, properties and functions of emulsions. When two fluid emulsion droplets are brought in contact, a reduction of the interfacial tension drives their coalescence into a larger droplet of the same total volume and reduced exposed area. This coalescence can be partially or totally hindered by the presence of nano or micron-size particles that coat the interface as in Pickering emulsions. We investigate numerically the dependance of the mechanical stability of these arrested shapes on the particles size, their shape anisotropy, their polydispersity, their interaction with the solvent, and the particle-particle interactions. We discuss structural shape changes that can be induced by tuning the particles interactions after arrest occurs, and provide design parameters for the relevant experiments.

  16. NEPTUNIUM SOLVENT EXTRACTION PROCESS

    DOEpatents

    Dawson, L.R.; Fields, P.R.

    1959-10-01

    The separation of neptunium from an aqueous solution by solvent extraction and the extraction of neptunium from the solvent solution are described. Neptunium is separated from an aqueous solution containing tetravalent or hexavalent neptunium nitrate, nitric acid, and a nitrate salting out agent, such as sodium nitrate, by contacting the solution with an organic solvent such as diethyl ether. Subsequently, the neptunium nitrate is extracted from the organic solvent extract phase with water.

  17. Solvent Recycling for Shipyards

    DTIC Science & Technology

    1993-05-01

    alternatives to solvent cleaning. Typical equipment types that can be effectively cleaned with recycled solvents include spray guns paint hoses pumps...in place of solvent-based coatings; or equipment changes, such as the use of airless or HVLP systems to reduce paint consumption and overspray...Using mechanical cleaning methods instead of solvent cleaning Change from conventional painting to solventless processes such as thermal spray or powder

  18. Sintering of polydisperse viscous droplets

    NASA Astrophysics Data System (ADS)

    Wadsworth, Fabian B.; Vasseur, Jérémie; Llewellin, Edward W.; Dingwell, Donald B.

    2017-03-01

    Sintering—or coalescence—of compacts of viscous droplets is driven by the interfacial tension between the droplets and the interstitial gas phase. The process, which occurs in a range of industrial and natural settings, such as the manufacture of ceramics and the welding of volcanic ash, causes the compact to densify, to become stronger, and to become less permeable. We investigate the role of droplet polydispersivity in sintering dynamics by conducting experiments in which populations of glass spheres with different size distributions are heated to temperatures above the glass transition interval. We quantify the progress of sintering by tracking changes in porosity with time. The sintering dynamics is modeled by treating the system as a random distribution of interstitial gas bubbles shrinking under the action of interfacial tension only. We identify the scaling between the polydispersivity of the initial droplets and the dynamics of bulk densification. The framework that we develop allows the sintering dynamics of arbitrary polydisperse populations of droplets to be predicted if the initial droplet (or particle) size distribution is known.

  19. The liquid droplet heat exchanger

    NASA Astrophysics Data System (ADS)

    Bruckner, A. P.

    Direct contact heat exchange between a gas and a molten metal dispersed into droplets offers an attractive new approach to increasing the efficiency and decreasing the specific weight of thermal power cycles for space applications. The ability of a droplet heat exchanger to transfer heat directly from a liquid metal to a working gas over a wide temperature range circumvents many of the material limitations of conventional tube type heat exchangers and does away with complicated plumbing systems and their tendency toward simple point failure. Droplet heat exchangers offer large surface to volume ratios in a compact geometry, very low pressure drop and high effectiveness. In the simplest configuration the molten material is sprayed axially through a counterflowing, high pressure inert working gas in an insulated cylindrical chamber. The droplets transfer heat directly to the gas by convection as they traverse the heat exchanger and are subsequently collected for recycling through the heat source. A number of suitable liquid metals and eutectic alloys having negligibly low vapor pressures in the temperature range of 350-1300 K were identified. Experimental studies of droplet formation with mercury demonstrated that near perfect control of droplet size can be easily achieved.

  20. Preparation of solid particle dispersions by solvent shifting

    NASA Astrophysics Data System (ADS)

    Brick, Mary Christine

    Organic solid particle dispersions are useful for a number of industrial applications, including photography, pharmaceuticals, food, biotechnology and inks. This work describes precipitation by solvent shifting to prepare dispersions as an alternative to media milling, which is energy intensive and time consuming. In particular, we have studied the precipitation of an organic dye useful in photographic film. In the solvent shifting technique, the dye is dissolved in a water-miscible organic solvent and added to an aqueous solution containing colloidal stabilizers. Under suitable conditions of composition and mixing, amorphous dye particles of colloidal dimensions are formed. We propose that as the dye solution enters the reactor, it is rapidly dispersed into the aqueous phase in the form of small droplets. Counter-diffusion of water and organic solvent occurs within each droplet, leading to rapid precipitation of dye as an amorphous phase. The particles are then stabilized and dispersed uniformly in the reactor. This mechanism is supported by the observation that the particle formation rate correlates with the local supersaturation xx* where x is the dye concentration in the feed and x* is the solubility of the amorphous dye in the bulk solution. The relationship holds with a variety of solvents and mixing conditions. Since the particle formation rate is determined by the local supersaturation ratio, the size and number of the particles is controllable in this process. Other organic materials were studied, and they also precipitated as amorphous particles using the solvent shifting technique. Equilibrium solubility measurements of the crystalline solid, together with the free energy of melting, are used to predict the equilibrium solubility of the amorphous phase and the degree of supersaturation during the precipitation process. The effect of process variables on particle growth rates was also studied. The results of these experiments support growth by diffusion

  1. Reduced Graphene Oxide Membranes for Ultrafast Organic Solvent Nanofiltration.

    PubMed

    Huang, Liang; Chen, Ji; Gao, Tiantian; Zhang, Miao; Li, Yingru; Dai, Liming; Qu, Liangti; Shi, Gaoquan

    2016-10-01

    Solvated reduced graphene oxide (S-rGO) membranes are stable in organic solvents, and strong acidic, alkaline, or oxidative media. They show high rejections to small molecules with charges the same as that of S-rGO coatings or neutral molecules larger than 3.4 nm, while retaining their high permeances to organic solvents.

  2. Liquid droplet radiator development status. [waste heat rejection devices for future space vehicles

    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.

  3. Liquid droplet radiator development status. [waste heat rejection devices for future space vehicles

    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.

  4. Solvents and sustainable chemistry

    PubMed Central

    Welton, Tom

    2015-01-01

    Solvents are widely recognized to be of great environmental concern. The reduction of their use is one of the most important aims of green chemistry. In addition to this, the appropriate selection of solvent for a process can greatly improve the sustainability of a chemical production process. There has also been extensive research into the application of so-called green solvents, such as ionic liquids and supercritical fluids. However, most examples of solvent technologies that give improved sustainability come from the application of well-established solvents. It is also apparent that the successful implementation of environmentally sustainable processes must be accompanied by improvements in commercial performance. PMID:26730217

  5. Solvent recycle/recovery

    SciTech Connect

    Paffhausen, M.W.; Smith, D.L.; Ugaki, S.N.

    1990-09-01

    This report describes Phase I of the Solvent Recycle/Recovery Task of the DOE Chlorinated Solvent Substitution Program for the US Air Force by the Idaho National Engineering Laboratory, EG G Idaho, Inc., through the US Department of Energy, Idaho Operations Office. The purpose of the task is to identify and test recovery and recycling technologies for proposed substitution solvents identified by the Biodegradable Solvent Substitution Program and the Alternative Solvents/Technologies for Paint Stripping Program with the overall objective of minimizing hazardous wastes. A literature search to identify recycle/recovery technologies and initial distillation studies has been conducted. 4 refs.

  6. Uniform-droplet spray forming

    SciTech Connect

    Blue, C.A.; Sikka, V.K.; Chun, Jung-Hoon; Ando, T.

    1997-04-01

    The uniform-droplet process is a new method of liquid-metal atomization that results in single droplets that can be used to produce mono-size powders or sprayed-on to substrates to produce near-net shapes with tailored microstructure. The mono-sized powder-production capability of the uniform-droplet process also has the potential of permitting engineered powder blends to produce components of controlled porosity. Metal and alloy powders are commercially produced by at least three different methods: gas atomization, water atomization, and rotating disk. All three methods produce powders of a broad range in size with a very small yield of fine powders with single-sized droplets that can be used to produce mono-size powders or sprayed-on substrates to produce near-net shapes with tailored microstructures. The economical analysis has shown the process to have the potential of reducing capital cost by 50% and operating cost by 37.5% when applied to powder making. For the spray-forming process, a 25% savings is expected in both the capital and operating costs. The project is jointly carried out at Massachusetts Institute of Technology (MIT), Tuffs University, and Oak Ridge National Laboratory (ORNL). Preliminary interactions with both finished parts and powder producers have shown a strong interest in the uniform-droplet process. Systematic studies are being conducted to optimize the process parameters, understand the solidification of droplets and spray deposits, and develop a uniform-droplet-system (UDS) apparatus appropriate for processing engineering alloys.

  7. Exploiting droplet formation in microfluidic devices to create functional particles

    NASA Astrophysics Data System (ADS)

    Nowak, Emilia; Simmons, Mark

    2014-11-01

    Microfluidic devices offer excellent capabilities for the formation of microstructured particles which have functional attributes e.g. in controlled delivery of pharmaceuticals, enhanced nutrition and flavours in food. In this work, a microfluidic device is employed to form microstructured particles in two steps: (i) by formation of single/double emulsions and (ii) solidification of the droplet by either gelation or solvent evaporation. Both may impart non-Newtonian properties to the component phases. The influence of phase flow rates (capillary number), surfactant type/concentration and the rheology of the component phases upon the particle formation and hydrodynamic behaviour are described. EPSRC Programme Grant, MEMPHIS, EP/K0039761/1.

  8. A QSPR study on the solvent-induced frequency shifts of acetone and dimethyl sulfoxide in organic solvents.

    PubMed

    Ou, Yu Heng; Chang, Chia Ming; Chen, Ying Shao

    2016-06-05

    In this study, solvent-induced frequency shifts (SIFS) in the infrared spectrum of acetone and dimethyl sulfoxide in organic solvents were investigated by using four types of quantum-chemical reactivity descriptors. The results showed that the SIFS of acetone is mainly affected by the electron-acceptance chemical potential and the maximum nucleophilic condensed local softness of organic solvents, which represent the electron flow and the polarization between acetone and solvent molecules. On the other hand, the SIFS of dimethyl sulfoxide changes with the maximum positive charge of hydrogen atom and the inverse of apolar surface area of solvent molecules, showing that the electrostatic and hydrophilic interactions are main mechanisms between dimethyl sulfoxide and solvent molecules. The introduction of the four-element theory model-based quantitative structure-property relationship approach improved the assessing quality and provided a basis for interpreting the solute-solvent interactions.

  9. A QSPR study on the solvent-induced frequency shifts of acetone and dimethyl sulfoxide in organic solvents

    NASA Astrophysics Data System (ADS)

    Ou, Yu Heng; Chang, Chia Ming; Chen, Ying Shao

    2016-06-01

    In this study, solvent-induced frequency shifts (SIFS) in the infrared spectrum of acetone and dimethyl sulfoxide in organic solvents were investigated by using four types of quantum-chemical reactivity descriptors. The results showed that the SIFS of acetone is mainly affected by the electron-acceptance chemical potential and the maximum nucleophilic condensed local softness of organic solvents, which represent the electron flow and the polarization between acetone and solvent molecules. On the other hand, the SIFS of dimethyl sulfoxide changes with the maximum positive charge of hydrogen atom and the inverse of apolar surface area of solvent molecules, showing that the electrostatic and hydrophilic interactions are main mechanisms between dimethyl sulfoxide and solvent molecules. The introduction of the four-element theory model-based quantitative structure-property relationship approach improved the assessing quality and provided a basis for interpreting the solute-solvent interactions.

  10. Dry Zones Around Frozen Droplets

    NASA Astrophysics Data System (ADS)

    Bisbano, Caitlin; Nath, Saurabh; Boreyko, Jonathan; Nature-Inspired Fluids; Interfaces Team

    2015-11-01

    The saturation pressure of water vapor above supercooled water exceeds that above ice at the same temperature. A frozen droplet will therefore grow by harvesting water vapor from neighboring supercooled condensate, which has recently been demonstrated to be a primary mechanism of in-plane frost growth on hydrophobic surfaces. The underlying physics of this source-sink interaction is still poorly understood. In this work, a deposited water droplet is frozen on a dry hydrophobic surface initially held above the dew point. We demonstrate that when the surface is then cooled beneath the dew point, the frozen droplet harvests nearby water vapor in the air. This results in an annular dry zone that forms between the frozen droplet and the forming supercooled condensation. For a given ambient temperature and humidity, the length of the dry zone varied strongly with surface temperature and weakly with droplet volume. The dependence of the dry zone on surface temperature is due to the fact that the vapor pressure gradients between the ambient and the surface and between the liquid and frozen water are both functions of temperature.

  11. Droplets merging through wireless ultrasonic actuation.

    PubMed

    Nayak, Praveen Priyaranjan; Kar, Durga Prasanna; Bhuyan, Satyanarayan

    2016-01-01

    A new technique of droplets merging through wireless ultrasonic actuation has been proposed and experimentally investigated in this work. The proposed method is based on the principle of resonant inductive coupling and piezoelectric resonance. When a mechanical vibration is excited in a piezoelectric plate, the ultrasonic vibration transmitted to the droplets placed on its surface and induces merging. It has been observed that the merging rate of water droplets depends on the operating frequency, mechanical vibration of piezoelectric plate, separation distance between the droplets, and volume of droplets. The investigated technique of droplets merging through piezoelectric actuation is quite useful for microfluidics, chemical and biomedical engineering applications.

  12. Eliminating the interferences from TRIS buffer and SDS in protein analysis by fused-droplet electrospray ionization mass spectrometry.

    PubMed

    Shieh, I-Fan; Lee, Chi-Yang; Shiea, Jentaie

    2005-01-01

    Multiply charged protein ions were detected from the solutions containing a high concentration of tris(hydroxymethyl) aminomethane buffer (TRIS) and sodium dodecyl sulfate (SDS) using fused-droplet electrospray ionization mass spectrometry (FD-ESI/MS). The sample aerosols were generated at ambient temperature with a pneumatic nebulizer commonly used to produce sample aerosols in an atmospheric pressure chemical ionization (APCI) source. The aerosols were carried by nitrogen gas to the tip of a capillary where charged methanol droplets had been continuously generated by electrospraying an acidic methanol solution. The neutral sample aerosols then fused with the charged methanol droplets and electrospray ionization proceeded from the newly formed fused droplets to generate multiply charged protein ions. Because of its low solubility in methanol, TRIS molecules (concentration as high as 1 M) were efficiently excluded from the newly formed droplets and the protein ion signals were detected and observed in the mass spectra. To remove the interferences from SDS, equal moles of positively charged cetyltrimethylammonium bromide (CTAB) was added into the SDS containing sample solution to form the dodecyl sulfate-cetyltrimethylammonium ion pair (DS-CTA). The DS-CTA ion pair has a low polarity and solubility in methanol and is excluded from the fused droplet. Protein ions were still detected from the solution containing 10(-2) M of SDS.

  13. 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.

  14. Application of light scattering in studies of transport, thermodynamics, light absorption, and electric properties of single droplets

    NASA Astrophysics Data System (ADS)

    Tu, Haohua

    2001-12-01

    coefficient of an extremely nonvolatile system at room conditions. It is reported that a charged droplet might not explode even above Rayleigh limit and droplet electron emission might happen well below the theoretical expectation.

  15. Charge fluctuations in nanoscale capacitors.

    PubMed

    Limmer, David T; Merlet, Céline; Salanne, Mathieu; Chandler, David; Madden, Paul A; van Roij, René; Rotenberg, Benjamin

    2013-09-06

    The fluctuations of the charge on an electrode contain information on the microscopic correlations within the adjacent fluid and their effect on the electronic properties of the interface. We investigate these fluctuations using molecular dynamics simulations in a constant-potential ensemble with histogram reweighting techniques. This approach offers, in particular, an efficient, accurate, and physically insightful route to the differential capacitance that is broadly applicable. We demonstrate these methods with three different capacitors: pure water between platinum electrodes and a pure as well as a solvent-based organic electrolyte each between graphite electrodes. The total charge distributions with the pure solvent and solvent-based electrolytes are remarkably Gaussian, while in the pure ionic liquid the total charge distribution displays distinct non-Gaussian features, suggesting significant potential-driven changes in the organization of the interfacial fluid.

  16. Charge Fluctuations in Nanoscale Capacitors

    NASA Astrophysics Data System (ADS)

    Limmer, David T.; Merlet, Céline; Salanne, Mathieu; Chandler, David; Madden, Paul A.; van Roij, René; Rotenberg, Benjamin

    2013-09-01

    The fluctuations of the charge on an electrode contain information on the microscopic correlations within the adjacent fluid and their effect on the electronic properties of the interface. We investigate these fluctuations using molecular dynamics simulations in a constant-potential ensemble with histogram reweighting techniques. This approach offers, in particular, an efficient, accurate, and physically insightful route to the differential capacitance that is broadly applicable. We demonstrate these methods with three different capacitors: pure water between platinum electrodes and a pure as well as a solvent-based organic electrolyte each between graphite electrodes. The total charge distributions with the pure solvent and solvent-based electrolytes are remarkably Gaussian, while in the pure ionic liquid the total charge distribution displays distinct non-Gaussian features, suggesting significant potential-driven changes in the organization of the interfacial fluid.

  17. Walking droplets in linear channels

    NASA Astrophysics Data System (ADS)

    Filoux, Boris; Hubert, Maxime; Schlagheck, Peter; Vandewalle, Nicolas

    2017-01-01

    When a droplet is placed onto a vertically vibrated bath, it can bounce without coalescing. Upon an increase of the forcing acceleration, the droplet is propelled by the wave it generates and becomes a walker with a well-defined speed. We investigate the confinement of a walker in different rectangular cavities, used as waveguides for the Faraday waves emitted by successive droplet bounces. By studying the walker velocities, we discover that one-dimensional confinement is optimal for narrow channels of width of D ≃1.5 λF . Thereby, the walker follows a quasilinear path. We also propose an analogy with waveguide models based on the observation of the Faraday instability within the channels.

  18. Droplet burning at zero G

    NASA Technical Reports Server (NTRS)

    Williams, F. A.

    1978-01-01

    Questions of the importance and feasibility of performing experiments on droplet burning at zero gravity in Spacelab were studied. Information on the physics and chemistry of droplet combustion, with attention directed specifically to the chemical kinetics, heat and mass transfer, and fluid mechanics of the phenomena involved, are presented. The work was divided into three phases, the justification, the feasibility, and the conceptual development of a preliminary design. Results from the experiments performed revealed a few new facts concerning droplet burning, notably burning rates in excess of theoretical prediction and a phenomenon of flash extinction, both likely traceable to accumulation of carbon produced by gas-phase pyrolysis in the fuel-rich zone enclosed by the reaction surface. These experiments also showed that they were primarily due to timing difficulties.

  19. Acoustically-controlled Leidenfrost droplets.

    PubMed

    Ng, Boon T; Hung, Yew Mun; Tan, Ming K

    2016-03-01

    Suppressing the Leidenfrost effect can significantly improve heat transfer from a heated substrate to a droplet above it. In this work, we demonstrate that by generating high frequency acoustic wave in the droplet, at sufficient vibration displacement amplitudes, the Leidenfrost effect can be suppressed due to the acoustic radiation pressure exerted on the liquid-vapor interface; strong capillary waves are observed at the liquid-vapor interface and subsequently leads to contact between the liquid and the heated substrate. Using this technique, with 10(5)Hz vibration frequency and 10(-6)m displacement amplitude of the acoustic transducer, a maximum of 45% reduction of the initial temperature (T0∼200-300°C) of the heated substrate can be achieved with a single droplet of volume 10(-5)l. Copyright © 2015 Elsevier Inc. All rights reserved.

  20. Shrinking instability of toroidal droplets

    PubMed Central

    Fragkopoulos, Alexandros A.; Pairam, Ekapop; Berger, Eric; Segre, Phil N.; Fernández-Nieves, Alberto

    2017-01-01

    Toroidal droplets are inherently unstable due to surface tension. They can break up, similar to cylindrical jets, but also exhibit a shrinking instability, which is inherent to the toroidal shape. We investigate the evolution of shrinking toroidal droplets using particle image velocimetry. We obtain the flow field inside the droplets and show that as the torus evolves, its cross-section significantly deviates from circular. We then use the experimentally obtained velocities at the torus interface to theoretically reconstruct the internal flow field. Our calculation correctly describes the experimental results and elucidates the role of those modes that, among the many possible ones, are required to capture all of the relevant experimental features. PMID:28251927

  1. The plasma levitation of droplets

    NASA Astrophysics Data System (ADS)

    Poulain, Cédric; Dugué, Antoine; Durieux, Antoine; Sadeghi, Nader; Duplat, Jérôme

    2015-08-01

    We show how to levitate a liquid droplet above a plasma. Submitting a conductive droplet to a voltage larger than 50 V, we get a levitation regime that looks like the one obtained with the well-known thermal Leidenfrost effect, except that light is emitted from beneath the droplet. Spectroscopic analysis shows that this light is emitted by a cold and dense plasma and also that lines coming from the cathode plate material are present revealing a local cathodic sputtering effect. We examine the conditions for the levitation to occur and show that the levitation is essentially of thermal origin. Assuming a stationary heat transfer, we present a model that accounts well for the observed levitation conditions. In particular, stable levitation is shown to be possible for thin cathode plates only.

  2. The Droplet Combustion Experiment (DCE)

    NASA Technical Reports Server (NTRS)

    2003-01-01

    The Droplet Combustion Experiment (DCE) was designed to investigate the fundamental combustion aspects of single, isolated droplets under different pressures and ambient oxygen concentrations for a range of droplet sizes varying between 2 and 5 mm. The DCE principal investigator was Forman Williams, University of California, San Diego. The experiment was part of the space research investigations conducted during the Microgravity Science Laboratory-1R mission (STS-94, July 1-17 1997). Advanced combustion experiments will be a part of investigations plarned for the International Space Station. (167KB, 5-second MPEG, screen 160 x 120 pixels; downlinked video, higher quality not available)A still JPG composite of this movie is available at http://mix.msfc.nasa.gov/ABSTRACTS/MSFC-0300166.html.

  3. Vibration-Induced Droplet Atomization

    NASA Technical Reports Server (NTRS)

    Smith, M. K.; James, A.; Vukasinovic, B.; Glezer, A.

    1999-01-01

    Thermal management is critical to a number of technologies used in a microgravity environment and in Earth-based systems. Examples include electronic cooling, power generation systems, metal forming and extrusion, and HVAC (heating, venting, and air conditioning) systems. One technique that can deliver the large heat fluxes required for many of these technologies is two-phase heat transfer. This type of heat transfer is seen in the boiling or evaporation of a liquid and in the condensation of a vapor. Such processes provide very large heat fluxes with small temperature differences. Our research program is directed toward the development of a new, two-phase heat transfer cell for use in a microgravity environment. In this paper, we consider the main technology used in this cell, a novel technique for the atomization of a liquid called vibration-induced droplet atomization. In this process, a small liquid droplet is placed on a thin metal diaphragm that is made to vibrate by an attached piezoelectric transducer. The vibration induces capillary waves on the free surface of the droplet that grow in amplitude and then begin to eject small secondary droplets from the wave crests. In some situations, this ejection process develops so rapidly that the entire droplet seems to burst into a small cloud of atomized droplets that move away from the diaphragm at speeds of up to 50 cm/s. By incorporating this process into a heat transfer cell, the active atomization and transport of the small liquid droplets could provide a large heat flux capability for the device. Experimental results are presented that document the behavior of the diaphragm and the droplet during the course of a typical bursting event. In addition, a simple mathematical model is presented that qualitatively reproduces all of the essential features we have seen in a burst event. From these two investigations, we have shown that delayed droplet bursting results when the system passes through a resonance

  4. Snell's law and walking droplets

    NASA Astrophysics Data System (ADS)

    Bush, John; Pucci, Giuseppe; Aubin, Benjamin; Brun, Pierre-Thomas; Faria, Luiz

    2016-11-01

    Droplets walking on the surface of a vibrating bath have been shown to exhibit a number of quantum-like features. We here present the results of a combined experimental and theoretical investigation of such droplets crossing a linear step corresponding to a reduction in bath depth. When the step is sufficiently large, the walker reflects off the step; otherwise, it is refracted as it crosses the step. Particular attention is given to an examination of the regime in which the droplet obeys a form of Snell's Law, a behavior captured in accompanying simulations. Attempts to provide theoretical rationale for the dependence of the effective refractive index on the system parameters are described. Supported by NSF through CMMI-1333242.

  5. Microstructures of undercooled germanium droplets

    NASA Technical Reports Server (NTRS)

    Devaud, G.; Turnbull, D.

    1987-01-01

    Undercoolings at crystal nucleation onset of liquid Ge droplets are measured and the microstructures of the droplets are examined. Undercooling values ranging from 150-415 + or 20 C were obtained. It is observed that for the samples undercooled less than 300 C prior to solidification the grain size was greater than 100 microns; for samples undercooled between 300-400 C the grain size was between 50-100 microns; and for samples undercooled greater than 400 C the grain size was 10-20 microns. Consideration is given to dendritic growth and interfacial undercooling. It is noted that there is a correlation between undercooling and as-crystallized grain structure.

  6. Film boiling of mercury droplets

    NASA Technical Reports Server (NTRS)

    Baumeister, K. J.; Schoessow, G. J.; Chmielewski, C. E.

    1975-01-01

    Vaporization times of mercury droplets in Leidenfrost film boiling on a flat horizontal plate are measured in an air atmosphere. Extreme care was used to prevent large amplitude droplet vibrations and surface wetting; therefore, these data can be compared to film boiling theory. For these data, diffusion from the upper surface of the drop is a dominant mode of mass transfer from the drop. A closed-form analytical film boiling theory is developed to account for the diffusive evaporation. Reasonable agreement between data and theory is seen.

  7. Film boiling of mercury droplets

    NASA Technical Reports Server (NTRS)

    Baumeister, K. J.; Schoessow, G. J.; Chmielewski, C. E.

    1975-01-01

    Vaporization times of mercury droplets in Leidenfrost film boiling on a flat horizontal plate are measured in an air atmosphere. Extreme care was used to prevent large amplitude droplet vibrations and surface wetting; therefore, these data can be compared to film boiling theory. Diffusion from the upper surface of the drop appears as a dominant mode of mass transfer from the drop. A closed-form analytical film boiling theory is developed to account for the diffusive evaporation. Reasonable agreement between data and theory is seen.

  8. Room temperature water Leidenfrost droplets.

    PubMed

    Celestini, Franck; Frisch, Thomas; Pomeau, Yves

    2013-10-28

    We experimentally investigate the Leidenfrost effect at pressures ranging from 1 to 0.05 atmospheric pressure. As a direct consequence of the Clausius–Clapeyron phase diagram of water, the droplet temperature can be at ambient temperature in a non-sophisticated lab environment. Furthermore, the lifetime of the Leidenfrost droplet is significantly increased in this low pressure environment. The temperature and pressure dependence of the evaporation rate is successfully tested against a recently proposed model. These results may pave the way for reaching efficient Leidenfrost micro-fluidic and milli-fluidic applications.

  9. Film boiling of mercury droplets

    NASA Technical Reports Server (NTRS)

    Baumeister, K. J.; Schoessow, G. J.; Chmielewski, C. E.

    1975-01-01

    Vaporization times of mercury droplets in Leidenfrost film boiling on a flat horizontal plate are measured in an air atmosphere. Extreme care was used to prevent large amplitude droplet vibrations and surface wetting; therefore, these data can be compared to film boiling theory. For these data, diffusion from the upper surface of the drop is a dominant mode of mass transfer from the drop. A closed-form analytical film boiling theory is developed to account for the diffusive evaporation. Reasonable agreement between data and theory is seen.

  10. Solute and solvent dynamics in confined equal-sized aqueous environments of charged and neutral reverse micelles: a combined dynamic fluorescence and all-atom molecular dynamics simulation study.

    PubMed

    Guchhait, Biswajit; Biswas, Ranjit; Ghorai, Pradip K

    2013-03-28

    Here a combined dynamic fluorescence and all-atom molecular dynamics simulation study of aqueous pool-size dependent solvation energy and rotational relaxations of a neutral dipolar solute, C153, trapped in AOT (charged) and IGPAL (neutral) reverse micelles (RMs) at 298 K, is described. RMs in simulations have been represented by a reduced model where SPC/E water molecules interact with a trapped C153 that possesses realistic charge distributions for both ground and excited states. In large aqueous pools, measured average solvation and rotation rates are smaller for the neutral RMs than those in charged ones. Interestingly, while the measured average solvation and rotation rates increase with pool size for the charged RMs, the average rotation rates for the neutral RMs exhibit a reverse dependence. Simulations have qualitatively reproduced this experimental trend and suggested interfacial location for the solute for all cases. The origin for the subnanosecond Stokes shift dynamics has been investigated and solute-interface interaction contribution quantified. Simulated layer-wise translational and rotational diffusions of water molecules re-examine the validity of the core-shell model and provide a resolution to a debate regarding the origin of the subnanosecond solvation component in dynamic Stokes shift measurements with aqueous RMs but not detected in ultrafast IR measurements.

  11. Study on droplet freezing characteristic by ultrasonic

    NASA Astrophysics Data System (ADS)

    Gao, Penghui; Cheng, Bo; Zhou, Xingye; Zhang, Donghai; Zhou, Guoqing

    2017-05-01

    The application of ultrasound to liquid freezing has focused growing attention over the last few years and its potential seems very promising. In order to make clear droplet freezing assisted by ultrasonic, the freezing nucleation free energy of droplet was analyzed in effect of ultrasonic and un-ultrasonic. Droplet freezing was studied based on ultrasonic theory, penetration theory of mass transfer and energy conservation. Besides, solid-liquid interface position of droplet in the process of freezing for different droplet radius was studied to reflect the freezing process. The results showed that ultrasonic could be favor to droplet freezing, which could deduce freezing nucleation free energy of droplet. Larger ultrasonic frequency would deduce smaller freezing nucleation free energy, and larger ultrasonic intensity would cause droplet to be cool and freeze easily.

  12. Materials science: Droplets leap into action

    NASA Astrophysics Data System (ADS)

    Vollmer, Doris; Butt, Hans-Jürgen

    2015-11-01

    What could cause a water droplet to start bouncing on a surface? It seems that a combination of evaporation and a highly water-repellent surface induces droplet bouncing when ambient pressure is reduced. See Letter p.82

  13. Ice and water droplets on graphite: A comparison of quantum and classical simulations

    SciTech Connect

    Ramírez, Rafael; Singh, Jayant K.; Müller-Plathe, Florian; Böhm, Michael C.

    2014-11-28

    Ice and water droplets on graphite have been studied by quantum path integral and classical molecular dynamics simulations. The point-charge q-TIP4P/F potential was used to model the interaction between flexible water molecules, while the water-graphite interaction was described by a Lennard-Jones potential previously used to reproduce the macroscopic contact angle of water droplets on graphite. Several energetic and structural properties of water droplets with sizes between 10{sup 2} and 10{sup 3} molecules were analyzed in a temperature interval of 50–350 K. The vibrational density of states of crystalline and amorphous ice drops was correlated to the one of ice Ih to assess the influence of the droplet interface and molecular disorder on the vibrational properties. The average distance of covalent OH bonds is found 0.01 Å larger in the quantum limit than in the classical one. The OO distances are elongated by 0.03 Å in the quantum simulations at 50 K. Bond distance fluctuations are large as a consequence of the zero-point vibrations. The analysis of the H-bond network shows that the liquid droplet is more structured in the classical limit than in the quantum case. The average kinetic and potential energy of the ice and water droplets on graphite has been compared with the values of ice Ih and liquid water as a function of temperature. The droplet kinetic energy shows a temperature dependence similar to the one of liquid water, without apparent discontinuity at temperatures where the droplet is solid. However, the droplet potential energy becomes significantly larger than the one of ice or water at the same temperature. In the quantum limit, the ice droplet is more expanded than in a classical description. Liquid droplets display identical density profiles and liquid-vapor interfaces in the quantum and classical limits. The value of the contact angle is not influenced by quantum effects. Contact angles of droplets decrease as the size of the water droplet

  14. Experimental and Theoretical Investigation on Rapid Evaporation of Ethanol Droplets and Kerosene Droplets During Depressurization

    NASA Astrophysics Data System (ADS)

    Liu, Lu; Bi, Qin-cheng; Liu, Wei-min; Qi, Fang-cheng; Bi, Xin-gang

    2011-01-01

    This paper reports an experimental and theoretical study of rapid evaporation of ethanol droplets and kerosene droplets during depressurization. For experimental method, an ethanol droplet or a kerosene droplet was suspended on a thermocouple, which was also used to measure the droplet center temperature transition. And the droplet shape variation was recorded by a high speed camera. A theoretical analysis was developed based on the heat balance to estimate the droplet center temperature transition, and the evaporation model proposed by Abramzon and Sirignano was used to describe the droplet vaporization. According to the experimental data and theoretical analysis, both of the environmental pressure and the initial droplet diameter have a prominent influence on the droplet temperature transition. Comparing the evaporation processes of ethanol droplets and kerosene droplets with water droplets, the ethanol droplets have the fastest evaporation rate, followed by water, and the evaporation rates of kerosene droplets are the slowest. Also it was found that a bubble can easily emerge within kerosene droplet, and its lifetime is more than 1 s.

  15. Dynamics of self-assembled droplet etching

    NASA Astrophysics Data System (ADS)

    Heyn, Ch.; Stemmann, A.; Hansen, W.

    2009-10-01

    We study the self-assembled local droplet etching of nanoholes in AlGaAs surfaces with Ga droplets. The data establish an unexpected delay of both the hole drilling process as well as the removal of the liquid material after etching. Furthermore, coarsening by Ostwald ripening is found to reduce the droplet density before drilling. Basing on these findings, we propose a growth, coarsening, drilling, and removal mechanism for the droplet etching process.

  16. Droplet centrifugation, droplet DNA extraction, and rapid droplet thermocycling for simpler and faster PCR assay using wire-guided manipulations

    PubMed Central

    2012-01-01

    A computer numerical control (CNC) apparatus was used to perform droplet centrifugation, droplet DNA extraction, and rapid droplet thermocycling on a single superhydrophobic surface and a multi-chambered PCB heater. Droplets were manipulated using “wire-guided” method (a pipette tip was used in this study). This methodology can be easily adapted to existing commercial robotic pipetting system, while demonstrated added capabilities such as vibrational mixing, high-speed centrifuging of droplets, simple DNA extraction utilizing the hydrophobicity difference between the tip and the superhydrophobic surface, and rapid thermocycling with a moving droplet, all with wire-guided droplet manipulations on a superhydrophobic surface and a multi-chambered PCB heater (i.e., not on a 96-well plate). Serial dilutions were demonstrated for diluting sample matrix. Centrifuging was demonstrated by rotating a 10 μL droplet at 2300 round per minute, concentrating E. coli by more than 3-fold within 3 min. DNA extraction was demonstrated from E. coli sample utilizing the disposable pipette tip to cleverly attract the extracted DNA from the droplet residing on a superhydrophobic surface, which took less than 10 min. Following extraction, the 1500 bp sequence of Peptidase D from E. coli was amplified using rapid droplet thermocycling, which took 10 min for 30 cycles. The total assay time was 23 min, including droplet centrifugation, droplet DNA extraction and rapid droplet thermocycling. Evaporation from of 10 μL droplets was not significant during these procedures, since the longest time exposure to air and the vibrations was less than 5 min (during DNA extraction). The results of these sequentially executed processes were analyzed using gel electrophoresis. Thus, this work demonstrates the adaptability of the system to replace many common laboratory tasks on a single platform (through re-programmability), in rapid succession (using droplets), and with a high level of

  17. Time resolved spectroscopy of 2-(dimethylamine)fluorene. Solvent effects and photophysical behavior.

    PubMed

    Sánchez, Francisco G; Díaz, Aurora N; Algarra, Manuel; Lovillo, Josefa; Aguilar, Alfonso

    2011-12-01

    The effect of different solvents on the fluorescent properties of 2-(dimethylamine)fluorene (DAF) were studied. In aprotic solvents we detected a strongly emissive intramolecular charge transfer (ICT) state that decayed by intersystem crossing to triplet. In proton-accepting solvents DAF exhibits in the excited state an intramolecular proton transfer. An ionized species is postulated, which simultaneously twists to a rotated conformation in the excited state. Thus, the specific solvent interactions supplement but do not replace the twist mechanism and accompany the charge transfer accepted as the prerequisite for twisted intramolecular charged transfer (TICT) state formation. Copyright © 2011 Elsevier B.V. All rights reserved.

  18. Time resolved spectroscopy of 2-(dimethylamine)fluorene. Solvent effects and photophysical behavior

    NASA Astrophysics Data System (ADS)

    Sánchez, Francisco G.; Díaz, Aurora N.; Algarra, Manuel; Lovillo, Josefa; Aguilar, Alfonso

    2011-12-01

    The effect of different solvents on the fluorescent properties of 2-(dimethylamine)fluorene (DAF) were studied. In aprotic solvents we detected a strongly emissive intramolecular charge transfer (ICT) state that decayed by intersystem crossing to triplet. In proton-accepting solvents DAF exhibits in the excited state an intramolecular proton transfer. An ionized species is postulated, which simultaneously twists to a rotated conformation in the excited state. Thus, the specific solvent interactions supplement but do not replace the twist mechanism and accompany the charge transfer accepted as the prerequisite for twisted intramolecular charged transfer (TICT) state formation.

  19. Structural proteomics: Topology and relative accessibility of plant lipid droplet associated proteins.

    PubMed

    Jolivet, Pascale; Aymé, Laure; Giuliani, Alexandre; Wien, Frank; Chardot, Thierry; Gohon, Yann

    2017-09-14

    Lipid droplets are the major stock of lipids in oleaginous plant seeds. Despite their economic importance for oil production and biotechnological issues (biofuels, lubricants and plasticizers), numerous questions about their formation, structure and regulation are still unresolved. To determine water accessible domains of protein coating at lipid droplets surface, a structural proteomic approach has been performed. This technique relies on the millisecond timescale production of hydroxyl radicals by the radiolysis of water using Synchrotron X-ray white beam. Thanks to the evolution of mass spectrometry analysis techniques this approach allows the creation of a map of the solvent accessibility for proteins difficult to study by other means. Using these results, a S3 oleosin water accessibility map is proposed. This is the first time that such a map on an oleosin co-purified with plant lipid droplets and other associated protein is presented. Lipid droplet associated proteins function is linked to stability, structure and probably formation and lipid mobilization of droplets. Structure of these proteins in their native environment, at the interface between bulk water and the lipidic core of these organelles is only based on hydrophobicity plot. Using hydroxyl radical footprinting and proteomics approaches we studied water accessibility of one major protein in these droplets: S3 oleosin of Arabidopsis thaliana seeds. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Unraveling the rationale behind organic solvent stability of lipases.

    PubMed

    Chakravorty, Debamitra; Parameswaran, Saravanan; Dubey, Vikash Kumar; Patra, Sanjukta

    2012-06-01

    Organic solvent-stable lipases have pronounced impact on industrial economy as they are involved in synthesis by esterification, interesterification, and transesterification. However, very few of such natural lipases have been isolated till date. A study of the recent past provided few pillars to rely on for this work. The three-dimensional structure, inclusive of the surface and active site, of 29 organic solvent-stable lipases was analyzed by subfamily classification and protein solvent molecular docking based on fast Fourier transform correlation approach. The observations revealed that organic solvent stability of lipases is their intrinsic property and unique with respect to each lipase. In this paper, factors like surface distribution of charged, hydrophobic, and neutral residues, interaction of solvents with catalytically immutable residues, and residues interacting with essential water molecules required for lipase activity, synergistically and by mutualism contribute to render a stable lipase organic solvent. The propensity of surface charge in relation to stability in organic solvents by establishing repulsive forces to exclude solvent molecules from interacting with the surface and prohibiting the same from gaining entry to the protein core, thus stabilizing the active conformation, is a new finding. It was also interesting to note that lipases having equivalent surface-exposed positive and negative residues were stable in a wide range of organic solvents, irrespective of their LogP values.

  1. Water droplet impact on elastic superhydrophobic surfaces

    NASA Astrophysics Data System (ADS)

    Weisensee, Patricia B.; Tian, Junjiao; Miljkovic, Nenad; King, William P.

    2016-07-01

    Water droplet impact on surfaces is a ubiquitous phenomenon in nature and industry, where the time of contact between droplet and surface influences the transfer of mass, momentum and energy. To manipulate and reduce the contact time of impacting droplets, previous publications report tailoring of surface microstructures that influence the droplet - surface interface. Here we show that surface elasticity also affects droplet impact, where a droplet impacting an elastic superhydrophobic surface can lead to a two-fold reduction in contact time compared to equivalent rigid surfaces. Using high speed imaging, we investigated the impact dynamics on elastic nanostructured superhydrophobic substrates having membrane and cantilever designs with stiffness 0.5-7630 N/m. Upon impact, the droplet excites the substrate to oscillate, while during liquid retraction, the substrate imparts vertical momentum back to the droplet with a springboard effect, causing early droplet lift-off with reduced contact time. Through detailed experimental and theoretical analysis, we show that this novel springboarding phenomenon is achieved for a specific range of Weber numbers (We >40) and droplet Froude numbers during spreading (Fr >1). The observation of the substrate elasticity-mediated droplet springboard effect provides new insight into droplet impact physics.

  2. Water droplet impact on elastic superhydrophobic surfaces

    PubMed Central

    Weisensee, Patricia B.; Tian, Junjiao; Miljkovic, Nenad; King, William P.

    2016-01-01

    Water droplet impact on surfaces is a ubiquitous phenomenon in nature and industry, where the time of contact between droplet and surface influences the transfer of mass, momentum and energy. To manipulate and reduce the contact time of impacting droplets, previous publications report tailoring of surface microstructures that influence the droplet - surface interface. Here we show that surface elasticity also affects droplet impact, where a droplet impacting an elastic superhydrophobic surface can lead to a two-fold reduction in contact time compared to equivalent rigid surfaces. Using high speed imaging, we investigated the impact dynamics on elastic nanostructured superhydrophobic substrates having membrane and cantilever designs with stiffness 0.5–7630 N/m. Upon impact, the droplet excites the substrate to oscillate, while during liquid retraction, the substrate imparts vertical momentum back to the droplet with a springboard effect, causing early droplet lift-off with reduced contact time. Through detailed experimental and theoretical analysis, we show that this novel springboarding phenomenon is achieved for a specific range of Weber numbers (We >40) and droplet Froude numbers during spreading (Fr >1). The observation of the substrate elasticity-mediated droplet springboard effect provides new insight into droplet impact physics. PMID:27461899

  3. Vaporization of perfluorocarbon droplets using optical irradiation

    PubMed Central

    Strohm, Eric; Rui, Min; Gorelikov, Ivan; Matsuura, Naomi; Kolios, Michael

    2011-01-01

    Micron-sized liquid perfluorocarbon (PFC) droplets are currently being investigated as activatable agents for medical imaging and cancer therapy. After injection into the bloodstream, superheated PFC droplets can be vaporized to a gas phase for ultrasound imaging, or for cancer therapy via targeted drug delivery and vessel occlusion. Droplet vaporization has been previously demonstrated using acoustic methods. We propose using laser irradiation as a means to induce PFC droplet vaporization using a method we term optical droplet vaporization (ODV). In order to facilitate ODV of PFC droplets which have negligible absorption in the infrared spectrum, optical absorbing nanoparticles were incorporated into the droplet. In this study, micron-sized PFC droplets loaded with silica-coated lead sulfide (PbS) nanoparticles were evaluated using a 1064 nm laser and ultra-high frequency photoacoustic ultrasound (at 200 and 375 MHz). The photoacoustic response was proportional to nanoparticle loading and successful optical droplet vaporization of individual PFC droplets was confirmed using photoacoustic, acoustic, and optical measurements. A minimum laser fluence of 1.4 J/cm2 was required to vaporize the droplets. The vaporization of PFC droplets via laser irradiation can lead to the activation of PFC agents in tissues previously not accessible using standard ultrasound-based techniques. PMID:21698007

  4. Sophisticated compound droplets on fiber networks

    NASA Astrophysics Data System (ADS)

    Weyer, Floriane; Lismont, Marjorie; Dreesen, Laurent; Vandewalle, Nicolas

    2015-11-01

    Droplets on fibers are part of our everyday lives. Indeed, many phenomena involve drops and fibers such as the formation of dew droplets on a spiderweb, the trapping of water droplets on cactus spines or the dyeing of cotton or wool fibers. Therefore, this topic has been widely studied in the recent years and it appears that droplets on fibers can be the starting point for an open digital microfluidics. We study the behavior of soapy water droplets on a fiber array. When a droplet slides along a vertical fiber and encounters a horizontal fiber, it can either stick there or continue its way. In the latter case, the droplet releases a tiny residue. We study the volume of these residues depending on the geometry of the node. By using this technique, a large number of small droplets can be trapped at the nodes of a fiber array. These residues can be encapsulated and collected by an oil droplet in order to create a multicompound droplet. Moreover, by using optical fibers, we can provoke and detect the fluorescence of the inner droplets. Fibers provide therefore an original way to study compound droplets and multiple reactions. F. Weyer is financially supported by an FNRS grant. This work is also supported by the FRFC 2.4504.12.

  5. Droplet Combustion and Soot Formation in Microgravity

    NASA Technical Reports Server (NTRS)

    Avedisian, C. Thomas

    1994-01-01

    One of the most complex processes involved in the combustion ot liquid fuels is the formation of soot. A well characterized flow field and simplified flame structure can improve considerably the understanding of soot formation processes. The simplest flame shape to analyze for a droplet is spherical with its associated one-dimensional flow field. It is a fundamental limit and the oldest and most often analyzed configuration of droplet combustion. Spherical symmetry in the droplet burning process will arise when there is no relative motion between the droplet and ambience or uneven heating around the droplet periphery, and buoyancy effects are negligible. The flame and droplet are then concentric with each other and there is no liquid circulation within the droplet. An understanding of the effect of soot on droplet combustion should therefore benefit from this simplified configuration. Soot formed during spherically symmetric droplet combustion, however, has only recently drawn attention and it appears to be one of the few aspects associated with droplet combustion which have not yet been thoroughly investigated. For this review, the broad subject of droplet combustion is narrowed considerably by restricting attention specifically to soot combined with spherically symmetric droplet burning processes that are promoted.

  6. Shock wave-droplet interaction

    NASA Astrophysics Data System (ADS)

    Habibi Khoshmehr, Hamed; Krechetnikov, Rouslan

    2016-11-01

    Disintegration of a liquid droplet under the action of a shock wave is experimentally investigated. The shock wave-pulse is electromagnetically generated by discharging a high voltage capacitor into a flat spiral coil, above which an isolated circular metal membrane is placed in a close proximity. The Lorentz force arising due to the eddy current induced in the membrane abruptly accelerates it away from the spiral coil thus generating a shock wave. The liquid droplet placed at the center of the membrane, where the maximum deflection occurs, is disintegrated in the process of interaction with the shock wave. The effects of droplet viscosity and surface tension on the droplet destruction are studied with high-speed photography. Water-glycerol solution at different concentrations is used for investigating the effect of viscosity and various concentrations of water-sugar and water-ethanol solution are used for studying the effect of surface tension. Here we report on how the metamorphoses, which a liquid drop undergoes in the process of interaction with a shock wave, are affected by varied viscosity and surface tension.

  7. SOLVENT EXTRACTION OF NEPTUNIUM

    DOEpatents

    Butler, J.P.

    1958-08-12

    A process is described for the recovery of neptuniunn from dissolver solutions by solvent extraction. The neptunium containing solution should be about 5N, in nitric acid.and about 0.1 M in ferrous ion. The organic extracting agent is tributyl phosphate, and the neptuniunn is recovered from the organic solvent phase by washing with water.

  8. Solvent-free synthesis

    EPA Science Inventory

    This chapter gives a brief introduction about solvent-free reactions whose importance can be gauged by the increasing number of publications every year during the last decade. The mechanistic aspects of the reactions under solvent-free conditions have been highlighted. Our observ...

  9. Solvent-free synthesis

    EPA Science Inventory

    This chapter gives a brief introduction about solvent-free reactions whose importance can be gauged by the increasing number of publications every year during the last decade. The mechanistic aspects of the reactions under solvent-free conditions have been highlighted. Our observ...

  10. Helium Droplets Doped with Sulfur and C60

    PubMed Central

    2014-01-01

    Clusters of sulfur are grown by passing superfluid helium nanodroplets through a pickup cell filled with sulfur vapor. In some experiments the droplets are codoped with C60. The doped droplets are collided with energetic electrons and the abundance distributions of positively and negatively charged cluster ions are recorded. We report, specifically, distributions of Sm+, Sm–, and C60Sm– containing up to 41 sulfur atoms. We also observe complexes of sulfur cluster anions with helium; distributions are presented for HenSm– with n ≤ 31 and m ≤ 3. The similarity between anionic and cationic C60Sm± spectra is in striking contrast to the large differences between spectra of Sm+ and Sm–. PMID:26045732

  11. 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).

  12. Alternative Green Solvents Project

    NASA Technical Reports Server (NTRS)

    Maloney, Phillip R.

    2012-01-01

    Necessary for safe and proper functioning of equipment. Mainly halogenated solvents. Tetrachloride, Trichloroethylene (TCE), CFC-113. No longer used due to regulatory/safety concerns. Precision Cleaning at KSC: Small % of total parts. Used for liquid oxygen (LOX) systems. Dual solvent process. Vertrel MCA (decafluoropentane (DFP) and trons-dichloroethylene) HFE-7100. DFP has long term environmental concerns. Project Goals: a) Identify potential replacements. b) 22 wet chemical processes. c) 3 alternative processes. d) Develop test procedures. e) Contamination and cleaning. f) Analysis. g) Use results to recommend alternative processes. Conclusions: a) No alternative matched Vertrel in this study. b) No clear second place solvent. c) Hydrocarbons- easy; Fluorinated greases- difficult. d) Fluorinated component may be needed in replacement solvent. e) Process may need to make up for shortcoming of the solvent. f) Plasma and SCC02 warrant further testing.

  13. Induction Charge Detector with Multiple Sensing Stages

    NASA Technical Reports Server (NTRS)

    Gamero-Castano, Manuel

    2008-01-01

    An induction charge detector with multiple sensing stages has been conceived for use in characterizing sprayed droplets, dust particles, large ionized molecules, and the like. Like related prior single-stage devices, each stage yields a measurement of the electric charge and the time of flight of the particle. In effect, an n-stage sensor yields n independent sets of such measurements from the same particle. The benefit of doing this is to increase the effective signal-to-noise ratio and thereby lower the charge-detection limit and the standard error of the charge measurement.

  14. Spreading of Thin Droplets of Perfect and Leaky Dielectric Liquids on Inclined Surfaces.

    PubMed

    Corbett, Andrew; Kumar, Satish

    2016-07-05

    The spreading of droplets may be influenced by electric fields, a situation that is relevant to applications such as coating, printing, and microfluidics. In this work we study the effects of an electric field on the gravity-driven spreading of two-dimensional droplets down an inclined plane. We consider both perfect and leaky dielectric liquids, as well as perfectly and partially wetting systems. In addition to the effects of electric fields, we examine the use of thermocapillary forces to suppress the growth of the capillary ridge near the droplet front. Lubrication theory is applied to generate a set of coupled partial differential equations for interfacial height and charge, which are then solved numerically with a finite-difference method. Electric fields increase the height of the capillary ridge in both perfect and leaky dielectric droplets due to electrostatic pressure gradients that drive liquid into the ridge. In leaky dielectrics, large interfacial charge gradients in the contact-line region create shear stresses that also enhance ridge growth and the formation of trailing minor ridges. The coalescence of these ridges can significantly affect the long-time thinning rate of leaky dielectric droplets. In partially wetting liquids, electric fields promote the splitting of smaller droplets from the primary droplet near the receding contact line due to the interplay between electrostatic forces and disjoining pressure. Cooling from below and heating from above generates thermocapillary forces that counteract the effects of electric fields and suppress the growth of the capillary ridge. The results of this work have important implications for manipulating the spreading of droplets down inclined surfaces.

  15. Take off of small Leidenfrost droplets.

    PubMed

    Celestini, Franck; Frisch, Thomas; Pomeau, Yves

    2012-07-20

    We put in evidence the unexpected behavior of Leidenfrost droplets at the later stage of their evaporation. We predict and observe that, below a critical size Rl, the droplets spontaneously take off due to the breakdown of the lubrication regime. We establish the theoretical relation between the droplet radius and its elevation. We predict that the vapor layer thickness increases when the droplets become smaller. A satisfactory agreement is found between the model and the experimental results performed on droplets of water and of ethanol.

  16. Dynamics of droplet motion under electrowetting actuation.

    PubMed

    Annapragada, S Ravi; Dash, Susmita; Garimella, Suresh V; Murthy, Jayathi Y

    2011-07-05

    The static shape of droplets under electrowetting actuation is well understood. The steady-state shape of the droplet is obtained on the basis of the balance of surface tension and electrowetting forces, and the change in the apparent contact angle is well characterized by the Young-Lippmann equation. However, the transient droplet shape behavior when a voltage is suddenly applied across a droplet has received less attention. Additional dynamic frictional forces are at play during this transient process. We present a model to predict this transient behavior of the droplet shape under electrowetting actuation. The droplet shape is modeled using the volume of fluid method. The electrowetting and dynamic frictional forces are included as an effective dynamic contact angle through a force balance at the contact line. The model is used to predict the transient behavior of water droplets on smooth hydrophobic surfaces under electrowetting actuation. The predictions of the transient behavior of droplet shape and contact radius are in excellent agreement with our experimental measurements. The internal fluid motion is explained, and the droplet motion is shown to initiate from the contact line. An approximate mathematical model is also developed to understand the physics of the droplet motion and to describe the overall droplet motion and the contact line velocities.

  17. Formation and Levitation of Unconfined Droplet Clusters

    NASA Technical Reports Server (NTRS)

    Liu, S.; Ruff, G. A.

    1999-01-01

    Combustion experiments using arrays of droplets seek to provide a link between single droplet combustion phenomena and the behavior of complex spray combustion systems. Both single droplet and droplet array studies have been conducted in microgravity to better isolate the droplet interaction phenomena and eliminate or reduce the confounding effects of buoyancy-induced convection. In most experiments involving droplet arrays, the droplets are supported on fibers to keep them stationary and close together before the combustion event. The presence of the fiber, however, disturbs the combustion process by introducing a source of heat transfer and asymmetry into the configuration. As the number of drops in a droplet array increases, supporting the drops on fibers becomes less practical because of the cumulative effect of the fibers on the combustion process. The overall objective of this research is to study the combustion of well-characterized drop clusters in a microgravity environment. Direct experimental observations and measurements of the combustion of droplet clusters would fill a large gap in our current understanding of droplet and spray combustion and provide unique experimental data for the verification and improvement of spray combustion models. This paper describes current work on the design and performance of an apparatus to generate and stabilize droplet clusters using acoustic and electrostatic forces.

  18. Continuous dielectrophoretic centering of compound droplets

    NASA Astrophysics Data System (ADS)

    Randall, Greg; Blue, Brent

    2012-02-01

    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 foam shell targets in inertial fusion energy work. A key constraint is a uniform foam shell thickness, which in turn requires a centered core 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. To apply centering to existing or future applications, it is imperative to develop a continuous droplet centering process by overcoming the additional complications from motion. Here, we present analysis and experimental data of a continuous droplet centering device that uses an electric field to force a core droplet to the center of a moving compound drop. Our analysis focuses on how interfacial rheology and electrohydrodynamic flows affect the centering dynamics and droplet deformation. Proof-of-principle experiments are performed in a vertical channel using buoyancy to drive a solution of compound droplets stabilized with phospholipid and protein emulsifiers through a kV/cm electric field.

  19. Formation and Levitation of Unconfined Droplet Clusters

    NASA Technical Reports Server (NTRS)

    Liu, S.; Ruff, G. A.

    1999-01-01

    Combustion experiments using arrays of droplets seek to provide a link between single droplet combustion phenomena and the behavior of complex spray combustion systems. Both single droplet and droplet array studies have been conducted in microgravity to better isolate the droplet interaction phenomena and eliminate or reduce the confounding effects of buoyancy-induced convection. In most experiments involving droplet arrays, the droplets are supported on fibers to keep them stationary and close together before the combustion event. The presence of the fiber, however, disturbs the combustion process by introducing a source of heat transfer and asymmetry into the configuration. As the number of drops in a droplet array increases, supporting the drops on fibers becomes less practical because of the cumulative effect of the fibers on the combustion process. The overall objective of this research is to study the combustion of well-characterized drop clusters in a microgravity environment. Direct experimental observations and measurements of the combustion of droplet clusters would fill a large gap in our current understanding of droplet and spray combustion and provide unique experimental data for the verification and improvement of spray combustion models. This paper describes current work on the design and performance of an apparatus to generate and stabilize droplet clusters using acoustic and electrostatic forces.

  20. Thermophoresis of water droplets inside carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Zambrano, Harvey; Walther, Jh; Oyarzua, Elton; Rojano, Andres

    2016-11-01

    Carbon Nanotubes (CNTs) offer unique possibilities as fluid conduits with applications ranging from lab on a chip devices to encapsulation media for drug delivery. CNTs feature high mechanical strength, chemical and thermal stability and biocompatibility therefore they are promising candidates for nanodevice fabrication. Thermal gradients have been proposed as mechanism to drive particles, fullerenes and droplets inside CNTs. Here, by conducting Molecular Dynamics (MD) simulations, we study thermophoresis of water droplets inside CNTs. We systematically change the size of the droplets, the axial thermal gradient and CNT chirality. We find that the droplet motion in the armchair CNTs exhibits two clearly delimited stages, a regime wherein the droplet is accelerated and subsequently, a regime wherein the droplet moves with constant velocity. Inside the zig zag CNTs, the droplet accelerates during a very short time and then it moves with constant velocity. We compute the net force during the droplet acceleration and find a correlation between the droplet acceleration and the magnitude of the thermal gradient without any dependence on the droplet size. Moreover, we conduct velocity constrained MD simulations to determine the friction and thermophoretic forces acting on the droplet. We acknowledge partial funding from FONDECYT through the Project No. 11130559 and from VRID Universidad de Concepcion.

  1. Passive droplet sorting using viscoelastic flow focusing.

    PubMed

    Hatch, Andrew C; Patel, Apurva; Beer, N Reginald; Lee, Abraham P

    2013-04-07

    We present a study of passive hydrodynamic droplet sorting in microfluidic channels based on intrinsic viscoelastic fluid properties. Sorting is achieved by tuning the droplets' intrinsic viscous and viscoelastic properties relative to the continuous oil phase to achieve a positive or negative lateral migration toward high or low shear gradients in the channel. In the presence of weakly viscoelastic fluid behavior, droplets with a viscosity ratio, κ, between 0.5-10 were found to migrate toward a high shear gradient near the channel walls. For all other κ-values, or Newtonian fluids, droplets would migrate toward a low shear gradient at the channel centerline. It was also found that for strongly viscoelastic fluids with low interfacial tension, droplets would migrate toward the edge even with κ-values lower than 0.5. The resulting bi-directional lateral droplet migration between different droplets allows size-independent sorting. Still, their sorting efficiencies are dependent on droplet size, intrinsic fluid elasticity, viscosity, droplet deformability, and overall fluid shear rates. Based on these findings, we demonstrate >200 Hz passive droplet sorting frequencies and achieve >100 fold enrichment factors without the need to actively sense and/or control active mechanisms. Using a low viscosity oil phase of 6.25 cPs, we demonstrate sorting discrimination of 1 cPs and 5 cPs aqueous droplets with κ-values of 0.2 and 0.8 respectively.

  2. Droplet lasers: a review of current progress

    NASA Astrophysics Data System (ADS)

    McGloin, D.

    2017-05-01

    It is perhaps surprising that something as fragile as a microscopic droplet could possibly form a laser. In this article we will review some of the underpinning physics as to how this might be possible, and then examine the state of the art in the field. The technology to create and manipulate droplets will be examined, as will the different classes of droplet lasers. We discuss the rapidly developing fields of droplet biolasers, liquid crystal laser droplets and explore how droplet lasers could give rise to new bio and chemical sensing and analysis. The challenges that droplet lasers face in becoming robust devices, either as sensors or as photonic components in the lab on chip devices, is assessed.

  3. Enhanced Droplet Control by Transition Boiling

    PubMed Central

    Grounds, Alex; Still, Richard; Takashina, Kei

    2012-01-01

    A droplet of water on a heated surface can levitate over a film of gas produced by its own evaporation in the Leidenfrost effect. When the surface is prepared with ratchet-like saw-teeth topography, these droplets can self-propel and can even climb uphill. However, the extent to which the droplets can be controlled is limited by the physics of the Leidenfrost effect. Here, we show that transition boiling can be induced even at very high surface temperatures and provide additional control over the droplets. Ratchets with acute protrusions enable droplets to climb steeper inclines while ratchets with sub-structures enable their direction of motion to be controlled by varying the temperature of the surface. The droplets' departure from the Leidenfrost regime is assessed by analysing the sound produced by their boiling. We anticipate these techniques will enable the development of more sophisticated methods for controlling small droplets and heat transfer. PMID:23056912

  4. Enhanced droplet control by transition boiling.

    PubMed

    Grounds, Alex; Still, Richard; Takashina, Kei

    2012-01-01

    A droplet of water on a heated surface can levitate over a film of gas produced by its own evaporation in the Leidenfrost effect. When the surface is prepared with ratchet-like saw-teeth topography, these droplets can self-propel and can even climb uphill. However, the extent to which the droplets can be controlled is limited by the physics of the Leidenfrost effect. Here, we show that transition boiling can be induced even at very high surface temperatures and provide additional control over the droplets. Ratchets with acute protrusions enable droplets to climb steeper inclines while ratchets with sub-structures enable their direction of motion to be controlled by varying the temperature of the surface. The droplets' departure from the Leidenfrost regime is assessed by analysing the sound produced by their boiling. We anticipate these techniques will enable the development of more sophisticated methods for controlling small droplets and heat transfer.

  5. Dancing droplets: Contact angle, drag, and confinement

    NASA Astrophysics Data System (ADS)

    Benusiglio, Adrien; Cira, Nate; Prakash, Manu

    2015-11-01

    When deposited on a clean glass slide, a mixture of water and propylene glycol forms a droplet of given contact angle, when both pure liquids spread. (Cira, Benusiglio, Prakash: Nature, 2015). The droplet is stabilized by a gradient of surface tension due to evaporation that induces a Marangoni flow from the border to the apex of the droplets. The apparent contact angle of the droplets depends on both their composition and the external humidity as captured by simple models. These droplets present remarkable properties such as lack of a large pinning force. We discuss the drag on these droplets as a function of various parameters. We show theoretical and experimental results of how various confinement geometries change the vapor gradient and the dynamics of droplet attraction.

  6. Enhanced Droplet Control by Transition Boiling

    NASA Astrophysics Data System (ADS)

    Grounds, Alex; Still, Richard; Takashina, Kei

    2012-10-01

    A droplet of water on a heated surface can levitate over a film of gas produced by its own evaporation in the Leidenfrost effect. When the surface is prepared with ratchet-like saw-teeth topography, these droplets can self-propel and can even climb uphill. However, the extent to which the droplets can be controlled is limited by the physics of the Leidenfrost effect. Here, we show that transition boiling can be induced even at very high surface temperatures and provide additional control over the droplets. Ratchets with acute protrusions enable droplets to climb steeper inclines while ratchets with sub-structures enable their direction of motion to be controlled by varying the temperature of the surface. The droplets' departure from the Leidenfrost regime is assessed by analysing the sound produced by their boiling. We anticipate these techniques will enable the development of more sophisticated methods for controlling small droplets and heat transfer.

  7. Active droplet sorting in microfluidics: a review.

    PubMed

    Xi, Heng-Dong; Zheng, Hao; Guo, Wei; Gañán-Calvo, Alfonso M; Ai, Ye; Tsao, Chia-Wen; Zhou, Jun; Li, Weihua; Huang, Yanyi; Nguyen, Nam-Trung; Tan, Say Hwa

    2017-02-28

    The ability to manipulate and sort droplets is a fundamental issue in droplet-based microfluidics. Various lab-on-a-chip applications can only be realized if droplets are systematically categorized and sorted. These micron-sized droplets act as ideal reactors which compartmentalize different biological and chemical reagents. Array processing of these droplets hinges on the competence of the sorting and integration into the fluidic system. Recent technological advances only allow droplets to be actively sorted at the rate of kilohertz or less. In this review, we present state-of-the-art technologies which are implemented to efficiently sort droplets. We classify the concepts according to the type of energy implemented into the system. We also discuss various key issues and provide insights into various systems.

  8. Separation of gas from solvent by membrane technology

    SciTech Connect

    Beaupre, R.F.; Jung, D.Y.

    1991-02-26

    This patent describes the method of separating a charge rich liquid containing gas dissolved in solvent. It comprises: maintaining the charge rich liquid containing gas dissolved in solvent therefore in liquid phase in contact with a gas-permeable, essentially solvent impermeable membrane of pore size of less than about 1000 A and molecular weight cutoff of below about 1,000 selected from the group consisting of cellulose acetate membrane, hydrolyzed cellulose membrane, and polyethyleneimine membrane, and; maintaining a pressure drop across the gas-permeable essentially solvent-impermeable membrane; passing the gas from the charge rich liquid containing gas dissolved in solvent therefore at the higher pressure side of the membrane through the membrane thereby forming lean liquid containing decreased quantities of gas dissolved in solvent on the higher pressure side of the membrane and, on the lower pressure side of the membrane, gas containing decreased quantities of liquid; recovering lean liquid containing decreased quantities of gas dissolved in solvent from the high pressure side of the membrane; and recovering gas containing decreased quantities of liquid from the lower pressure side of the membrane.

  9. SOLVENT EXTRACTION PROCESS

    DOEpatents

    Jonke, A.A.

    1957-10-01

    In improved solvent extraction process is described for the extraction of metal values from highly dilute aqueous solutions. The process comprises contacting an aqueous solution with an organic substantially water-immiscible solvent, whereby metal values are taken up by a solvent extract phase; scrubbing the solvent extract phase with an aqueous scrubbing solution; separating an aqueous solution from the scrubbed solvent extract phase; and contacting the scrubbed solvent phase with an aqueous medium whereby the extracted metal values are removed from the solvent phase and taken up by said medium to form a strip solution containing said metal values, the aqueous scrubbing solution being a mixture of strip solution and an aqueous solution which contains mineral acids anions and is free of the metal values. The process is particularly effective for purifying uranium, where one starts with impure aqueous uranyl nitrate, extracts with tributyl phosphate dissolved in carbon tetrachloride, scrubs with aqueous nitric acid and employs water to strip the uranium from the scrubbed organic phase.

  10. Repulsion between Oppositely Charged Planar Macroions

    PubMed Central

    Jho, YongSeok; Brown, Frank L. H.; Kim, MahnWon; Pincus, Philip A.

    2013-01-01

    The repulsive interaction between oppositely charged macroions is investigated using Grand Canonical Monte Carlo simulations of an unrestricted primitive model, including the effect of inhomogeneous surface charge and its density, the depth of surface charge, the cation size, and the dielectric permittivity of solvent and macroions, and their contrast. The origin of the repulsion is a combination of osmotic pressure and ionic screening resulting from excess salt between the macroions. The excess charge over-reduces the electrostatic attraction between macroions and raises the entropic repulsion. The magnitude of the repulsion increases when the dielectric constant of the solvent is lowered (below that of water) and/or the surface charge density is increased, in good agreement with experiment. Smaller size of surface charge and the cation, their discreteness and mobility are other factors that enhance the repulsion and charge inversion phenomenons. PMID:23940518

  11. Splash Suppression by Solvent Viscosity in Dense Suspension Impact

    NASA Astrophysics Data System (ADS)

    Zhang, Wendy; Dodge, Kevin; Peters, Ivo; Klein Schaarsberg, Martin; Jaeger, Heinrich

    2015-03-01

    When a dense suspension droplet impacts a hard surface, it will either break apart (``splash'') or remain in a compact configuration without ejecting any particles. We use experiments and discrete particle simulations in which relative particle motions are penalized by lubrication-flow drag to analyze the influence of solvent viscosity on splashing. We find that suspension splash is driven by particle inertia. It can be suppressed in 2 different ways. At low solvent viscosity, lubrication drag due to viscous flow has a negligible effect. Splash is suppressed by surface tension overcoming particle inertia. At high solvent viscosity, lubrication drag alone suppresses splashing. Because impact produces an expanding flow that stretches the suspension radially, suppression in the high-viscosity regime is largely accomplished by lubrication-flow drag preventing initially nearby particle pairs from separating fully. Energy dissipation by viscous flow during collisions plays a smaller role. Present Address: Physics of Fluids Group, University of Twente.

  12. Integrated microfluidic system capable of size-specific droplet generation with size-dependent droplet separation.

    PubMed

    Lee, Sangmin; Hong, Seok Jun; Yoo, Hyung Jung; Ahn, Jae Hyun; Cho, Dong-il Dan

    2013-06-01

    Droplet-based microfluidics is receiving much attention in biomedical research area due to its advantage in uniform size droplet generation. Our previous results have reported that droplet size plays an important role in drug delivery actuated by flagellated bacteria. Recently, many research groups have been reported the size-dependent separation of emulsion droplets by a microfluidic system. In this paper, an integrated microfluidic system is proposed to produce and sort specificsized droplets sequentially. Operation of the system relies on two microfluidic transport processes: initial generation of droplets by hydrodynamic focusing and subsequent separation of droplets by a T-junction channel. The microfluidic system is fabricated by the SU-8 rapid prototyping method and poly-di-methyl-siloxane (PDMS) replica molding. A biodegradable polymer, poly-capro-lactone (PCL), is used for the droplet material. Using the proposed integrated microfluidic system, specific-sized droplets which can be delivered by flagellated bacteria are successfully generated and obtained.

  13. Droplet actuator analyzer with cartridge

    NASA Technical Reports Server (NTRS)

    Smith, Gregory F. (Inventor); Sturmer, Ryan A. (Inventor); Paik, Philip Y. (Inventor); Srinivasan, Vijay (Inventor); Pollack, Michael G. (Inventor); Pamula, Vamsee K. (Inventor); Brafford, Keith R. (Inventor); West, Richard M. (Inventor)

    2011-01-01

    A droplet actuator with cartridge is provided. According to one embodiment, a sample analyzer is provided and includes an analyzer unit comprising electronic or optical receiving means, a cartridge comprising self-contained droplet handling capabilities, and a wherein the cartridge is coupled to the analyzer unit by a means which aligns electronic and/or optical outputs from the cartridge with electronic or optical receiving means on the analyzer unit. According to another embodiment, a sample analyzer is provided and includes a sample analyzer comprising a cartridge coupled thereto and a means of electrical interface and/or optical interface between the cartridge and the analyzer, whereby electrical signals and/or optical signals may be transmitted from the cartridge to the analyzer.

  14. Evaluation of permanently charged electrofibrous filters

    SciTech Connect

    Biermann, A.H.; Lum, B.Y.; Bergman, W.

    1982-10-18

    These studies showed that loading the permanently charged filters with captured aerosols will lead to a neutralization of the filter charge. The transfer from the captured aerosol to the fiber surface and the subsequent neutralization of fiber charge. The increased efficiency is due to the add